JPH06128748A - Method and device for forming deposited film by microwave plasma cvd - Google Patents

Abstract

PURPOSE:To form a deposited non-single crystal semiconductor film excellent in electrical characteristic and reduced in light deterioration by interposing a mesh of conductive metal between a space where the raw gas is decomposed and a substrate and impressing a DC voltage on the mesh. CONSTITUTION:A microwave energy lower than the microwave energy necessary to completely decompose the raw gas at the internal pressure of <=50mTorr is allowed to act on the raw gas, and an rf energy higher than the acting microwave energy is allowed to act on the raw gas at the same time. Meanwhile, a mesh 113 of conductive metal is interposed between the space where the raw gas is mainly decomposed by the acting microwave energy and a substrate 104, and a DC voltage is impressed on the mesh 113. Consequently, the device characteristic or yield is improved, and an electronic device is produced at a lower cost.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deposited film forming method by a microwave plasma CVD method in which a raw material gas for forming a deposited film is decomposed by microwave energy to form a deposited film on a substrate, and more particularly to a photovoltaic device. , A thin film transistor, a sensor, a photoreceptive member for electrophotography and the like, and a functional deposited film forming method suitable for the same.

The present invention also relates to microwave plasma CVD.
The present invention relates to an apparatus for forming a functionally deposited film by the method, and more particularly to an apparatus for continuously forming a photovoltaic element such as a solar cell. More specifically, the present invention relates to an apparatus for mass-producing photovoltaic elements such as solar cells using the roll-to-roll method.

[0003]

2. Description of the Related Art Conventionally, a plasma CVD method is generally widely used for forming a functional deposited film such as a photovoltaic element using an a-Si film, and has been commercialized. There is.
However, in order to establish this as a photovoltaic element that can meet the power demand, the photovoltaic element to be used must have sufficiently high photoelectric conversion efficiency and excellent characteristic stability, and be mass-produced. It is basically required to be able to do. To this end, in film formation of a photovoltaic element using an a-Si film or the like, electrical, optical, photoconductive or mechanical characteristics and fatigue characteristics in repeated use or use environment characteristics are improved. At the same time, it is necessary to achieve reproducible mass production by high-speed film formation while achieving a large area and uniform film thickness and film quality. .

From such a point of view, many reports have been made on the method of forming a deposited film by the microwave plasma CVD method.

For example, "Chemical Vapor
deposition of a-SiGe: Hf
ilms utilizing a microvav
e-excited plasma "T. Watana
be, M .; Tanaka, K .; Azuma, M .; Nak
atani, T .; Sonobe, T .; Simada, J
apanese Journal of Applie
d Physics, Vol. 26, No. 4, Apr
il, 1987, pp. L288-L290, "Mic
rowave-excited plasma CVD
of a-Si: H films utilizin
ga adrogen plasma strea
m or by direct excitation
ofsilane "T. Watanabe, M. Ta
naka, K .; Azuma, M .; Nakatani,
T. Sonobe, T .; Simada, Japanes
eJournal of Applied Physi
cs, Vol. 26, No. 8, August, 198
7, pp. 125-1218 and the like describe a microwave plasma CVD method using ECR.

Further, Japanese Patent Laid-Open Publication No. 59-16328 “Plasma vapor phase reactor” and Japanese Laid-Open Patent Publication No. 59-567.
24 "Microwave plasma thin film formation method"
A method of depositing a semiconductor film by a microwave plasma CVD method is shown.

Further, in the rf plasma CVD method, a method of forming a deposited film in which a mesh-shaped third electrode is provided between an anode and a cathode is "Preparation of".
highly photosensitive hy
drowned amorphous Si-G
e alloys using a triodepl
asma reactor "A.Matsuda e
t. al. , Applied Physics Let
ters, Vol. 47 No. 10,15 Novem
ber 1985 pp. 1061-1063.

Further, in a power generation method using a photovoltaic element, a form in which unit modules are connected in series or in parallel and unitized to obtain a desired current and voltage is often adopted. Is required not to cause disconnection or short circuit. In addition, it is important that there is no variation in output voltage or output current between modules. For this reason, at least at the stage of forming the unit module, it is required to secure the characteristic uniformity of the semiconductor layer itself, which is the largest characteristic determining factor. Further, from the viewpoint of facilitating the module design and simplifying the module assembling process, it is possible to provide a semiconductor deposited film having excellent property uniformity over a large area, thereby improving the mass productivity of photovoltaic devices. It is required to increase the production cost and to significantly reduce the production cost.

In the photovoltaic element, a semiconductor layer which is an important component thereof has a semiconductor junction such as a so-called pn junction or pin junction. When a thin film semiconductor such as a-Si is used, phosphine (PH ₃ ) and diborane (B ₂
A raw material gas containing an element serving as a dopant such as H ₆ ) is mixed with silane, which is a main raw material gas, and glow discharge decomposed to obtain a semiconductor film having a desired conductivity type. It is known that the aforementioned semiconductor junction can be easily achieved by sequentially forming semiconductor films. From this fact, in forming an a-Si photovoltaic element, an independent film forming chamber for forming each semiconductor layer is provided, and each semiconductor layer is formed in the film forming chamber. A method of doing is proposed.

Incidentally, US Pat. No. 4,400,409 discloses a roll-to-roll (Roll to R) method.
There is disclosed a continuous plasma CVD apparatus adopting the Oll system. According to this apparatus, a plurality of glow discharge regions are provided, and a sufficiently long flexible substrate having a desired width is arranged along a path through which the substrates sequentially pass through the glow discharge regions. It is said that an element having a semiconductor junction can be continuously formed by continuously transporting the substrate in the longitudinal direction while depositing a conductive type semiconductor layer required in the discharge region. In this specification, a gas gate is used to prevent the dopant gas used in forming each semiconductor layer from diffusing and mixing into another glow discharge region. Specifically, the glow discharge regions are separated from each other by a slit-like separation passage, and the separation passage is provided with, for example, A
Means for forming a film of a flow of scavenging gas such as r or H ₂ is adopted. For this reason, this roll-to-roll system is a system suitable for mass production of semiconductor devices, but as described above, in order to popularize a large number of photovoltaic devices, further photoelectric conversion efficiency, characteristic stability, and It is desired to improve property uniformity and reduce film formation cost.

In particular, in order to improve the photoelectric conversion efficiency and the characteristic stability, the photoelectric conversion efficiency and the characteristic deterioration rate of each unit module should be improved in 0.1% increments (corresponding to about 1.01 times in proportion). Of course, when the unit modules are connected in series or in parallel and made into a unit, the unit module having the minimum current or voltage characteristic among the unit modules constituting the unit is the rate-determining unit. Because the characteristics are determined,
Not only improve the average characteristics of each unit module,
It is very important to reduce the characteristic variation. Therefore, it is desired to secure the characteristic uniformity of the semiconductor layer itself, which is the largest characteristic determining factor, at the stage of forming the unit module. Further, in order to reduce the film formation cost, it is strongly desired to improve the yield by reducing defects in the semiconductor layer so that disconnection or short circuit does not occur in each module.

Therefore, in the deposition of the semiconductor layer on the continuously moving strip-shaped member, the uniformity of the characteristics is ensured,
It is desired to provide a manufacturing device at an early stage to reduce defects.

[0013]

However, the conventional method of forming a deposited film by the microwave plasma CVD method has the following problems.

(1) For example, when a non-single crystal semiconductor film (for example, amorphous silicon a-Si: H) is deposited, the deposition rate is slow, the electrical characteristics are poor, and the film is used for a long time under light irradiation. There was a problem that there was a lot of deterioration. In particular, when the deposition rate was increased, the electrical characteristics of the semiconductor film, the adhesion to the substrate, and the like were significantly deteriorated.

(2) There is a problem that the plasma is unstable in a region where the raw material gas for forming the deposited film is small.

(3) The plasma is likely to be non-uniform, and the thickness and characteristics of the deposited film formed are likely to be uneven, resulting in device characteristics such as solar cells, thin film transistors, and electrophotographic light-receiving members. There is a problem that the yield is reduced.

(4) During the formation of the deposited film, there are many damages to the surface of the deposited film by unnecessary ions and electrons which adversely affect the structure of the film and the characteristics of the deposited film. Also, there is a problem in that the characteristics become poor.

Therefore, the present invention has been made in view of the above problems of the prior art, and an object thereof is to solve the following problems.

(1) To provide a method for uniformly and stably forming a deposited film of a non-single-crystal semiconductor film, which has excellent electric characteristics even when the deposition rate is increased to 1 nm / sec or more and has little photodegradation.

(2) By increasing the uniformity and stability of plasma, the uniformity of the thickness and characteristics of the deposited film formed,
Provided is a method of improving reproducibility and, as a result, improving device characteristics and yield of photovoltaic elements, thin film transistors, sensors, electrophotography, etc., and reducing the manufacturing cost of these electronic devices.

(3) While suppressing the occurrence of abnormal discharge that adversely affects the characteristics of the deposited film, active species having energy that effectively contributes to structural relaxation of the film during the formation of the deposited film are uniformly supplied over a large area. It is possible to uniformly form a deposited film having desired characteristics by reducing damage to the surface of the deposited film by unnecessary ions and electrons that adversely affect the characteristics of the deposited film. Provided is a deposited film forming method capable of improving the yield and characteristics of devices.

The present invention also has the following objects.

(4) To provide an apparatus for uniformly and stably forming a deposited film of a non-single-crystal semiconductor film, which has excellent electric characteristics and little photodegradation even when the deposition rate is increased to several 1 nm / sec or more.

(5) The instability factor of the microwave plasma caused by the continuously moving strip-shaped member is eliminated, the plasma is stabilized for a long time, and the layer thickness of the semiconductor film and the unevenness of characteristics are reduced. As a result, there is provided an apparatus which improves device characteristics and yield of a photovoltaic element, a thin film transistor, a sensor, a photoreceptive member for electrophotography, etc., and reduces the film forming cost of these electronic devices.

[0025]

[Means for Solving Problems] (1) to (3)
The present invention that achieves the above object is a deposited film forming method as described below. That is, (1) In a microwave plasma CVD method in which a raw material gas for forming a deposited film is decomposed by microwave energy under a low pressure to form a deposited film on a substrate, the raw material gas is 100 % Microwave energy smaller than the microwave energy required for decomposition is applied to the raw material gas, and at the same time, rf energy larger than the applied microwave energy is applied to the raw material gas, and Forming a deposited film by a microwave plasma CVD method, characterized in that a mesh made of a conductive metal is interposed between a space in which a source gas is mainly decomposed and a substrate, and a DC bias voltage is applied to the mesh. Method.

(2) In a microwave plasma CVD method in which a raw material gas for forming a deposited film is decomposed by microwave energy under a low pressure to form a deposited film on a substrate, an internal pressure of 50 mT
At a vacuum degree of orr or less, a microwave energy smaller than the microwave energy required for 100% decomposition of the source gas is applied to the source gas, and at the same time, an rf energy larger than the microwave energy to be applied is applied to the source gas. A mesh made of a conductive metal is interposed between the substrate and the space in which the source gas is mainly decomposed by the microwave energy to be caused to act, and the mesh is kept at 100 ° C. when the deposited film is formed.
A method of forming a deposited film by a microwave plasma CVD method, which comprises heating and holding at the above temperature.

(3) In a microwave plasma CVD method in which a raw material gas for forming a deposited film is decomposed by microwave energy under a low pressure to form a deposited film on a substrate, an internal pressure of 50 mT
At a vacuum degree of orr or less, a microwave energy smaller than the microwave energy required for 100% decomposition of the source gas is applied to the source gas, and at the same time, an rf energy larger than the microwave energy to be applied is applied to the source gas. A mesh made of a conductive metal is interposed between the substrate and the space in which the source gas is mainly decomposed by the microwave energy to be caused to act, and an rf bias voltage is applied to the mesh. A characteristic method for forming a deposited film by a microwave plasma CVD method.

The present invention which achieves the above objects (4) and (5) is a deposited film forming apparatus as described below. That is, (4) a film forming space is provided in a vacuum container that can be evacuated, and the belt-shaped member is continuously conveyed in its longitudinal direction to penetrate the film forming space, In a device for producing a functional deposited film that decomposes a raw material gas by microwave plasma on a surface to form a deposited film, one or both of a carry-in side and a carry-out side of the strip-shaped member in the film formation space, a predetermined range An apparatus for producing a deposited film, characterized in that a porous conductive member is arranged over the entire length of the strip-shaped member so as to be close to the deposition surface.

(5) A film forming space is provided in a vacuum container capable of being evacuated, and the belt-shaped member is continuously conveyed in the longitudinal direction thereof to penetrate the film forming space, and the belt-shaped member in the film forming space. In the apparatus for producing a functional deposited film, which decomposes a raw material gas by microwave plasma to form a deposited film on the surface of a porous conductive member over the entire deposition surface of the strip-shaped member in the film formation space. Is disposed so as to be close to the deposition surface.

Further, in the above-mentioned device of the present invention, the porous conductive member is a mesh made of a conductive metal, and the porous conductive member and the belt-shaped member are electrically connected by a conductive material. The pressure in the film formation space is 50
Those having mTorr or less are particularly preferable.

The present invention will be described in detail below.

[0032]

The details of the deposition mechanism in the method of forming a deposited film according to the present invention described in (1) to (3) above are not completely clear yet, but it is considered as follows.

By applying a microwave energy smaller than the microwave energy required for 100% decomposition of the source gas to the source gas, a large rf energy is applied to the source gas simultaneously with the microwave energy to form a deposited film. It is believed that the active species suitable for forming can be selected. Furthermore, when the internal pressure in the deposition chamber when decomposing the source gas is 50 mTorr or less, it is considered that the gas phase reaction is suppressed as much as possible because the mean free path of active species suitable for forming a good quality deposited film is sufficiently long. . It is also considered that when the internal pressure in the deposition chamber is 50 mTorr or less, the rf energy has almost no effect on the decomposition of the source gas, and controls the potential between the plasma and the deposition chamber inner wall including the mesh. .

That is, when only microwave energy is input, the potential difference between the plasma and the inner wall surface of the deposition chamber is small, but the potential difference between the plasma and the inner wall surface of the deposition chamber ( In general, the plasma side becomes positive with respect to the wall surface of the deposition chamber). Since the plasma potential is positively high with respect to the inner wall surface of the deposition chamber, positive ions accelerated by the plasma potential among the active species decomposed by microwave energy mainly pass through the mesh and collide with each other on the substrate. It is considered that by giving the surface energy, the relaxation reaction on the surface of the deposited film is promoted and a good quality deposited film can be obtained. This effect is particularly remarkable when the deposition rate is 1 nm / sec or more.

Further, since rf has a high frequency unlike DC, the potential difference between the plasma and the inner wall surface of the deposition chamber is determined by the distribution of ionized ions and electrons. That is, the potential difference between the mesh and the plasma is determined by the synergy of ions and electrons. Therefore, in the microwave plasma CVD method in which the rf energy is superimposed, it has been found that abnormal discharge is unlikely to occur in the deposition chamber.

Even if an abnormal discharge should occur,
By interposing a mesh made of a conductive metal between the plasma and the substrate, it is possible to reduce the adverse effect of abnormal discharge on the substrate.

At this time, the presence of the mesh makes it possible to effectively reduce damage to the deposited film caused by unwanted ions and electrons reaching the substrate.

Further, by applying an appropriate DC bias voltage to the mesh, it is possible to correct and enhance the effect due to the electric field as described above, and by applying an appropriate acceleration to the ions passing through the mesh. It is possible to optimize the energy applied to the surface of the deposited film, and at the same time, it is possible to effectively reduce the impact of unnecessary ions and electrons that adversely affect the deposited film.

By heating and holding the mesh at a temperature of 100 ° C. or higher during formation of the deposited film, the life of active species having energy that effectively contributes to structural relaxation in the film during the process of forming the deposited film It becomes possible to extend and supply the active species in abundance to the surface of the deposited film. As a result, structural relaxation in the deposited film is promoted during the formation process of the deposited film, disturbance of the network in the deposited film is reduced, and electrical characteristics and reliability of the electronic device to be deposited can be improved.

By applying an appropriate rf bias voltage to the mesh, the electric field strength determined by the synergy of ionized ions and electrons can be obtained between the mesh and the substrate. This electric field provides effective acceleration to ions and electrons, effectively selecting active species having energy that contributes to structural relaxation in the deposited film formation process, and at the same time, unnecessary electrons that cause harmful damage to the deposited film. By effectively reducing the influence of ions, it is possible to reduce the disorder of the network in the deposited film.
Further, it has been found that when an rf bias voltage is applied to the mesh, abnormal discharge due to an electric field between the mesh and the substrate is unlikely to occur.

Next, in the apparatus of the present invention described in (4) above, the raw material gas is decomposed by microwave plasma in the film forming space formed by one side of the continuously moving strip-shaped member to form the strip-shaped member. In a microwave CVD apparatus for forming a deposited film, a mesh made of a porous conductive member is close to a loading side and a loading side of the band-shaped member in the deposition space or both of them over a predetermined range. It is possible to reduce the ion bombardment to the surface of the belt-shaped member and to form the deposited film in the environment where the ion bombardment is reduced, which is a buffer layer function. It has been found to have. The presence of the buffer layer enables improvement of the characteristics due to the physical properties of the interface and mass production of photovoltaic devices with excellent uniformity and few defects.

Further, the mesh and the belt-shaped member are
By connecting with a conductive material, it is possible to increase the trapping of ions and electrons by the mesh and to increase the effect of the mesh.
By keeping it at 0 mTorr or less, it becomes possible to select active species that contribute to deposition, and it is possible to continuously form a functional deposition film that can solve the above-mentioned problems.

The present device is capable of improving the characteristics due to the physical properties of the interface and mass-producing photovoltaic elements having excellent uniformity and few defects.

At the present moment, although the mechanism by which the above-mentioned effects are obtained has not been completely clarified, it can be inferred that the internal pressure of the film-forming space when decomposing the source gas is 5
In the state of 0 mTorr or less, the average free path of the active species suitable for forming a high quality deposited film is sufficiently long, so that the gas phase reaction is suppressed as much as possible, and the selection of the active species related to deposition can be realized and the film characteristics and It is considered that the deposition with excellent uniformity of the deposition rate becomes possible.

Further, it is possible to reduce the impact of high-energy ion species in the microwave plasma on the surface of the deposited film on the strip-shaped member passing through the film formation space by capturing with a mesh, which is preferable. It is believed that it is possible to form a buffer layer having interface physical properties.

Then, the above-mentioned various problems are solved and the above-mentioned various requirements are met by forming the photovoltaic element by using the apparatus for continuously depositing the above-mentioned photovoltaic element of the present invention. It is possible to form a photovoltaic element having high quality, excellent uniformity, and few defects on the filled and continuously moving strip-shaped member.

The apparatus of the present invention described in (5) above is
In a microwave CVD method in which a source gas is decomposed by microwave plasma in a film forming space formed by one side of a continuously moving band-shaped member to form a deposited film on the band-shaped member, the band-shaped member is formed in the film-forming space. A device for continuously depositing a functional deposited film, characterized in that a mesh made of a porous conductive member is arranged so as to be close to the entire deposition surface of the member, and the result of this configuration. As an action of the present invention, the plasma can be confined in the film formation space surrounded by the mesh, thereby improving the stability.

At the present moment, although the mechanism by which the above-mentioned effect is obtained has not been completely clarified, it can be inferred that a slight vibration generated when the strip-shaped member continuously moves in the film forming space is generated. It is considered that this affects the stability of plasma in the film space and affects the film characteristics.

Further, the high energy ion species in the microwave plasma is applied to the surface of the belt-like member passing through the film forming space to reduce the ion impact by capturing the ion impact, and the microwave energy is absorbed in the film forming space. By confining it stably, the microwave plasma was stabilized for a long time and the characteristics of the functional deposited film were improved.

By forming a photovoltaic element by using the above-mentioned apparatus for continuously forming a photovoltaic element of the present invention, the aforementioned problems are solved and the aforementioned requirements are satisfied. It is possible to form a photovoltaic element having high quality, excellent uniformity, and few defects on a continuously moving strip-shaped member.

The deposited film preferably manufactured by the above-described deposited film forming method and deposited film manufacturing apparatus of the present invention is a non-single crystal semiconductor film, particularly an amorphous hydrogenated silicon film (abbreviated as a-Si: H), Amorphous hydrogenated silicon halide film (a-Si:
HX), an amorphous hydrogenated silicon germanium film (abbreviated as a-SiGe: H), an amorphous hydrogenated silicon germanium halide film (abbreviated as a-SiGe: HX),
Amorphous hydrogenated silicon carbide film (abbreviated as a-SiC: H)
And an amorphous hydrogenated halogenated silicon carbide film (a-Si
C: abbreviated as HX) (all or part of the hydrogen may be replaced with deuterium) and the like.

The deposited film forming method and deposited film forming apparatus of the present invention will be described in more detail with reference to the drawings.

First, the method (1) of the present invention will be described.

FIG. 1 is a schematic diagram for explaining an example of a manufacturing apparatus system suitable for applying the deposited film forming method of the present invention. FIG. 2 is a schematic explanatory view of an example of a photovoltaic element formed by the deposited film forming method of the present invention. Figure 3
FIG. 4 is a schematic explanatory diagram of a DC magnetron sputtering apparatus for depositing a light reflection layer and a light reflection enhancement layer on a substrate when forming a photovoltaic element. FIG. 4 is a schematic explanatory view of a resistance heating vacuum vapor deposition apparatus for depositing a transparent electrode and a collector electrode of a photovoltaic element.

The deposited film forming method of the present invention will be described based on the manufacturing apparatus system schematically shown in FIG. The manufacturing apparatus system shown in FIG. 1 includes a manufacturing apparatus 100 and a source gas supply device 1020.

The manufacturing apparatus 100 includes a deposition chamber 101, a dielectric window 102 for introducing microwaves, a gas introduction tube 103, a substrate 104, a heater 105, a vacuum gauge 106, a conductance valve 107, an auxiliary valve 108, and a leak valve 1.
09, a waveguide section 110 for introducing microwaves, a bias power source 111 for applying a bias voltage to plasma, a bias rod 112, a mesh 113, a DC bias power source 114 for applying a DC bias voltage to the mesh, and the like. ing.

As a material forming the mesh 113 that is preferably used in the deposited film forming method of the present invention, Ni,
Stainless steel, Al, Cr, Mo, Au, Nb, Ta,
Examples include simple metals such as V, Ti, Pt, Pb, and Sn, and alloys thereof. Particularly, Al is preferable because it is easy to process and has high electric conductivity. In addition, stainless steel, Ni, etc. are preferable because they have high durability against plasma. The material is appropriately selected and used from these materials to form a desired deposited film.

As the shape of the mesh 113 which is preferably used in the deposited film forming method of the present invention, a linear material is knitted, or a plate-shaped material is expanded with fine cuts (expanded metal). ), Various materials such as punching metal can be used, but it is preferable that the maximum diameter of the mesh opening is 10 mm or less in order to secure the selectivity of active species and the stability of plasma, and the opening ratio is 1
It is preferably 0% or more from the viewpoint of increasing the utilization factor of the source gas and reducing the pressure unevenness inside the film forming chamber. The distance between the mesh 113 and the substrate 104 is appropriately determined according to various conditions such as the aperture ratio of the mesh 113, the internal pressure, and the DC bias voltage. Usually, the thickness and characteristics of the deposited film are uneven within a range of 2 to 30 mm. Is set and the characteristics are optimized.

In order to apply a DC bias voltage to the mesh 113, the mesh is electrically insulated from the substrate 104, the deposition chamber 101, etc., and is connected to the mesh DC bias power source 114. There is.

The mesh 113 is at least the substrate 1
It is installed so as to cover the surface of 04, and may be installed so as to divide the inside of the deposition chamber 101 into two as shown in FIG. 1, or the substrate 104 and the heater 10.
It may be installed so as to surround 5.

Further, it is preferable to control the formation of the deposited film on the substrate 104 by installing a shutter 115 that can be operated from outside the deposition chamber 101 in the vicinity of the substrate 104. It is preferable to install the shutter 115 between the mesh 113 and the substrate 104 because the opening and closing of the shutter 115 has less influence on plasma.

Further, in FIG. 1, the substrate 104 and the mesh 1
Although 13 is installed perpendicularly to the microwave introduction direction, the present invention is not limited to this, and it is also possible to install it in parallel or obliquely.

Further, it is preferable that the mesh 113 can be substantially removed by an operation from the outside while keeping the vacuum in the deposition chamber 101 according to a desired deposition film forming condition. Similarly, it is more preferable that the mesh can be exchanged for another type and shape by an external operation. Further, it is preferable that the mesh 113 can be moved continuously or intermittently (for example, a device including a delivery roll and a winding roll) because the influence of a deposited film attached to the mesh can be reduced.

The raw material gas supply device 1020 includes the introduction valves 1041 to 1046 for introducing the raw material gas, the mass flow controllers 1021 to 1026, the primary valves 1031 to 1036 of the mass flow controller, and the pressure regulator 10.
61 to 1066, cylinder valves 1051 to 1056,
It is composed of raw material gas cylinders 1071 to 1076 and the like.

An example of the film forming procedure by the above film forming system will be described below.

First, a substrate 104 for forming a deposited film is mounted in the deposition chamber 101 shown in FIG. 1, and the deposition chamber is evacuated to a level of 10.sup.- ⁵ Torr or less. A turbo molecular pump is suitable for this exhaust, but an oil diffusion pump may be used. However, when an oil diffusion pump is used, gases such as H ₂ , He, Ar, Ne, Kr, and Xe are introduced into the deposition chamber when the internal pressure of the deposition chamber 101 becomes 10 ⁻⁴ or less so that the oil does not diffuse back into the deposition chamber. Is preferably introduced into After sufficiently exhausting the inside of the deposition chamber, H ₂ , He, Ar, Ne, Kr, X
A gas such as e is introduced into the deposition chamber so that the pressure in the deposition chamber is almost the same as when the source gas for forming the deposited film is flowed. The pressure inside the deposition chamber is 0.5 to 50 mTorr.
Is the optimum range. When the internal pressure in the deposition chamber has stabilized, the substrate heating heater 105 is turned on to turn the substrate 100-
Heat to 500 ° C. When the temperature of the substrate stabilizes at a predetermined temperature, the gases such as H ₂ , He, Ar, Ne, Kr, and Xe are stopped, and a predetermined amount of the raw material gas for forming the deposited film is introduced into the deposition chamber from the gas cylinder through the mass flow controller. To do.
The supply amount of the source gas for forming the deposited film introduced into the deposition chamber is appropriately determined depending on the volume of the deposition chamber, desired characteristics of the deposited film, and the like. The pressure in the deposition chamber when the source gas for forming the deposited film is introduced into the deposition chamber is a very important factor in the method of the present invention, and the optimum internal pressure in the deposition chamber is 0.5 to 50 mTorr.

In the method of the present invention, the microwave energy input into the deposition chamber for forming the deposited film is an important factor. The magnitude of the microwave energy is appropriately determined depending on the flow rate of the source gas introduced into the deposition chamber, the volume of the deposition chamber, the shape of the deposition chamber, the position of the substrate, and other conditions. The energy is smaller than the microwave energy required for 100% decomposition, and the preferable range is 0.02 to 1 W / cm.
^{Is 3} . As a preferable frequency range of microwave energy, 0.5 to 10 GHz can be mentioned.
A frequency near 2.45 GHz is particularly suitable. Further, in order to form a deposited film with reproducibility by the deposited film forming method of the present invention and to form a deposited film on a long substrate continuously conveyed for several hours to several tens of hours, microwave energy is required. The frequency stability of is very important. It is preferable that the frequency variation is within ± 2%. Further, the ripple of the microwave is preferably within ± 2%.

The fact that the microwave energy input is smaller than the microwave energy required for 100% decomposition of the raw material gas is determined by conducting an experiment as described below in advance. I can confirm.

The conditions other than the microwave energy are made equal and constant at the time of the actual formation of the deposited film, the deposition film single film is formed while changing only the microwave energy value to be input, and the deposition rate of the single film and the microwave are changed. Examine the relationship between wave energy values. Then, when the source gas is decomposed 100% by the microwave energy and contributes to the formation of the deposited film, the deposition rate has no or small dependence on the microwave energy value (source gas flow rate-controlled state).
However, when the value is smaller than the microwave energy required for 100% decomposition of the source gas, it can be understood that the dependence of the deposition rate on the microwave energy is large (microwave energy rate-determining state). That is, in the deposited film forming method of the present invention, the deposited film is formed in the microwave energy rate-determining state, which can be confirmed by examining the relationship between the microwave energy and the deposition rate.

Further, in the method of forming a deposited film of the present invention, r is introduced into the deposition chamber at the same time as the microwave energy.
The f energy is a very important factor in combination with the microwave energy, and a preferable range of the rf energy is 0.04 to 2 W / cm ³ , and a bias rod installed in the plasma generation space in the deposition chamber. Is applied to the plasma through.

A preferable frequency range of the rf energy is 1 to 100 MHz. Also r
The fluctuation of the frequency of f is preferably within ± 2% and the waveform is smooth.

Further, in addition to the rf energy, a DC bias voltage may be applied to the bias rod 112 in an overlapping manner. The polarity of the DC bias voltage depends on the deposition chamber 101.
It is preferable to apply a voltage so that the bias rod 112 becomes positive. The preferable range of the DC bias voltage is 300 V or less.

When a bias voltage is applied to the bias rod 112 before the generation of plasma by the introduction of microwaves, abnormal discharge is rarely found in an unstable state at the beginning of plasma generation, which is a characteristic of the deposited film. It is preferable that the bias voltage be applied to the bias rod 112 after the plasma is stabilized, because it may adversely affect the temperature.

The microwave energy is introduced into the deposition chamber from the waveguide 110 through the dielectric window 102, and the deposition chamber 1
After the source gas introduced into 01 is decomposed to generate plasma and the plasma is stabilized, rf energy is introduced from the bias power source 111 into the deposition chamber via the bias rod 112. Then, a DC bias voltage is applied to the mesh 113. The value of the DC bias voltage applied to the mesh 113 is appropriately determined by parameters such as the structure and size in the deposition chamber 101 and the desired characteristics of the deposited film, but is preferably 300 V or less.

When a DC bias voltage is applied to the mesh 113 before the generation of plasma by the introduction of microwaves, abnormal discharge is rarely seen in an unstable state at the beginning of plasma generation, which is a characteristic of the deposited film. Therefore, it is preferable that the DC bias voltage be applied to the mesh 113 after the plasma is stabilized.

With the gas flow rate, deposition chamber pressure, plasma, bias current, etc. being stable, the shutter 113 is opened to form a deposition film having a desired film thickness on the substrate 104 for a desired time. When the thickness of the deposited film reaches a desired value, the shutter 113 is closed, and the mesh D
C bias voltage application, microwave energy, rf energy, introduction of source gas was stopped, the inside of the deposition chamber 101 was evacuated, and the inside of the deposition chamber 101 was sufficiently filled with gas such as N ₂ , He, Ar, Ne, Kr, and Xe. After purging, the substrate 104 on which the non-single crystal semiconductor film is deposited is taken out from the deposition chamber 101.

Next, the method (2) of the present invention will be described.

FIG. 5 is a schematic diagram for explaining an example of a manufacturing apparatus system suitable for applying the deposited film forming method of the present invention. 2A and 2B are schematic explanatory views of examples of photovoltaic elements formed by the deposited film forming method of the present invention.

The deposited film forming method of the present invention will be described based on the manufacturing apparatus system schematically shown in FIG. The manufacturing apparatus system shown in FIG. 5 basically complies with the manufacturing apparatus system of the method of the present invention described in (1) above, and includes a manufacturing apparatus 100 and a source gas supply device 1020.

The manufacturing apparatus 100 includes a deposition chamber 101, a dielectric window 102 for introducing microwaves, a gas introduction tube 103, a substrate 104, a heater 105, a vacuum gauge 106, a conductance valve 107, an auxiliary valve 108, and a leak valve 1.
09, a waveguide section 110 for introducing microwaves, a bias power source 111 for applying a bias voltage to plasma, a bias rod 112, a mesh 113, a temperature controller 116 for adjusting the temperature of the mesh, and the like.

The basic operation and apparatus in this method of the present invention are the same as those of the method of the present invention described in (1) above, but the deposited film is formed while heating and holding the mesh 113 at 100 ° C. or higher. It is characterized by that.

As a method of adjusting the temperature of the mesh 113, a filament made of a refractory metal such as tungsten is placed in contact with the mesh or in the vicinity of the mesh, and an AC or DC current is passed through the filament to generate heat. Then, the mesh 113 is heated, and at the same time, the temperature of the mesh 113 is measured using a temperature measuring element such as a thermocouple,
A suitable method is to control this.

As another method for adjusting the temperature of the mesh 113, a halogen lamp or the like is installed near the mesh and the mesh 113 is irradiated with light.
A method in which 3 is heated and at the same time the temperature of the mesh 113 is measured using a temperature measuring element such as a thermocouple and the temperature is controlled can also be mentioned as a suitable method.

As another method of adjusting the temperature of the mesh 113, an electric current of AC or DC is applied to the mesh 113 to generate heat due to the electric resistance of the mesh itself, and at the same time, a temperature measuring element such as a thermocouple is used.
A method of measuring the temperature of 13 and controlling it can also be mentioned as a suitable method.

In order to adjust the temperature of the mesh 113, it is necessary to provide a cooling means such as a water cooling mechanism and a Peltier element in addition to the above heating means.
It is effective and preferable for finely adjusting the temperature of.

Also in the method of the present invention, a bias voltage may be applied to the mesh 113 as in the case of (1). In that case, the mesh needs to be electrically insulated from the substrate 104, the deposition chamber 101 and the like, and a bias power source needs to be connected to the mesh. Further, when the mesh has the same potential as that of the deposition chamber 101, a conductive member for electrically connecting the mesh to the wall surface of the deposition chamber may be provided between the mesh and the deposition chamber 101. Good.

Hereinafter, one example of the film forming procedure based on the manufacturing apparatus system shown in FIG. 5 will be shown, but it goes without saying that the film forming procedure is not limited to this.

First, a substrate 104 for forming a deposited film is mounted in the deposition chamber 101 shown in FIG. 5, and the deposition chamber is evacuated to a level of 10.sup.- ⁵ Torr or less. A turbo molecular pump is suitable for this exhaust, but an oil diffusion pump may be used. However, when an oil diffusion pump is used, gases such as H ₂ , He, Ar, Ne, Kr, and Xe are introduced into the deposition chamber when the internal pressure of the deposition chamber 101 becomes 10 ⁻⁴ or less so that the oil does not diffuse back into the deposition chamber. Is preferably introduced into After sufficiently exhausting the inside of the deposition chamber, H ₂ , He, Ar, Ne, Kr, X
A gas such as e is introduced into the deposition chamber so that the pressure in the deposition chamber is almost the same as when the source gas for forming the deposited film is flowed. The pressure inside the deposition chamber is 0.5 to 50 mTorr.
Is the optimum range. When the internal pressure in the deposition chamber has stabilized, the substrate heating heater 105 is turned on to turn the substrate 100-
Heat to 500 ° C. When the temperature of the substrate stabilizes at a predetermined temperature, the gases such as H ₂ , He, Ar, Ne, Kr, and Xe are stopped, and a predetermined amount of the raw material gas for forming the deposited film is introduced into the deposition chamber from the gas cylinder through the mass flow controller. To do.
The supply amount of the source gas for forming the deposited film introduced into the deposition chamber is appropriately determined depending on the volume of the deposition chamber, desired characteristics of the deposited film, and the like. The pressure in the deposition chamber when the source gas for forming the deposited film is introduced into the deposition chamber is a very important factor in the deposition film forming method of the present invention, and the optimum internal pressure in the deposition chamber is 0.5 to 50 mTorr. Is.

Further, the temperature of the mesh 113 is set to a predetermined temperature of 100 ° C. or higher by operating the temperature controller 114 for the mesh 113.

In the deposited film forming method of the present invention, the microwave energy input into the deposition chamber for forming the deposited film is an important factor.

With the gas flow rate, the pressure in the deposition chamber, the plasma, the bias current and the like being stable, the shutter 113 is opened to form a deposited film having a desired film thickness on the substrate 104 for a desired time. When the thickness of the deposited film reaches a desired value, the shutter 113 is closed, application of the bias voltage to the bias rod 112, microwave energy, and introduction of the source gas are stopped, and the inside of the deposited film 101 is evacuated. ₂ , He,
The substrate 10 on which the non-single-crystal semiconductor film is deposited after the inside of the deposition chamber 101 is sufficiently purged with a gas such as Ar, Ne, Kr, or Xe.
4 is taken out from the deposition chamber 101.

Next, the method (3) of the present invention will be described.

FIG. 8 is a schematic diagram for explaining an example of a manufacturing apparatus system suitable for applying the deposited film forming method of the present invention.

The deposited film forming method of the present invention will be described based on the manufacturing apparatus system schematically shown in FIG. The manufacturing apparatus system shown in FIG. 8 includes a manufacturing apparatus 100 and a source gas supply device 1020.

The manufacturing apparatus 100 includes a deposition chamber 101, a dielectric window 102 for introducing microwaves, a gas introduction tube 103, a substrate 104, a heater 105, a vacuum gauge 106, a conductance valve 107, an auxiliary valve 108, and a leak valve 1.
09, a waveguide section 110 for introducing microwaves, a bias power source 111 for applying a bias voltage to plasma, a bias rod 112, a mesh 113, an rf bias power source 117 for applying an rf bias voltage to the mesh, and the like. ing.

Also in this method, the basic operation and apparatus are the same as those in the above-mentioned case (1), but the feature is that an rf bias voltage is applied to the mesh 113.

As a method of applying the rf voltage, microwave energy is introduced from the waveguide section 110 into the deposition chamber through the dielectric window 102 to decompose the source gas introduced into the deposition chamber 101 to generate plasma. After the plasma is stabilized, rf energy is introduced from the bias power source 111 into the deposition chamber via the bias rod 112. Then, an rf bias voltage is applied to the mesh 113. The frequency of the rf bias voltage applied to the mesh 113 depends on parameters such as the structure and size in the deposition chamber 101.
Further, although it is appropriately determined depending on the desired characteristics of the deposited film, it preferably has a frequency of 1 to 100 MHz. The voltage value of the bias voltage applied to the mesh 113 is appropriately determined by parameters such as the structure and size in the deposition chamber 101 and the desired characteristics of the deposited film, but is preferably peak-to-peak. Is 1 kV or less. Also, the frequency fluctuation is ± 2%
It is preferable that the waveform is smooth within the range.

When the rf bias voltage is applied to the mesh 113 before the generation of plasma by the introduction of microwaves, abnormal discharge is rarely seen in an unstable state at the initial stage of plasma generation, which is a characteristic of the deposited film. It is preferable that the rf bias voltage is applied to the mesh 113 after the plasma is stabilized, since it may adversely affect the above.

With the gas flow rate, deposition chamber pressure, plasma, bias current, etc. stabilized, the shutter 113 is opened to form a deposited film having a desired film thickness on the substrate 104 for a desired time. When the thickness of the deposited film reaches a desired value, the shutter 113 is closed and the mesh 113 is r
The application of the f-bias voltage, the microwave energy, the rf energy, and the introduction of the source gas are stopped, the inside of the deposition chamber 101 is evacuated, and the inside of the deposition chamber 101 is sufficiently filled with a gas such as N ₂ , He, Ar, Ne, Kr, or Xe. After purging, the substrate 104 on which the non-single crystal semiconductor film is deposited is taken out from the deposition chamber 101.

Here, the raw material gas suitable for the present invention will be described.

The source gas for depositing silicon is silicon.
A compound containing a con atom and capable of being gasified is preferable, for example,
For example, SiH_Four, SiH₆, SiF_Four, SiFH₃, Si
F₂H₂, SiF₃H, Si₃H₈, SiD_Four, SiH
D₃, SiH₂D₂, SiH ₃D, SiFD₃, SiF
₂D₂, SiD₃H, Si₂H₆, Si₂D₆, Si ₂
D₃H₃Etc. can be mentioned.

As a source gas for depositing germanium,
A compound that contains a germanium atom and is gasifiable is preferable.
So, for example, GeH_Four, GeD_Four, GeF_Four, GeFH
₃, GeF₂H₂, GeF₃H, GeHD₃, GeH₂
D₂, GeH₃D, Ge₂H ₆, Ge₂D₆Etc.
be able to.

As the source gas for depositing carbon atoms, a compound containing carbon atoms and capable of being gasified is preferable.
H ₄ , CD ₄ , C _n H _{2n + 2} (n is an integer), C _n H _2n (n
Is an integer), C ₂ H ₂ , C ₆ H _{6 and the} like.

Further, as the substance introduced into the non-single crystal semiconductor layer for controlling the conduction type of the non-single crystal semiconductor layer, there can be mentioned Group III atoms and Group V atoms of the periodic table.

Effectively used as a starting material for introducing a Group III atom are B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ and B ₆ for introducing a boron atom. H ₁₀ ,
Borohydrides such as B ₆ H ₁₂ and B ₆ H ₁₄ , and BF ₃ ,
Examples thereof include boron halides such as BCl ₃ . In addition to this, AlCl ₃ , GaCl ₃ , InCl ₃ ,
TlCl _{3 and the} like can also be mentioned.

Effective as a starting material for introducing a Group V atom
PH used for introducing phosphorus atoms is used.₃, P₂H
_FourPhosphorus hydride such as, and PH_FourI, PF₃, PF_Five, P
Cl ₃, PCl_Five, PBr₃, PBr_Five, PI₃Etc.
Mention may be made of phosphorus-containing phosphorus. In addition, AsH₃,
AsF₃, AsCl₃, AsBr₃, AsF_Five, SbH
₃, SbF_Five, SbF_Five, SbCl₃, SbCl_Five, B
iH₃, BiCl₃, BiBr₃And so on
It

In order to control the conductivity type of the amorphous crystalline semiconductor layer to be almost i-type, the introduction amount of the group III atom and the group V atom of the periodic table to the layer is preferably 1000 ppm or less. You can Further, in order to control the conduction type to be almost i-type, an atom of group III and an atom of group V of the periodic table may be added so as to be simultaneously compensated.

The introduced amount of the group III atom of the periodic table and the group V atom of the periodic table introduced for controlling the conductivity type of the non-single-crystal semiconductor layer to p-type or n-type is 100 ppm to 10%.
Can be mentioned as a preferable range.

Further, the above-mentioned gasifiable compound is added to N ₂ , D
The gas may be appropriately diluted with a gas such as ₂ , He, Ne, Ar, Xe, and Kr and introduced into the deposition chamber. In particular, N ₂ , D ₂ , and H are the most suitable gases for diluting the above-mentioned gasifiable compounds.
e can be mentioned.

Next, a preferred application example of the present invention will be described.

As described above, the deposited film forming method of the present invention is
The method is suitable for forming semiconductor layers used in various electronic devices such as photovoltaic elements, sensors, thin film transistors, and electrophotographic image forming members. Hereinafter, the case where the deposited film forming method of the present invention is applied to the production of a photovoltaic element will be described, but it goes without saying that the present invention is not limited to this and can be applied to other electronic devices. .

<Application to Photovoltaic Element> FIGS. 2A and 2B are schematic explanatory views of a photovoltaic element used for a solar cell, a sensor, or the like. In FIG. 2A, the photovoltaic element 200 includes a conductive substrate 201, a light reflection layer 202,
Light reflection increasing layer 203, n-type (p-type) conductivity type layer 204, i
Type layer 205, p-type (n-type) conductivity type layer 206, transparent electrode 2
07 and the collector electrode 208. Then, the light is emitted from the transparent electrode 207 side.

Further, the first conductivity type layer, the i-type layer and the second conductivity type layer may be used as one unit to form a double cell or triple cell structure in which 2 units and 3 units of these units are stacked. The structure of the double cell is schematically shown in FIG. In FIG. 2B, the photovoltaic element 210
Is the conductive substrate 211, the light reflection layer 212, the light reflection increasing layer 213, the first n-type (p-type) conductivity type layer 214, and the first i.
Type layer 215, first p-type (n-type) conductivity type layer 216, second
N-type (p-type) conductivity type layer 217, second i-type layer 218,
It is composed of a second p-type (n-type) conductivity type layer 219, a transparent electrode 220, and a collector electrode 221. Then, the light is emitted from the transparent electrode 220 side.

On the other hand, a member having a substantially light-transmitting property is used for the substrate, and a transparent electrode, each semiconductor layer and a light-reflecting metal electrode are provided in this order on the substrate, and light is incident from the transparent substrate side. The deposited film forming method of the present invention can be applied to a photovoltaic element.

Further, it is preferable to texture at least one of the conductive substrate, the light reflection layer, the light reflection increasing layer and the transparent electrode because the photocurrent of the photovoltaic element can be increased.

The construction of the photovoltaic element suitable for the present invention will be described below. However, it is needless to say that the following description is one mode of the present invention and the present invention is not limited to this and can be applied to a photovoltaic element having another configuration.

<Structure of Photovoltaic Device> Conductive Substrate The conductive substrate may be a conductive material. A support is formed of an electrically insulating material or a conductive material, and a conductive treatment is performed thereon. It may be one. Examples of the conductive material preferably used in the present invention include Ni, stainless steel, Al, Cr, Mo, Au, Nb, Ta, V, and Ti.
Examples include simple metals such as Pt, Pb, and Sn or alloys thereof.

The electrically insulating material preferably used in the present invention is a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide. , Glass, ceramics, paper, and the like. It is preferable that at least one surface of these electrically insulating materials is subjected to an electric conduction treatment, and a photovoltaic layer is provided on the surface side subjected to the electric conduction treatment.

For example, in the case of glass, N
iCr, Al, Cr, Mo, Ir, Nb, Ta, V, T
i, Pt, Pb, In₂O₃, SnO₂, ITO (In
₂O ₃+ SnO₂By providing a thin film of
To provide conductivity, or when using polyester film, etc.
For synthetic resin film, NiCr, Al, Ag, P
b, Zn, Ni, Au, Cr, Mo, Ir, Nb, T
Vacuum deposition of thin metal films such as a, V, Tl, Pt, etc.
It is provided on the surface by vapor deposition, sputtering, etc., or
Laminate the surface with metal and conduct electricity to the surface
Imparts sex. The shape of the support is smooth surface or uneven surface
The surface can be sheet-like. Its thickness is as desired
The photovoltaic power is determined as appropriate so that
When flexibility as an element is required, use it as a support
Be as thin as possible within the range where all functions are fully exhibited.
You can However, on the support film formation and handling
In terms of mechanical strength, etc., it is usually 10 μm or more.
ItLight reflection layer The light reflecting layer may be Ag, Al, Cu, AlSi, or the like.
Metals with high reflectance from visible light to near infrared light are suitable.
It As a method of forming the light reflecting layer made of these metals,
Resistance heating vacuum deposition, electron beam vacuum deposition, co-deposition
And the sputtering method may be mentioned as a preferable method.
it can. The layer thickness of these metals as a light reflecting layer is
A suitable layer thickness is 10 nm to 5000 nm.
You can How to texture the surface of the light reflecting layer
There are several methods such as sandblast method, chemical etching method, etc.
It is well known that these metal layers are on a support.
A method of controlling the temperature during formation to 200 ° C. or higher, or the metal
Spontaneously textured by making layers relatively thick
This is a simple and reproducible method.Reflection enhancement layer ZnO, SnO as the reflection increasing layer₂, In₂O₃, I
TO, TiO₂, CdO, Cd₂SnO_Four, Bi
₂O₃, MoO₃, Na_xWO₃, And so on
Can be listed.

Suitable methods for depositing the reflection-increasing layer include vacuum vapor deposition method, sputtering method, CVD method, spray method, spin-on method, dip method and the like.

The optimum value of the thickness of the reflection increasing layer varies depending on the refractive index of the material of the reflection increasing layer and the like, but a preferable range is 50 nm to 10 μm. P-type layer or n-type layer (first and second conductivity type layers) The p-type layer or n-type layer is an important layer that influences the characteristics of the photovoltaic element.

As an amorphous material (denoted as a-) of a p-type layer or an n-type layer (of course, a microcrystalline material (denoted as μc-) is also included in the category of amorphous materials). , A-Si: H, a-Si: HX (X is a halogen atom such as F or Cl), a-SiC: H, a-SiC: HX,
a-SiGe: H, a-SiGeC: H, a-SiO:
H, a-SiN: H, a-SiON: HX, a-SiO
CN: HX, μc-Si: H, μc-SiC: H, μc
-Si: HX, μc-SiC: HX, μc-SiGe:
H, μc-SiO: H, μc-SiGeC: H, μc-
SiN: H, μc-SiON: HX, μc-SiOC
N: HX, etc., such as a p-type valence electron control agent (group III atom B, Al, Ge, In, Tl of the periodic table) or an n-type valence electron control agent (group V atom of the periodic table, P, As a material containing a high concentration of As, Sb, Bi), a polycrystalline material (pol
(displayed as y-), for example, poly-Si:
H, poly-Si: HX, poly-SiC: H, p
poly-SiC: HX, poly-SiGe: H, po
ly-Si, poly-SiC, poly-SiGe,
And a p-type valence electron control agent (group III atom B of the periodic table,
Examples thereof include Al, Ge, In, Tl) and n-type valence electron control agents (group V atom of the periodic table, P, As, Sb, Bi) added in high concentration.

Particularly, for the p-type layer or the n-type layer on the light incident side, a crystalline semiconductor layer with little light absorption or an amorphous semiconductor layer with a wide band gap is suitable.

The amount of Group III atoms added to the p-type layer and the amount of Group V atoms added to the n-type layer are 0.1 to 0.1%.
50% can be mentioned as the optimum amount.

Hydrogen atoms (H, D) or halogen atoms contained in the p-type layer or the n-type layer serve to compensate dangling bonds in the p-type layer or the n-type layer, and It improves the doping efficiency of the layer. The optimum amount of hydrogen atoms or halogen atoms added to the p-type layer or the n-type layer is 0.1 to 40%. Especially when the p-type layer or the n-type layer is crystalline, the hydrogen atom or halogen atom is 0.1
-8% can be mentioned as the optimum amount. In addition, hydrogen atoms or / on the interface sides of the p-type layer / i-type layer and the n-type layer / i-type layer
And those in which the content of halogen atoms is large are listed as a preferable distribution form, and the content of hydrogen atoms and / or halogen atoms in the vicinity of the interface is 1.1 to 2 times the content in the bulk. The range can be mentioned as a preferable range. Thus, by increasing the content of hydrogen atoms or halogen atoms in the vicinity of each interface of the p-type layer / i-type layer and the n-type layer / i-type layer, the defect level and stress near the interface can be reduced. Therefore, the photovoltaic power and photocurrent of the photovoltaic device of the present invention can be increased.

Regarding the electric characteristics of the p-type layer and the n-type layer of the photovoltaic element, the activation energy is preferably 0.2 eV or less, and most preferably 0.1 eV or less. The specific resistance is preferably 100 Ωcm or less, and most preferably 1 Ωcm or less. Furthermore, the layer thickness of the p-type layer and the n-type layer is 1 to 5
0 nm is preferable and 3 to 10 nm is optimum.

As the source gas suitable for depositing the p-type layer or the n-type layer of the photovoltaic element, a gasifiable compound containing a silicon atom, a gasifiable compound containing a germanium atom, or a carbon atom was contained. Examples thereof include compounds that can be gasified or mixed gas of the compounds.

Specifically, gasification containing silicon atoms
SiH as the compound to be obtained_Four, SiH₆, SiF_Four, S
iFH₃, SiF₂H₂, SiF₃H, Si₃H₈, S
iD _Four, SiHD₃, SiH₂D₂, SiH₃D, Si
FD₃, SiF₂D₂, SiD₃H, Si₂D₃H₃,
Etc. can be mentioned.

Specifically, as the gasifiable compound containing a germanium atom, GeH ₄ , GeD ₄ , GeF ₄ ,
GeFH ₃ , GeF ₂ H ₂ , GeF ₃ H, GeHD ₃ ,
_{GeH 2 D 2, GeH 3 D} , mention may be made of _{Ge 2 H 6, Ge 2 D} 6 , and the like.

Specifically gasifiable containing carbon atoms
CH as a compound_Four, CD_Four, C _nH_{2n + 2}(N is an integer
Number) C_nH_2n(N is an integer), C₂H₂, C₆H₆, CO
₂, CO and the like.

Examples of the substance introduced into the p-type layer or the n-type layer for controlling the valence electrons include Group III atoms and Group V atoms of the periodic table.

Effective as a starting material for introducing a Group III atom
Specifically, the boron atom introduced is used for
For use, B₂H₆, B_FourH_Ten, B_FiveH₉, B
_FiveH₁₁, B ₆H_Ten, B₆H₁₂, B₆H₁₄Borohydride
Elementary, BF₃, BCl₃, Boron halides, etc.
You can In addition to this, AlCl₃, GaCl₃,
InCl₃, TlCl₃Etc. can also be mentioned. In particular
B₂H₆, BF₃Is suitable.

Effective as a starting material for introducing a Group V atom
Specifically used is PH for introducing a phosphorus atom.
₃, P₂H_FourPhosphorus hydride, PH, etc._FourI, PF₃, P
F_Five, PCl₃, PCl_Five, PBr₃, PBr_Five, PI
₃And the like. Besides this A
sH₃, AsF₃, AsCl₃, AsBr₃, As
F_Five, SbH₃, SbF₃, SbF_Five, SbCl₃, S
bCl_Five, BiH₃, BiCl ₃, BiBr₃Etc.
You can Especially PH₃, PF₃Is suitable.

The p-type layer or the n-type layer deposition method suitable for the photovoltaic device is an rf plasma CVD method and a microwave plasma CVD method.

When depositing by the rf plasma CVD method, the capacitive coupling type rf plasma CVD method is suitable.

When a p-type layer or an n-type layer is deposited by the rf plasma CVD method, the substrate temperature in the deposition chamber is 100 to 3
50 ° C., internal pressure 0.1 to 10 Torr, rf energy 0.05 to 1.0 W / cm ² , deposition rate 0.1.
The optimum condition is 01 to 3 nm / sec.

Also, the gasifiable compound may be H ₂ , He,
It may be appropriately diluted with a gas such as Ne, Ar, Xe, or Kr and introduced into the deposition chamber.

In particular, when depositing a layer having a small band of light absorption or a wide bandgap such as a microcrystalline semiconductor or a-SiC: H, the source gas is diluted with hydrogen gas 2 to 100 times, and the rf energy is relatively large. It is preferable to introduce power. The frequency of rf is 1MHz-100M
Hz is a suitable range, and particularly a frequency near 13.56 MHz is optimum.

Microwave plasma C is used for the p-type layer or the n-type layer.
When depositing by the VD method, the microwave plasma CVD apparatus is preferably a method of introducing microwaves into the deposition chamber through a dielectric window (alumina ceramics or the like) using a waveguide.

The p-type layer or the n-type layer formed by the microwave plasma CVD method is also suitable for the deposition film forming method of the present invention, but a deposition film applicable to a photovoltaic element is formed under wider deposition conditions. can do.

When a p-type layer or an n-type layer is deposited by a microwave plasma CVD method other than the method of the present invention, the substrate temperature in the deposition chamber is 100 to 400 ° C., and the internal pressure is 0.5 to 30 m.
Torr, microwave power 0.01 to 1 W / c
A preferable range of m ³ and microwave frequency is 0.5 to 10 GHz.

Further, the gasifiable compound may be H ₂ , He,
It may be appropriately diluted with a gas such as Ne, Ar, Xe, or Kr and introduced into the deposition chamber.

In particular, when depositing a layer such as a microcrystalline semiconductor or a-SiC: H having a small light absorption or a wide hand gap, the source gas is diluted with hydrogen gas to 2 to 100 times, and the microwave power is relatively high. It is preferable to introduce a large power. i-Type Layer In a photovoltaic device, the i-type layer is an important layer that generates and transports carriers for irradiation light.

The material for the i-type layer need not be a strictly i-type material, and a slightly p-type or slightly n-type material can be used.

The i-type layer of the photovoltaic element of the present invention is an amorphous material such as a-Si: H, a-Si: HX, a-.
SiC: H, a-SiC: HX, a-SiGe: H, a
-SiGe: HX, a-SiGeC: HX, etc. can be mentioned.

In particular, as the i-type layer, an intrinsic material is formed by adding a group III atom and / or a group V atom of the periodic table to the above amorphous material as a valence electron control agent.
Suitable materials may be mentioned.

The hydrogen atom (H, D) or halogen atom (X) contained in the i-type layer serves to compensate dangling bonds of the i-type layer, and the mobility and life of carriers in the i-type layer. To improve the product of Further, it serves to compensate the interface states generated at the interfaces of the p-type layer / i-type layer and the n-type layer / i-type layer, and improves the photovoltaic power, photocurrent and photoresponsiveness of the photovoltaic device. It is effective. The optimum content of hydrogen atoms and / or halogen atoms contained in the i-type layer can be 1 to 40%. In particular, p-type layer / i-type layer, n
A preferable distribution form is one in which the content of hydrogen atoms and / or halogen atoms is largely distributed on each interface side of the type layer / i-type layer, and the content of hydrogen atoms and / or halogen atoms near the interface is included. The amount is 1.1 to 2 of the content in the bulk.
A double range can be mentioned as a preferable range.

The layer thickness of the i-type layer depends on the structure of the photovoltaic element (for example, single cell, double cell, triple cell) and i
Although it is appropriately determined depending on various conditions such as optical and electrical characteristics of the mold layer, 0.1 to 1.0 μm can be mentioned as the optimum layer thickness.

Further, it is preferable that the band gap of the i-type layer is designed to be wide on the interface side of each of the p-type layer / i-type layer and the n-type layer / i-type layer. By designing in this way, the photovoltaic power and photocurrent of the photovoltaic element can be increased, and further photodegradation and the like when used for a long time can be reduced.

The deposited film forming method of the present invention is most suitable for the i-type layer of the photovoltaic element. Transparent electrode ZnO, Sn are suitable materials for the transparent electrode.
O ₂ , In ₂ O ₃ , ITO, TiO ₂ , CdO, Cd _{2
SnO 4, Bi 2 O 3,} MoO 3, Na x WO 3, and the like.

The transparent electrode is deposited as follows.

The sputtering method and the vacuum evaporation method are the most suitable deposition methods for depositing the transparent electrode.

As a sputtering apparatus suitable for depositing a transparent electrode, a DC magnetron sputtering apparatus schematically shown in FIG. 3 can be mentioned.

The DC magnetron sputtering apparatus schematically shown in FIG. 3 suitable for depositing a transparent electrode includes a deposition chamber 301, a substrate 302, a heater 303, targets 304, 3
08, insulating supports 305, 309, DC power supply 306,
310, shutters 307, 311, vacuum gauge 312, conductance valve 313, gas introduction valves 314, 3
15, mass flow controllers 316, 317 and the like.

In a DC magnetron sputtering apparatus, when a transparent electrode made of indium oxide is deposited on a substrate, a target made of metal indium (In) or indium oxide (In ₂ O ₃ ) is used.

When a transparent electrode made of indium-tin oxide is further deposited on the substrate, the target is metal tin, metal indium or an alloy of metal tin and metal indium, tin oxide, indium oxide, indium-tin oxide, etc. Are used in combination as appropriate.

When depositing by the sputtering method, the substrate temperature is an important factor, and 25 ° C. to 600 ° C. can be mentioned as a preferable range. In addition, as a gas for sputtering when depositing the transparent electrode by a sputtering method, an inert gas such as argon gas (Ar), neon gas (Ne), xenon gas (Xe), and helium gas (He) can be mentioned. Ar gas is the optimum one. Further, it is preferable to add oxygen gas (O ₂ ) to the inert gas as needed. Especially when a metal is used as a target, oxygen gas (O ₂ ) is essential.

Further, when the target is sputtered with the inert gas or the like, the pressure in the discharge space is 0.1 to 50 mTorr in order to effectively sputter.
Can be mentioned as a preferable range.

In addition, as a power source for the sputtering method, a DC power source and an rf power source are suitable. The power for sputtering is 10 to 10
00W is a suitable range.

The deposition rate of the transparent electrode depends on the pressure of the discharge space and the discharge power, and the optimum deposition rate is 0.01
The range is from 10 nm / sec.

The layer thickness of the transparent electrode is preferably deposited under the conditions that satisfy the conditions of the antireflection film. As a specific layer thickness of the transparent electrode, 50 to 300 nm can be mentioned as a preferable range.

As a second method suitable for depositing the transparent electrode, a vacuum vapor deposition method can be mentioned.

The vacuum vapor deposition apparatus is, as schematically shown in FIG. 4, a deposition chamber 401, a substrate 402, a heater 403,
The vapor deposition source 404, the vapor deposition source heater 404, the AC power source 406, the shutter 407, the vacuum gauge 408, the conductance valve 409, the gas introduction valve 410, the mass flow controller 411, the leak valve 412, and the film thickness monitor 413 are included.

Suitable vapor deposition sources for depositing transparent electrodes in the vacuum vapor deposition method include metal tin, metal indium, and indium-tin alloy.

The suitable substrate temperature for depositing the transparent electrode is 25 ° C. to 600 ° C.

Further, when depositing the transparent electrode, the pressure of the deposition chamber is reduced to 10 ^-6 Torr or less, and then oxygen gas (O ₂ ) is introduced into the deposition chamber in the range of 5 × 10 ^-5 Torr to 9 × 10 ^-4 Torr. It is necessary to introduce.

By introducing oxygen in this range, the metal vaporized from the vapor deposition source reacts with oxygen in the vapor phase to deposit a good transparent electrode.

Further, plasma may be generated by introducing rf electric power at the above-mentioned degree of vacuum and vapor deposition may be carried out through the plasma.

The preferable range of the deposition rate of the transparent electrode under the above conditions is 0.01 to 10 nm / sec.
If the deposition rate is less than 0.01 nm / sec, the productivity will be reduced, and if it is more than 10 nm / sec, a rough film will be formed and the transmittance, conductivity and adhesion will be reduced.

Next, the manufacturing apparatus of the present invention will be described with reference to the drawings.

FIG. 9 is a schematic explanatory view showing a typical example of the manufacturing apparatus of the present invention in (4) above, which is particularly suitable for continuously forming photovoltaic elements.

In the figure, a vacuum container 2100 (see FIG.
1), which is formed of a film forming container 2101 for forming an i-type semiconductor film having a substantially rectangular parallelepiped shape and a belt-shaped member 2150,
Second and third film forming spaces 2102, 2103, and 2104 are formed. Vacuum container 2100 and film forming container 2101
Are metallic and are electrically connected to each other.
The belt-shaped member 2150 on which the deposited film is formed is the vacuum container 210.
0 through the gas gate 2129 (FIG. 11) attached to the side wall on the left side of FIG.
Is introduced into the first, second, and third film-forming spaces 2102,
2103 and 2104 are penetrated respectively, and the vacuum container 210
0 is discharged to the outside of the vacuum container 2100 through a gas gate 2130 (FIG. 11) attached to the side wall on the right side of FIG. Film forming container 210
First, second, and third applicators 2105, 2106, and 2107 are provided in the strip-shaped member 2 in the first, second 103, and second 104.
It is attached so as to be lined up along the moving direction of 150. The applicators 2105, 2106, and 2107 are for introducing microwave energy into the film formation space, and the other ends of the waveguides 2111, 2112, and 2113 each having one end connected to a microwave power source (not shown) are respectively It is connected. Also, applicators 2105, 2106, 2
Each of the attachment portions of 107 to the film formation space is formed of a microwave permeable member 2 made of a material that transmits microwaves.
It is composed of 108, 2109 and 2110.

On the bottom surface of the film forming container 2101, the first, second and third gas introducing means 211 for releasing the source gas are provided.
7, 2118, and 2119 are attached respectively, and a large number of gas discharge holes for discharging the raw material gas are provided in the belt-shaped member 21.
It is arranged facing 50. These gas releasing means are connected to a gas supply facility (not shown). Further, exhaust punching boards 2120, 2121, and 2122 are attached to the opposite side of the applicator, that is, the side wall on the front side in the figure, to confine microwave energy in the film formation space and to connect to exhaust pipes 2125 and 2126 (FIG. 11). The exhaust throttle valves 2127 and 2128 are connected to an exhaust means (not shown) such as a vacuum pump.

The apparatus shown in FIG. 11 is an apparatus for continuously forming a functional deposited film, and includes vacuum containers 2301 and 2302 for feeding and winding the belt-shaped member 2150, and a first conductivity type layer for film formation. Vacuum container 2100n, vacuum container 2100 for forming i-type layer, and vacuum container 21 for forming second conductive type layer
00p is connected via a gas gate.

Vacuum container 2100 for depositing first conductivity type layer
n and the vacuum container 2100p for forming the second conductivity type layer has a single applicator with respect to the structure in the vacuum container 2100 for forming the i-type layer described above.
2100p each have a substantially rectangular parallelepiped container 21.
01n, 2101p and the strip-shaped member 2150
102n and 2102p are formed. Vacuum container 2 of FIG.
100n, 2100p and film forming containers 2101n, 21
01p is metallic and electrically connected.

Reference numeral 2303 denotes a feeding bobbin for the belt-shaped member 2150, and 2304 a winding bobbin for the belt-shaped member 2150. The belt-shaped member is conveyed in the direction of the arrow in the figure. Of course, this can also be reversed and conveyed. Further, the vacuum containers 2303 and 2304 may be provided with winding and feeding means of interleaving paper used for surface protection of the belt-shaped member 2150. As the material of the interleaving paper, polyimide, Teflon, glass wool and the like which are heat resistant resins are preferably used. Denoted at 2305 and 2306 are conveying rollers for adjusting tension and positioning the belt-shaped member. Two
Reference numerals 314 and 2315 are pressure gauges. 2127n, 2127, 2
128, 2128p, 2307, 2308 are throttle valves for adjusting conductance, 2125n, 212
Reference numerals 5, 2126, 2125p, 2310, and 2311 denote exhaust pipes, which are connected to exhaust pumps (not shown).

2129n, 2129, 2130, 212
9p is a gas gate, and 2131n, 2131, 21
Reference numerals 32 and 2131p are gate gas introduction pipes, which are connected to gas supply equipment (not shown). 2105n, 21
Reference numerals 05, 2106, 2107, and 2105p are applicators for introducing microwaves, and the microwave permeable members 2108n, 2108, 2109, and 211 are provided at their tip ends.
0, 2108p are attached to the waveguides 2111n, 2111, 2112, 2113, 2111, respectively.
It is connected to a microwave power source (not shown) through p. A large number of infrared lamp heaters 2124n, 2124, 2124 are provided on the opposite side of the film forming space with the strip-shaped member 2150 of each film forming container 2101n, 2101, 2101p interposed therebetween.
p and lamp houses 2123n, 2123, 2123p for efficiently concentrating the radiant heat from these infrared lamp heaters on the belt-shaped member 2150. Further, thermocouples 2134n, 2134, and 2134p for monitoring the temperature of the strip-shaped member 2150 are connected so as to be in contact with the strip-shaped member 2150, respectively.

The main part of the apparatus will be described in more detail below. (Porous conductive member) In the figure, 2135 and 2136 are porous conductive members. This conductive member is preferably a mesh made of a conductive metal.

As a material forming such a mesh, a member made of a metal, a semiconductor material or the like is preferably used from the viewpoint of durability against microwave plasma damage.
Specifically, Ni, stainless steel, Al, Cr, Mo, A
Examples include metals such as u, Nb, Ta, V, Ti, Pt, Pb, and Sn, and alloys thereof. Semiconductors include silicon, germanium, carbon, and
Other compound semiconductors, those composed of a simple substance or a composite of these, and the like can be given, and those whose conductive treatment is performed on the surface of the insulating member by a method such as plating, vapor deposition, sputtering, coating or the like can be given. be able to. Particularly, Al is preferable because it is easy to process and has high electric conductivity.
Also, stainless steel, Ni, etc. are preferable because they have high durability against plasma. The material is appropriately selected and used from these materials to form a desired deposited film.

[0180] Further, as the preferable shape of the mesh, various materials such as a knitted material of a linear material, a material of a plate material which is expanded by making fine cuts (expanded metal), a punching metal and the like are available. Although it can be used, it is preferable that the maximum diameter of the mesh opening is in the range of 1 to 10 mm from the viewpoint of securing the selectivity of the active species and the microwave blocking property, and the opening ratio is 10% or more. Is preferable from the viewpoint of increasing the utilization rate of the source gas and reducing the pressure unevenness inside the film forming chamber. Mesh 2133, 2133n, 2133
The distance between p and the strip-shaped member 2150 is appropriately determined according to various conditions such as the aperture ratio of the mesh, the internal pressure and the DC bias voltage, but normally the layer thickness and characteristics of the deposited film appear uneven within the range of 2 to 30 mm. And the characteristics are set to be optimum.

In order to keep the meshes 2135 and 2136 and the strip-shaped member 2150 at the same potential, it is preferable to electrically connect the mesh and the strip-shaped member 2150 with a conductive material in order to increase the effect of the mesh.

Such conductive materials include Ni, stainless steel, Al, Cu, Ag, Fe, Cr, Mo and A.
Examples include metals such as u, Nb, Ta, V, Ti, Pt, Pb, and Sn, and alloys thereof.
Further, it is also possible to use a simple substance or a complex of a semiconductor compound such as silicon, germanium or carbon. Furthermore,
The surface of the insulating member may be subjected to conductive treatment by a method such as plating, vapor deposition, sputtering or coating.

Further, the meshes 2135 and 2136 cover at least the surface of the belt-shaped member 2150 so that the belt-shaped member 2 is covered.
It is installed in the film formation space as shown in FIG. 9 so that it is installed over the width of 150 and does not come into contact with it. (Applicator) In the device of the present invention, the microwave applicator is arranged perpendicular to the moving direction of the belt-shaped member, which will be described more specifically. 240 in FIG.
Reference numerals 1 and 2402 denote microwave permeable members, which are fixed to the inner cylinder 2424 and the outer cylinder 2405 using a metal seal 2412 and a fixing ring 2406, and are vacuum-sealed. A cooling medium 2409 flows between the inner cylinder 2404 and the outer cylinder 2405, and an O-ring 2410 is sealed at one end to uniformly cool the entire microwave applicator 2400. Has become. As the cooling medium 2409, water, freon,
Oil, cooling air and the like are preferably used. A microwave matching disk 2403 is provided on the microwave transparent member 2401.
a, 2403b are fixed. A choke flange 2407 having a groove 2411 formed therein is connected to the outer cylinder 2405. Further, reference numerals 2413 and 2414 are cooling air introduction holes and / or discharge holes, which are used for cooling the inside of the applicator. (Strip-shaped member) The material of the strip-shaped member that is preferably used in the present invention is one that has little deformation and distortion at the temperature required for semiconductor film formation, has desired strength, and has conductivity. Preferably, specifically, specifically, a thin plate of metal such as stainless steel, aluminum and its alloys, iron and its alloys, copper and its alloys, and a composite thereof, and a metal thin film and / or SiO of different materials on their surfaces. _{2, Si 3 N 4, Al} 2 O 3, sputtering an insulating thin film such as AlN, a vapor deposition method, which was subjected to surface coating treatment by plating method or the like. In addition, a sheet of a heat-resistant resin such as polyimide, polyamide, polyethylene terephthalate, or epoxy, or a composite of glass fiber, carbon fiber, boron fiber, metal fiber, or the like, with a simple metal or an alloy, and a transparent conductive oxide. (T
CO) and the like, and those subjected to a conductive treatment by a method such as plating, vapor deposition, sputtering, coating and the like can be mentioned.

Further, the thickness of the belt-shaped member is possible in consideration of cost, storage space, etc. as long as it is within a range in which the curved shape formed during the transportation by the transportation means can be maintained. It is desirable to be as thin as possible. Specifically, the thickness is preferably 0.01 mm to 5 mm, more preferably 0.02 mm to 2 mm, and most preferably 0.05 mm to 1 mm. However, when a thin plate such as metal is used, the thickness is relatively small. Even if it is thin, desired strength can be easily obtained.

The width of the belt-like member is not particularly limited and is determined by the size of the semiconductor film forming means, the container thereof or the like.

The length of the belt-like member is not particularly limited, and may be such a length that it can be wound into a roll, and a longer one is further lengthened by welding or the like. May be

When the band-shaped member is electrically conductive such as metal, it may be used as an electrode for direct current extraction. When it is electrically insulating such as synthetic resin, it may be formed on the side where the semiconductor film is formed. Al, Ag, Pt, Au, Ni, Ti, on the surface
Mo, W, Fe, V, Cr, Cu, stainless steel, brass, nichrome, SnO ₂ , In ₂ O ₃ , ZnO, SnO
A so-called simple metal or alloy such as _{2-In 2} O ₃ (ITO) and a transparent conductive oxide (TCO) are subjected to surface treatment in advance by a method such as plating, vapor deposition and sputtering to form an electrode for current extraction. It is desirable to keep it.

When the band-shaped member is a non-translucent material such as a metal, a reflective conductive film for improving the reflectance of long wavelength light on the substrate surface is formed on the band-shaped member. Are preferred as mentioned above. Examples of materials that are preferably used as the material of the reflective conductive film include Ag, Al, and Cr.

On the substrate, a metal layer or the like is used as a reflective conductive film for the purpose of preventing mutual diffusion of constituent elements between the substrate material and the semiconductor film or a buffer layer for preventing short circuit. It is preferably provided on the side where the semiconductor film is formed. ZnO is preferably used as the material of the buffer layer.
Can be mentioned.

Further, since the band-shaped member is relatively transparent,
In the case of a solar cell having a layer structure in which light is incident from the side of the belt-shaped member, it is desirable to deposit and form a conductive thin film such as the transparent conductive oxide or a metal thin film in advance.

The surface property of the belt-shaped member may be a so-called smooth surface or a minute uneven surface. In the case of forming a minute uneven surface, it has a spherical shape, a conical shape, a pyramidal shape, and the maximum height (Rmax) is preferably 50.
When the thickness is set to nm to 500 nm, the light reflection on the surface becomes irregular reflection, and the optical path length of the reflected light on the surface increases. (Gas Gate) In the present invention, a vacuum container for feeding and winding the belt-shaped member and a vacuum container for forming a semiconductor film are separated and independent, and the belt-shaped member is continuously conveyed through them. A gas gate means is preferably used. It is necessary for the gas gate means to have the ability not to diffuse the atmospheres of the raw material gases for semiconductor film formation that are mutually used due to the pressure difference generated between the containers. Therefore, the basic concept can employ the gas gate means disclosed in US Pat. No. 4,438,723, but its capabilities need to be further improved. Specifically, it is necessary to withstand a pressure difference of up to about 10 ⁶ times, and as the exhaust pump, an oil diffusion pump, a turbo molecular pump, a mechanical booster pump, or the like having a large exhaust capacity is preferably used. In addition, the cross-sectional shape of the gas gate is a slit shape or a shape similar to this, and their dimensions are calculated and designed by using a general conductance calculation formula together with the overall length and the exhaust capacity of the exhaust pump used. . Further, it is preferable to use a gate gas together in order to enhance the separation ability. For example, a rare gas such as Ar, He, Ne, Kr, Xe, Rn or H.
₂ Diluting gas for forming a semiconductor film such as
The gate gas flow rate is appropriately determined depending on the conductance of the entire gas gate, the capacity of the exhaust pump used, and the like. For example, a pressure gradient as shown in FIG. 10 may be created. In FIG. 10, if a point at which the pressure is maximized is provided in the substantially central portion of the gas gate, the gate gas flows from the central portion of the gas gate to the vacuum container side on both sides to minimize mutual gas diffusion between the containers on both sides. Can be suppressed to In practice, the optimum conditions are determined by measuring the amount of gas that diffuses using a mass spectrometer and analyzing the composition of the semiconductor film.

The photovoltaic element preferably manufactured by the device of the present invention will be described below.

16 to 18 are schematic explanatory views showing a typical constitutional example of a photovoltaic element suitably manufactured by the device of the present invention.

In the example shown in FIG. 16, the belt-shaped member 2501 (2
150), lower electrode 2502, first conductivity type layer 250
3, an i-type layer 2504, a second conductivity type layer 2505, an upper electrode 2506, and a collector electrode 2507.

In the example shown in FIG. 17, the band gap and /
Alternatively, it is a so-called tandem photovoltaic element configured by laminating two photovoltaic elements 2511 and 2512 using two types of semiconductor layers having different layer thicknesses as i-type layers, and a belt-shaped member 2501 (2150), Lower electrode 2502, first conductivity type layer 2503, i-type layer 2504, second conductivity type layer 25
05, the first conductivity type layer 2503, the i-type layer 2504, the second
Conductivity type layer 2505, upper electrode 2506, current collecting electrode 25
It is composed of 07.

In the example shown in FIG. 18, the band gap and /
Alternatively, it is a so-called triple photovoltaic element constituted by stacking three photovoltaic elements 2511, 2512, 2513 using three types of semiconductor layers having different layer thicknesses as i-type layers, and a strip-shaped member 2501 ( 2150), lower electrode 250
2, first conductivity type layer 2503, i-type layer 2504, second conductivity type layer 2505, first conductivity type layer 2503, i-type layer 2
504, second conductivity type layer 2505, first conductivity type layer 25
03, i-type layer 2504, second conductivity type layer 2505, upper electrode 2506, and collector electrode 2507.

The constitution of these photovoltaic elements will be described below, but the explanation is one aspect of the present invention and does not limit the present invention. <Structure of Photovoltaic Element> Strip-Shaped Member The strip-shaped member 2501 (215 used in the present invention
0) is preferably made of a flexible material, and may be conductive or electrically insulating. Further, although they may be translucent or non-translucent, the band-shaped member 25
When light is incident from the 01 (2150) side, it is of course necessary that the light is transmissive.

Specific examples thereof include the band-shaped member 2150 used in the present invention.
By using 150, it is possible to reduce the weight of the photovoltaic element to be formed, improve its strength, and reduce the transportation space. Electrodes In the present photovoltaic element, appropriate electrodes are selected and used depending on the configuration of the element. For those electrodes,
Examples thereof include a lower electrode, an upper electrode (transparent electrode), and a collector electrode. (However, the upper electrode referred to here means the one provided on the light incident side, and the lower electrode means the one provided so as to face the upper electrode with the semiconductor layer in between.) The electrodes will be described in detail below. (I) Lower Electrode As the lower electrode 2502 used in the present invention,
Since the surface of the belt-shaped member 2501 irradiated with light for generating photovoltaic power differs depending on whether or not the material of the belt-shaped member 2501 is translucent (for example, when the belt-shaped member 2501 is a non-translucent material such as metal) The transparent electrode 250 as shown in FIG.
Light for photovoltaic generation is emitted from the 6 side. ) The place where it is installed is different.

Specifically, in the case of the layer structure as shown in FIGS. 16, 17 and 18, it is provided between the strip member 2501 and the first conductivity type layer 2503. However, the strip 250
When 1 is conductive, the strip-shaped member can also serve as the lower electrode. However, if the sheet member 2501 is conductive but has a high sheet resistance, the lower part may be used as a low resistance electrode for current extraction or for the purpose of effectively utilizing incident light by increasing the reflectance on the substrate surface. Electrode 2502
May be installed.

As the electrode material, Ag, Au, Pt, N
Examples thereof include metals such as i, Cr, Cu, Al, Ti, Zn, Mo, and W, or alloys thereof. Thin films of these metals are formed by vacuum evaporation, electron beam evaporation, sputtering, or the like.
In addition, the formed metal thin film must be considered so as not to become a resistance component with respect to the output of the photovoltaic element, and the sheet resistance value is preferably 50 Ω or less, more preferably 10 Ω.
Ω or less is desirable.

Lower electrode 2502 and first conductivity type layer 250
Although not shown in the figure, a buffer layer for preventing short-circuiting and diffusion of ZnO or the like may be provided between the layer 3 and 3. As the effect of the buffer layer, not only the metal element forming the lower electrode 2502 is prevented from diffusing into the first conductivity type layer 2503, but also a slight resistance value is provided to sandwich the semiconductor layer. Lower electrode 2502 and transparent electrode 250
6 and 6 can prevent short-circuiting caused by defects such as pinholes, and multiple interference due to thin films can be generated to confine incident light in the photovoltaic element. (II) Upper Electrode (Transparent Electrode) The transparent electrode 2506 used in the present invention has a light transmittance of 85% or more in order to efficiently absorb light from the sun, a white fluorescent lamp or the like into the semiconductor layer. Furthermore, it is desirable that the sheet resistance value is 100Ω or less so that it does not electrically become a resistance component with respect to the output of the photovoltaic element. Materials having such characteristics include SnO ₂ , In ₂ O ₃ , ZnO, CdO, and Cd ₂ SnO.
₄ , a metal oxide such as ITO (In ₂ O ₃ + SnO ₂ ), a metal thin film formed by forming a metal such as Au, Al, or Cu in an extremely thin and semitransparent state. Since the transparent electrode is laminated on the second conductivity type layer 2505 in FIGS. 16 to 18, it is necessary to select those having good adhesion to each other. A resistance heating vapor deposition method, an electronic boom heating vapor deposition method, a sputtering method, a spraying method, or the like can be used as a film forming method for these, and it is appropriately selected as desired. (III) Collector Electrode The collector electrode 2507 used in the present invention is a transparent electrode 2 for the purpose of reducing the surface resistance value of the transparent electrode 2506.
506 is provided. The electrode material is Ag, Cr,
Ni, Al, Ag, Au, Ti, Pt, Cu, Mo, W
And the like, or alloys thereof. These thin films can be laminated and used. Further, the shape and area of the semiconductor layer are appropriately designed so as to secure a sufficient amount of light incident on the semiconductor layer.

For example, it is desirable that its shape is uniformly spread over the light receiving surface of the photovoltaic element, and its area is preferably 15% or less, more preferably 10% or less with respect to the light receiving area.

The sheet resistance value is preferably 5
It is desirable to be 0Ω or less, and more preferably 10Ω or less. 1st and 2nd conductivity type layer As a material used for the 1st and 2nd conductivity type layers in the photovoltaic device of the present invention, 1 atom of Group IV of the periodic table is used.
Non-single crystal semiconductors consisting of one or more species are suitable. Furthermore, the conductive layer on the light irradiation side is most preferably a microcrystallized semiconductor. The grain size of the fine crystals is preferably 3 nm to 20 n.
m, and optimally 3 nm to 10 nm.

When the conductivity type of the first or second conductivity type layer is n-type, an atom of Group VA of the periodic table is suitable as the additive contained in the first or second conductivity type layer. There is. Among them, phosphorus (P), nitrogen (N), arsenic (As) and antimony (Sb) are most suitable.

When the conductivity type of the first or second conductivity type layer is p-type, as an additive contained in the first or second conductivity type layer, a Group IIIA element of the periodic table is suitable. There is. Among them, boron (B), aluminum (Al), and gallium (Ga) are most suitable.

The layer thickness of the first and second conductivity types is preferably 1 nm to 50 nm, and most preferably 3 nm to 10 nm.

Further, in order to further reduce light absorption in the conductive layer on the light irradiation side, it is preferable to use a semiconductor layer having a bandgap larger than that of the semiconductor forming the i-type layer. For example, when the i-type layer is amorphous silicon, it is optimal to use non-single crystal silicon carbide for the conductive type layer on the light irradiation side. i-Type Layer As a semiconductor material used for the i-type layer in the photovoltaic device of the present invention, Si, Ge, C, SiC, GeC, SiS composed of one or more atoms of Group IV of the periodic table is used.
Semiconductors such as n, GeSn and SnC may be mentioned. As III-V group compound semiconductors, GaAs, Ga
P, GaSb, InP, InAs, II-VI group compound semiconductors such as ZnSe, ZnS, ZnTe, CdS, CdS
e, CdTe, I-III-VI group compound semiconductor, C
uAlS ₂ , CuAlSe ₂ , CuAlTe ₂ , CuI
nS ₂ , CuInSe ₂ , CuInTe ₂ , CuGaA
s ₂ , CuGaSe ₂ , CuGaTe, AgInS
e ₂ , AgInTe ₂ , and II-IV-V group compound semiconductors include ZnSiP ₂ , ZnGeAs ₂ , CdSiA.
s ₂ , CdSnP ₂ , Cu ₂ O as an oxide semiconductor,
TiO ₂ , In ₂ O ₃ , SnO ₂ , ZnO, CdO, B
Examples thereof include i ₂ O ₃ and CdSnO ₄ .

Furthermore, in the present invention, the layer thickness of the i-type layer is
It is an important parameter that influences the characteristics of the photovoltaic device of the present invention. The preferable layer thickness of the i-type layer is 100 nm to 100 nm.
0 nm and the optimum layer thickness is 200 nm to 600 nm. It is desirable that these layer thicknesses are designed within the above range in consideration of the absorption coefficient of the i-type layer and the interface layer and the spectrum of the light source.

In the present invention, the following can be mentioned as the source gases suitable for the microwave glow discharge decomposition method for forming the first and second conductivity type layers, the i-type layer and the interface layer.

As the raw material gas for supplying Si used in the present invention, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Si ₄ H ₁₀ or other gas-state or gasifiable silicon hydrides (silanes) are mentioned as being effectively used. Particularly, it is easy to handle the layer formation work, and the Si supply efficiency is good. In this respect, SiH ₄ and Si ₂ H ₆ are preferable.

Many halogen compounds can be cited as effective source gases for supplying halogen atoms in the present invention. Preferable examples include halogen compounds in the gas state or gasifiable such as halogen gas, halides, interhalogen compounds, and silane derivatives substituted with halogen.

Further, a silicon compound containing a halogen atom, which has a silicon atom and a halogen atom as constituent elements and is in a gas state or can be gasified, can be mentioned as an effective one in the present invention.

Halogen compounds which can be preferably used in the present invention include, specifically, halogen gas of fluorine, chlorine, bromine and iodine, BrF, ClF, ClF ₃ and BrF.
₅ , interhalogen compounds such as BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr can be mentioned.

As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom,
Specifically, for example, SiF ₄ , Si ₂ F ₆ , SiCl ₄ ,
Silicon halides such as SiBr ₄ can be mentioned as preferable ones.

In the present invention, for supplying halogen atoms
The halogen compounds or halogens described above as the source gas
Silicon compounds containing nitrogen atoms are effectively used
In addition, HF, HCl, HBr, HI
Hydrogen halide such as SiH ₃F, SiH₂F₂, Si
HF₃, SiH₂I₂, SiH₂Cl₂, SiHC
l ₃, SiH₂Br₂, SiHBr₃Halogen substitution
Water in gas state or gasifiable such as silicon hydride
Halides containing elementary atoms as one of the constituent elements are also effective sources.
It can be mentioned as a charge gas.

The halide containing these hydrogen atoms is
At the same time as the supply of halogen atoms into the layer formed during layer formation, hydrogen atoms that are extremely effective in controlling electrical or photoelectric properties are also supplied. Used as raw material gas.

In the present invention, as the raw material gas for supplying hydrogen atoms, in addition to the above, H ₂ , SiH ₄ , or Si
Examples thereof include silicon hydrides such as ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ .

In the present invention, for supplying germanium atoms
As gas, GeH_Four, Ge₂H ₆, Ge₃H₈, G
e_FourH_Ten, Ge_FiveH₁₂, Ge₆H₁₄, Ge₇H₁₆, Ge
₈H ₁₈, Ge₉H₂₀Such as germanium hydride and GeH
F₃, GeH₂F₂, GeH ₃F, GeHCl₃, Ge
H₂Cl₂, GeH₃Cl, GeHBr₃, GeH₂B
r₂, GeH₃Br, GeHI₃, GeH₂I₂, Ge
H₃Hydrogen atoms such as hydrogenated germanium halides such as I
, Which is one of the constituent elements, GeF _Four, Ge
Cl_Four, GeBr_Four, GeI_Four, GeF₂, GeC
l₂, GeBr₂, GeI₂Halogenated germanium such as
Examples thereof include germanium compounds such as aluminum.

Examples of the carbon atom-containing compound as a raw material for supplying carbon atoms include saturated hydrocarbons having 1 to 4 carbon atoms,
Examples thereof include ethylene-based hydrogen having 2 to 4 carbon atoms and acetylene-based hydrocarbon having 2 to 3 carbon atoms.

Specifically, as the saturated hydrocarbon,
(CH_Four), Ethane (C₂H₆), Propane (C₃H
₈), N-butane (n-C_FourH_Ten), Pentane (C_FiveH
₁₂), Ethylene-based hydrocarbons include ethylene (C₂H
_Four), Propylene (C₃H₆), Butene-1 (C
_FourH₈), Butene-2 (C_FourH₈), Isobutylene (C
_FourH ₈), Penten (C_FiveH_Ten), Acetylated carbonized water
As an element, acetylene (C ₂H₂), Methyl acetyl
(C₃H_Four), Butin (C_FourH₆) And so on
it can.

Examples of the source gas containing Si, C and H as constituent atoms include alkyl silicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₄ ) ₄ .

When glow discharge is used to form a layer containing a group III atom or a group V atom, the starting material used as a source gas for forming the layer is a starting material for the silicon atom described above. A starting material for supplying a Group III atom or a Group V atom is added to an appropriately selected substance. As the starting material for supplying such a group III atom or a group V atom, a substance in a gas state containing a group III atom or a group V atom or a gasifiable substance can be gasified. , Any of them may be used.

Starting for Supplying Group III Atoms in the Present Invention
Specifically, what is effectively used as a substance is
B for supplying boron atoms₂H₆, B_FourH_Ten, B
_FiveH₉, B _FiveH₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄Etc.
Boron hydride, BF₃, BCl₃, BBr₃Halogen etc.
Boron bromide and the like can be mentioned, but in addition to this, AlCl₃,
GaCl₃, InCl₃, TlCl₃And so on
You can do it.

Starting Material for Supplying Group V Atoms in the Present Invention
In terms of quality, what is effectively used is
PH for supplying phosphorus atoms₃, P₂H_FourHydrogenation of
Phosphorus, PH_FourI, PF₃, PF_Five, PCl₃, PCl_Five,
PBr₃, PBr_Five, PI₃, AsH₃, AsF₃, A
sCl₃, AsBr₃, AsF_Five, SbH₃, Sb
F₃, SbF_Five, SbCl₃, SbCl_Five, BiH₃,
BiCl₃, BiBr₃, N ₂, NH₃, H₂NN
H₂, HN₃, NH_FourN₃, F₃N, F_FourN₂Etc.
You can

In the present invention, the oxygen atom supply gas is oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (N
O), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N
₂ O), nitrogen trioxide (N ₂ O ₃ ), trinitrogen oxide (N
₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitric oxide (N
O ₃ ), silicon atom (Si), oxygen atom (O) and hydrogen atom (H) as constituent atoms, for example, disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ SiO 2).
Lower siloxanes such as SiH ₂ OSiH ₃ ) and the like can be mentioned.

In the present invention, the nitrogen atom supply gas is nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium (NH ₄ N ₃ ). And nitrogen compounds such as nitrogenous substances and azides. In addition to this, nitrogen trifluoride (F ₃
N) and nitrogen halide compounds such as nitrogen tetrafluoride (F ₄ N ₂ ) can be mentioned.

In the present invention, a II-VI group compound semiconductor is formed.
A compound containing a group II atom of the periodic table, which is used to
As the compound, specifically, Zn (CH₃)₂, Zn (C
₂H _Five)₂, Zn (OCH₃)₂, Zn (OC₂H_Five)
₂, Cd (CH₃)₂, Cd (C₂H_Five)₂, Cd (C
H₃)₂, Cd (C₂H_Five)₂, Cd (C₃H₇)₂,
Cd (C_FourH₉), Hg (CH₃)₂, Hg (C
₂H_Five)₂, Hg (C₆H_Five)₂, Hg [(C = (C₆
H_Five)]₂Etc. can be mentioned. Periodic table group VI
Specific examples of the compound containing atoms include NO and N₂O,
CO₂, CO, H₂S, SCl₂, S₂Cl₂, SOC
l₂, SeH₂, SeCl₂, Se₂Br₂, Se (C
H₃)₂, Se (C₂H_Five)₂, TeH, Te (C
H₃)₂, Te (C ₂H_Five)₂Can be mentioned
It Of course, these raw materials are not only one type, but two or more types.
It can also be used as a mixture.

Examples of the valence electron control agent used for controlling the valence electrons of the II-VI group compound semiconductor formed in the present invention include compounds containing an atom of group I, III, IV or V of the periodic table. Can be listed as valid. Specifically, as those containing a group I atom, LiCHLi
(Sec-CHg) SLiN etc. can be mentioned as a suitable thing.

As the compound containing a group III atom, B is
X₃, B₂H₆, B_FourH_Ten, B_FiveH ₉, B_FiveH₁₁, B₆
H_Ten, B (CH₃)₃, B (C₂H_Five)₃, B₆H₁₂,
AlX₃, Al (CH₃)₂Cl, Al (CH₃)₃,
Al (OCH₃)₃, Al (CH₃) Cl₂, Al (C
₂H_Five)₃, Al (OC₂H_Five)₃, Al (CH₃) ₃
Cl₃, Al (i-C_FourH₉)₃, Al (i-C
₃H₇)₃, Al (C₃H₇)₃, Al (OC_FourH₉)
₃, GaX₃Ga (OCH₃)₃, Ga (OC₂H_Five)
₃, Ga (OC₃H₇), Ga (OC_FourH₉)₃, Ga
(CH₃)₃, Ga₂H₆, GaH (C₂H_Five)₂, G
a (OC₂H_Five), (C₂H_Five)₂, In (C
H₃)₃, In (C_FourH₇)₃, In (C_FourH₉)₃,
NH as a compound containing a group V atom₃, HN₃, N₂H
_FiveN₃, N₂H_Four, NH_FourN₃, PX₃, P (OC
H₃)₃, P (OC₂H_Five)₃, P (C₃H₇)₃, P
(OC_FourH₉)₃, P (CH₃)₃, P (C
₂H_Five)₃, P (C_FourH₉)₃, P (OCH₃)₃, P
(OC₂H_Five)₃, P (OC₂H_Five)₃, P (OC₃H
₇)₃, P (OC_FourH₉) ₃, P (SCN)₃, P₂H
_Four, PH₃, AsH, AsH₃, As (OCH₃) ₃,
As (OC₂H_Five)₃, As (OC₃H₇)₃, As
(OC_FourH₉)₃, As (CH₃)₃, As (C
₆H_Five)₃, SbX₃, Sb (OCH₃)₃, Sb (O
C₂H_Five)₃, Sb (OC₃H₇)₃, Sb (OC_FourH
₉)₃, Sb (CH₃)₃, Sb (C₃H₇)₃, Sb
(C_FourH₉)₃Etc. can be mentioned. [However, X is
Halogen atom, specifically selected from F, Cl, Br, I
Represents at least one ] Of course, these raw materials
It is possible to use not only one type of quality but also a mixture of two or more types.
Wear.

As the valence electron control agent used for controlling the valence electrons of the III-V group compound semiconductor formed in the present invention, compounds containing an atom of Group II, IV or VI of the Periodic Table are effective. Can be listed as

Specifically, as the compound containing a group II atom, Zn (CH ₃ ) ₂ , Zn (C ₂ H ₅ ) ₂ , Zn (O
CH ₃ ) ₂ , Zn (C ₂ H ₅ ) ₂ , Cd (CH ₃ ) ₂ ,
Cd (C ₂ H ₅ ) ₂ , Cd (C ₃ H ₇ ) ₂ , Cd (C _{4
H 9) 2, Hg (CH} 3) 2, Hg (C 2 H 5) 2, H
_{g (C 6 H 5) 2} , Hg [C≡C (C ₆ H _5)] can be mentioned ₂ such as valid. Compounds containing a group VI atom include NO, N ₂ O, CO ₂ , CO and H.
₂ S, SCl ₂ , S ₂ Cl ₂ , SOCl ₂ , SeH ₂ ,
SeCl ₂ , Se ₂ Br ₂ , Se (CH ₃ ) ₂ , Se
(C ₂ H ₅ ) ₂ , TeH, Te (CH ₃ ) ₂ , Te (C
₂ H ₅ ) _{2 and the} like can be mentioned. Of course, these raw materials may be used alone or in combination of two or more. Furthermore, examples of the compound containing a group IV atom include the compounds described above.

In the present invention, the raw material compounds described above are H
It may be introduced by mixing with a rare gas such as e, Ne, Ar, Kr, Xe, or Rn, and a diluent gas such as H ₂ , HF, or HCl.

As a material forming the gas introducing means arranged in the present invention, a material which is not damaged in microwave plasma is preferably used. In particular,
Heat-resistant metals such as stainless steel, nickel, titanium, niobium, tantalum, tungsten, vanadium, molybdenum, and those obtained by thermal spraying these on ceramics such as alumina, silicon nitride and quartz, and alumina,
Examples include simple ceramics such as silicon nitride and quartz, and composite ceramics.

By forming a photovoltaic element by using the above-mentioned apparatus for continuously forming a photovoltaic element of the present invention, the aforementioned problems can be solved and the aforementioned requirements can be satisfied. It is possible to form a photovoltaic element having high quality, excellent uniformity, and few defects on a continuously moving strip-shaped member.

Next, the above-mentioned (5) production apparatus of the present invention will be described with reference to the drawings.

FIG. 19 is a schematic explanatory view showing an example of the device of the present invention of (5), which is suitable for continuously forming a photovoltaic element.

In the figure, the vacuum container 3100 (see FIG.
1), which is formed of a substantially rectangular parallelepiped film-forming container 3101 for film-forming a semiconductor and a band-shaped member 3150,
Second and third film forming spaces 3102, 3103, and 3104 are formed. Vacuum container 3100 and film forming container 3101
Are metallic and are electrically connected to each other.
The belt-shaped member 3150 on which the deposited film is formed is a vacuum container 310.
0 through the gas gate 3129 (FIG. 21) attached to the side wall on the left side of FIG.
Is introduced into the first, second, and third film-forming spaces 3102,
3103 and 3104 are penetrated respectively, and vacuum container 310
0 on the right side in the drawing, that is, through the gas gate 3130 (FIG. 21) attached to the side wall on the carry-out side, the product is carried out to the outside of the vacuum container 3100. Film formation space 310
First, second, and third applicators 3105, 3106, and 3107 are provided in the band-shaped member 3 in 2, 3103, and 3104.
It is attached so as to be lined up along the moving direction of 150. The respective applicators 3105, 3106, 3107 are for introducing microwave energy into the film forming space, and the other ends of the waveguides 3111, 3112, 3113, which are connected to one end of a microwave power source (not shown), respectively, It is connected. Also, applicators 3105, 3106, 3
The attachment of 107 to the film formation space is made up of microwave transmitting members 3108, 3109, and 3110 made of a material that transmits microwaves.

Further, on the bottom surface of the film forming container 3101, first, second and third gas introducing means 311 for releasing the raw material gas are provided.
7, 3118 and 3119 are attached respectively, and a large number of gas discharge holes for discharging the raw material gas are provided in the belt-shaped member 315.
It is arranged facing 0. These gas releasing means are connected to a gas supply facility (not shown). Further, exhaust punching boards 3120, 3121, 3122 are attached to the opposite side of the applicator, that is, the side wall on the front side in the figure, to confine microwave energy in the film formation space and to connect to exhaust pipes 3125, 3126 (FIG. 21). The exhaust throttle valves 3127 and 3128 are connected to an exhaust means (not shown) such as a vacuum pump.

The apparatus shown in FIG. 21 is an apparatus for continuously forming a functional deposited film, and includes vacuum containers 3301 and 3302 for feeding and winding the belt-shaped member 3150, and a vacuum for forming the first conductivity type layer. Container 3100n, vacuum container 3100 for forming i-type layer, vacuum container 31 for forming second conductive type layer
00p is connected via a gas gate.

Vacuum container 3100 for depositing first conductivity type layer
n and the vacuum container 3100p for forming the second conductivity type layer has a single applicator with respect to the structure in the vacuum container 3100 for forming the i-type layer described above.
Each of the 3100p has a substantially rectangular parallelepiped container 31.
01n, 3101p and the band-shaped member 3150
102n and 3102p are formed. Vacuum container 3 of FIG.
100n and 3100p and film forming containers 3101n and 31
01p is metallic and electrically connected.

Reference numeral 3303 is a bobbin for sending out the belt-shaped member 3150, and 3304 is a bobbin for winding the belt-shaped member 3150, and the belt-shaped member is conveyed in the direction of the arrow in the figure. Of course, this can also be reversed and conveyed. Further, the vacuum containers 3303 and 3304 may be provided with winding and feeding means of interleaving paper used for surface protection of the belt-shaped member 3150. As the material of the interleaving paper, polyimide, Teflon, glass wool and the like which are heat resistant resins are preferably used. Reference numerals 3305 and 3306 are conveying rollers that also adjust the tension and position the belt-shaped member.
3314 and 3315 are pressure gauges. 3127n, 3127,
3128, 3128p, 3307, and 3308 are conductance adjusting slot valves 3125n and 312.
5, 3126, 3125p, 3310, 3311 are exhaust pipes, each connected to an exhaust pump (not shown).

3129n, 3129, 3130, 312
9p is a gas gate, and 3131n, 3131, 31
Reference numerals 23 and 3131p are gate gas introduction pipes, each of which is connected to a gas supply facility (not shown). 3105n, 31
Reference numerals 05, 3106, 3107, and 3105p are applicators for introducing microwaves, and microwave-transmissive members 3108n, 3108, 3109, and 311 are provided at their tips.
0, 3108p are attached to each of the waveguides 3111n, 3111, 3112, 3113, 3101.
It is connected to a microwave power source (not shown) through p.

Each film forming container 3101n, 3101 and 310
A large number of infrared lamp heaters 3124n and 312 are provided on the opposite side of the film forming space with the 1p band member 3150 interposed therebetween.
4, 3124p and lamp houses 3123n, 3123, 3123p for efficiently concentrating the radiant heat from the infrared lamp heaters on the belt-shaped member 3150 are provided. Also, thermocouples 3134n, 3134, 3134p for monitoring the temperature of the strip member 3150.
Are connected so as to contact the strip-shaped member 3150.

The main part of the apparatus will be described in more detail below. (Porous Conductive Member) In the figure, 3133 is a porous conductive member. A mesh made of a conductive metal is preferable as the porous conductive member.

As a material for forming such a mesh, a member made of metal, semiconductor material or the like is preferably used from the viewpoint of durability against microwave plasma damage.
Specifically, Ni, stainless steel, Al, Cr, Mo, A
Examples include metals such as u, Nb, Ta, V, Ti, Pt, Pb, and Sn, and alloys thereof. Examples of the semiconductor include silicon, germanium, carbon, and other compound semiconductors, and simple substances or composites thereof. Further, plating on the surface of the insulating member, steaming, spatter, Examples thereof include those that have been subjected to a conductive treatment by a method such as coating. Especially, Al is preferable because it is easy to process and has high electric conductivity. Also, stainless steel, Ni, etc. are preferable because they have high durability against plasma. The material is appropriately selected and used from these materials to form a desired deposited film.

As a preferable shape of the mesh, various materials such as a knitted material of a linear material, a material of a plate material which is expanded by making fine cuts (expanded metal), a punching metal and the like are used. Although it is obtained, it is preferable that the maximum diameter of the mesh opening is in the range of 1 to 10 mm from the viewpoint of securing the selectivity of the active species and the microwave blocking property, and the opening ratio is 10% or more. This is preferable from the viewpoint of increasing the gas utilization rate and reducing the pressure unevenness inside the film forming chamber. The distance between the meshes 3133, 3133n, 3133p and the belt-shaped member 3150 is appropriately determined according to various conditions such as the aperture ratio of the mesh, the internal pressure and the DC bias voltage, but usually the layer thickness of the deposited film is within the range of 2 to 30 mm. The characteristic is set so that the characteristic does not appear uneven and the characteristic is optimal.

Further, the meshes 3133, 3133n, 31
In order to keep the 33p and the strip-shaped member 3150 at the same potential, the mesh and the strip-shaped member 3150 are electrically connected by a conductive member.

Also, the meshes 3133, 3133n, 31
33p is installed so as to cover at least the surface of the belt-shaped member 3150, and is installed in the film forming space as shown in FIGS. (Applicator) In the present invention, the microwave applicator is arranged perpendicular to the moving direction of the strip-shaped member,
A more specific description will be given. In FIG. 22, 3401, 3
Reference numeral 402 denotes a microwave transparent member, which is a metal seal 3
412 and the fixing ring 3406, the inner cylinder 34
24, fixed to the outer cylinder 3405 and vacuum-sealed. A cooling medium 3409 flows between the inner cylinder 3404 and the outer cylinder 3405, and one end is sealed by an O-ring 3410 to uniformly cool the entire microwave applicator 3400. Has become. As the cooling medium 3409, water, freon, oil, cooling air or the like is preferably used. The microwave permeable member 3410 includes a microwave matching disk 3403a,
3403b is fixed. Groove 34 on outer cylinder 3405
Eleven machined choke flanges 3407 are connected. Further, 3413 and 3414 are cooling air introduction holes,
And / or discharge holes, which are used to cool the interior of the applicator. (Strip-shaped member) The material of the strip-shaped member that is preferably used in the present invention is one that has little deformation and distortion at the temperature required for semiconductor film formation, has desired strength, and has conductivity. Preferably, specifically, specifically, a thin plate of metal such as stainless steel, aluminum and its alloys, iron and its alloys, copper and its alloys, and a composite thereof, and a metal thin film and / or SiO of different materials on their surfaces. _2. An insulating thin film such as ₂ , Si ₃ N ₄ , Al ₂ O ₃ or AlN that has been surface-coated by a sputtering method, a vapor deposition method, a plating method or the like. In addition, a sheet of a heat-resistant resin such as polyimide, polyamide, polyethylene terephthalate, or epoxy, or a composite of glass fiber, carbon fiber, boron fiber, metal fiber, or the like, with a simple metal or an alloy, and a transparent conductive oxide. (T
CO) or the like which has been subjected to a conductive treatment by a method such as plating, vapor deposition, sputtering or coating.

The thickness of the belt-shaped member is possible in consideration of cost, storage space, etc. as long as it is within a range in which the curved shape formed during the transfer by the transfer means can be maintained. It is desirable to be as thin as possible. Specifically, it is preferably 0.01 mm without 5 mm, more preferably 0.02 mm to 2 mm, and most preferably 0.05 mm to 1 mm. However, when using a thin plate such as metal, the thickness is relatively small. Even if it is thin, desired strength can be easily obtained.

The width of the belt-like member is not particularly limited and is determined by the size of the semiconductor film forming means, its container or the like.

The length of the belt-like member is not particularly limited, and may be such a length that it can be wound into a roll, and a longer one is further lengthened by welding or the like. May be

When the band-shaped member is electrically conductive such as metal, it may be used as an electrode for direct current extraction. When it is electrically insulating such as synthetic resin, it may be formed on the side where the semiconductor film is formed. Al, Ag, Pt, Au, Ni, Ti, on the surface
Mo, W, Fe, V, Cr, Cu, stainless steel, brass, nichrome, SnO ₂ , In ₂ O ₃ , ZnO, SnO
_{2, -In 2 O 3 (ITO} ) so-called metal alone or an alloy, and a transparent conductive oxide such as a (TCO) plating, vapor deposition,
It is desirable to perform surface treatment in advance by a method such as sputtering to form an electrode for current extraction.

When the band-shaped member is a non-translucent material such as metal, a reflective conductive film for improving the reflectance of long wavelength light on the substrate surface is formed on the band-shaped member. Are preferred as mentioned above. Examples of materials that are preferably used as the material of the reflective conductive film include Ag, Al, and Cr.

A metal layer or the like is used as a reflective conductive film on the substrate for the purpose of preventing mutual diffusion of constituent elements between the substrate material and the semiconductor film or a buffer layer for preventing short circuit. It is preferably provided on the side where the semiconductor film is formed. ZnO is preferably used as the material of the buffer layer.
Can be mentioned.

Further, the belt-shaped member is relatively transparent,
In the case of a solar cell having a layer structure in which light is incident from the side of the belt-shaped member, it is desirable to previously deposit and form a conductive thin film such as the transparent conductive oxide or the metal thin film.

The surface property of the belt-shaped member may be a so-called smooth surface or a minute uneven surface. In the case of forming a minute uneven surface, it has a spherical shape, a conical shape, a pyramidal shape, and the maximum height (Rmax) is preferably 50.
When the thickness is set to nm to 500 nm, the light reflection on the surface becomes irregular reflection, and the optical path length of the reflected light on the surface increases. (Gas Gate) In the present invention, a vacuum container for feeding and winding the belt-shaped member and a vacuum container for forming a semiconductor film are separated and independent, and the belt-shaped member is continuously conveyed through them. A gas gate means is preferably used. It is necessary for the gas gate means to have the ability not to diffuse the atmospheres of the raw material gases for semiconductor film formation which are mutually used due to the pressure generated between the respective containers. Therefore, the basic concept can employ the gas gate means disclosed in US Pat. No. 4,438,723, but its capabilities need to be further improved. Specifically, it is necessary to withstand a pressure difference of up to about 10 ⁶ times, and as the exhaust pump, an oil diffusion pump, a turbo molecular pump, a mechanical booster pump, or the like having a large exhaust capacity is preferably used. In addition, the cross-sectional shape of the gas gate is a slit shape or a shape similar to this, and their dimensions are calculated and designed by using a general conductance calculation formula together with the overall length and the exhaust capacity of the exhaust pump used. . Further, it is preferable to use a gate gas in combination in order to enhance the separation ability. For example, a rare gas such as Ar, He, Ne, Kr, Xe, or Rn or a diluting gas for forming a semiconductor film such as H ₂ can be used. The gate gas flow rate is appropriately determined according to the conductance of the entire gas gate and the capacity of the exhaust pump used.For example, if a point at which the pressure is maximized is provided at approximately the center of the gas gate, the gate gas will flow from the center of the gas gate to both sides. The gas flows to the vacuum container side, and mutual gas diffusion between the containers on both sides can be minimized. In practice, the optimum conditions are determined by measuring the amount of gas that diffuses using a mass spectrometer and analyzing the composition of the semiconductor film.

Next, a photovoltaic element which is suitably manufactured by this deposited film forming apparatus will be described.

26 to 28 are schematic explanatory views showing a typical constitutional example of a photovoltaic element suitably manufactured by the device of the present invention.

In the example shown in FIG. 26, the belt-shaped member 3501 (3
150), lower electrode 3502, first conductivity type layer 350
3, an i-type layer 3504, a second conductivity type layer 3505, an upper electrode 3506, and a collector electrode 3507.

In the example shown in FIG. 27, the band gap and /
Alternatively, it is a so-called tandem photovoltaic element configured by laminating two photovoltaic elements 3511 and 3512 using two types of semiconductor layers having different layer thicknesses as i-type layers, and a belt-shaped member 3510 (3150), Lower electrode 3502, first conductivity type layer 3503, i-type layer 3504, second conductivity type layer 35
05, the first conductivity type layer 3503, the i-type layer 3504, the second
Conductivity type layer 3505, upper electrode 3506, collector electrode 35
It is composed of 07.

In the example shown in FIG. 28, the band gap and /
Alternatively, it is a so-called triple photovoltaic element constituted by stacking three photovoltaic elements 3511, 3512, 3513 using three types of semiconductor layers having different layer thicknesses as i-type layers, and a strip-shaped member 3510 ( 3150), lower electrode 350
2, first conductivity type layer 3503, i-type layer 3504, second conductivity type layer 3505, first conductivity type layer 3503, i-type layer 3
504, second conductivity type layer 3505, first conductivity type layer 35
03, i-type layer 3504, second conductivity type layer 3505, upper electrode 3506, and collector electrode 3507.

Hereinafter, preferable structures of these photovoltaic elements will be described. However, it goes without saying that the following description is one aspect of the present invention, and the present invention is not limited to this. <Structure of Photovoltaic Element> Band- Shaped Member Band-shaped member 3501 (315) used in the present invention.
0) is preferably made of a flexible material, and may be conductive or electrically insulating. Further, although they may be translucent or non-translucent, the band-shaped member 35
When light is incident from the 01 (3150) side,
Of course, it needs to be transparent.

Specific examples thereof include the belt-shaped member 3150 used in the present invention.
By using 150, it is possible to reduce the weight of the photovoltaic element to be formed, improve its strength, and reduce the transportation space. Electrodes In the present photovoltaic element, appropriate electrodes are selected and used depending on the configuration of the element. For those electrodes,
Examples thereof include a lower electrode, an upper electrode (transparent electrode), and a collector electrode. (However, the upper electrode referred to here means the one provided on the light incident side, and the lower electrode means the one provided so as to face the upper electrode with the semiconductor layer in between.) The electrodes will be described in detail below. (I) Lower Electrode As the lower electrode 3502 used in the present invention,
The surface of the belt-shaped member 3501 irradiated with the light for generating photovoltaic power differs depending on whether or not the material of the belt-shaped member 3501 is translucent (for example, when the belt-shaped member 3501 is a non-translucent material such as metal). As shown in FIG. 26, the transparent electrode 350
Light for photovoltaic generation is emitted from the 6 side. ) The place where it is installed is different.

Specifically, in the case of the layer structure as shown in FIGS. 26, 27 and 28, it is provided between the belt-shaped member 3501 and the first conductivity type layer 3503. However, the belt-shaped member 350
When 1 is conductive, the strip-shaped member can also serve as the lower electrode. However, even if the strip-shaped member 3501 is conductive, if the sheet resistance value is high, the lower part is used as a low resistance electrode for current extraction or for the purpose of effectively utilizing incident light by increasing the reflectance on the substrate surface. Electrode 3502
May be installed.

As electrode materials, Ag, Au, Pt, N
Examples thereof include metals such as i, Cr, Cu, Al, Ti, Zn, Mo and W or alloys thereof, and thin films of these metals are formed by vacuum vapor deposition, electron beam vapor deposition, sputtering or the like. In addition, the formed metal thin film must be considered so as not to become a resistance component to the output of the photovoltaic element, and the sheet resistance value is preferably 50Ω or less, more preferably 10Ω or less. .

Lower electrode 3502 and first conductivity type layer 350
Although not shown in the figure, a buffer layer for preventing short-circuiting and diffusion of ZnO or the like may be provided between the layer 3 and 3. As an effect of the buffer layer, not only is the metal element forming the lower electrode 3502 prevented from diffusing into the first conductivity type layer 3503, but the buffer layer is provided with a slight resistance value so as to sandwich the semiconductor layer. Lower electrode 3502 and transparent electrode 350
6 and 6 can prevent short-circuiting caused by defects such as pinholes, and multiple interference due to thin films can be generated to confine incident light in the photovoltaic element. (II) Upper Electrode (Transparent Electrode) The transparent electrode 3506 used in the present invention has a light transmittance of 85% or more in order to efficiently absorb light from the sun or a white fluorescent lamp into the semiconductor layer. It is desirable that the sheet resistance value is 100Ω or less so that it does not electrically become a resistance component to the output of the photovoltaic element. Materials having such characteristics include SnO ₂ , In ₂ O ₃ , ZnO, CdO, and Cd ₂ SnO.
₄ , a metal oxide such as ITO (In ₂ O ₃ + SnO ₂ ), a metal thin film formed by forming a metal such as Au, Al, or Cu in an extremely thin and semitransparent state. Since the transparent electrode is laminated on the second conductivity type layer 3505 in FIGS. 26 to 28, it is necessary to select those having good adhesion to each other. A resistance heating vapor deposition method, an electron beam heating vapor deposition method, a sputtering method, a spraying method, or the like can be used as a film forming method for these, and it is appropriately selected as desired. (III) Collector Electrode The collector electrode 3507 used in the present invention is a transparent electrode 3 for the purpose of reducing the surface resistance value of the transparent electrode 3506.
506 is provided. Ag, Cr, N as electrode materials
Examples thereof include thin films of metals such as i, Al, Ag, Au, Ti, Pt, Cu, Mo and W or alloys thereof.
These thin films can be laminated and used.

Further, the shape and area of the semiconductor layer are appropriately designed so as to secure a sufficient amount of light incident on the semiconductor layer. For example, its shape is uniformly spread over the light receiving surface of the photovoltaic element, and its area is preferably 15% of the light receiving area.
It is desirable that the amount is below, more preferably 10% or below.

Also, the sheet resistance value is preferably 5
It is desirable to be 0Ω or less, and more preferably 10Ω or less. 1st and 2nd conductivity type layer As a material used for the 1st and 2nd conductivity type layers in the photovoltaic device of the present invention, 1 atom of Group IV of the periodic table is used.
Non-single crystal semiconductors consisting of one or more species are suitable. Furthermore, the conductive layer on the light irradiation side is most preferably a microcrystallized semiconductor. The grain size of the fine crystals is preferably 3 nm to 20 n.
m, and optimally 3 nm to 10 nm.

When the conductivity type of the first or second conductivity type layer is n-type, an atom of Group VA of the periodic table is suitable as an additive contained in the first or second conductivity type layer. There is. Among them, phosphorus (P), nitrogen (N), arsenic (As) and antimony (Sb) are most suitable.

When the conductivity type of the first or second conductivity type layer is p-type, as an additive contained in the first or second conductivity type layer, an atom of Group IIIA of the periodic table is suitable. There is. Among them, boron (B), aluminum (Al), and gallium (Ga) are most suitable.

The layer thickness of the first and second conductivity types is preferably 1 nm to 50 nm, optimally 3 nm to 10 nm.

Further, in order to further reduce light absorption in the conductive layer on the light irradiation side, it is preferable to use a semiconductor layer having a band gap larger than that of the semiconductor forming the i-type layer. For example, when the i-type layer is amorphous silicon, it is optimal to use non-single crystal silicon carbide for the conductive type layer on the light irradiation side. i-Type Layer As a semiconductor material used for the i-type layer in the photovoltaic device of the present invention, Si, Ge, C, SiC GeC, SiS, which is composed of one or more atoms of Group IV of the periodic table,
Semiconductors such as n, GeSn and SnC may be mentioned. As III-V group compound semiconductors, GaAs, Ga
P, GaSb, InP, InAs, II-VI group compound semiconductors such as ZnSe, ZnS, ZnTe, CdS, CdS
e, CdTe, I-III-VI group compound semiconductor, C
uAlS ₂ , CuAlSe ₂ CuAlTe ₂ , CuIn
S ₂ , CuInSe ₂ , CuInTe ₂ , CuGA
s ₂ , CuGaSe ₂ , CuGaTe, AgInS
e ₂ , AgInTe ₂ , and II-IV-V group compound semiconductors include ZnSiP ₂ , ZnGeAs ₂ , CdSiA.
s ₂ , CdSnP ₂ , Cu ₂ O as an oxide semiconductor,
TiO ₂ , In ₂ O ₂ , SnO ₂ , ZnO, CdO, B
Examples thereof include i ₂ O ₃ and CdSnO ₄ .

Furthermore, in the present invention, the layer thickness of the i-type layer is
It is an important parameter that influences the characteristics of the photovoltaic device of the present invention. The preferable layer thickness of the i-type layer is 100 nm to 100 nm.
0 nm and the optimum layer thickness is 200 nm to 600 nm. It is desirable that these layer thicknesses are designed within the above range in consideration of the absorption coefficient of the i-type layer and the interface layer and the spectrum of the light source.

In the present invention, source gases suitable for the microwave glow discharge decomposition method for forming the first and second conductivity type layers, the i-type layer and the interface layer are as follows.

The source gas for supplying Si used in the present invention includes SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Si ₄ H ₁₀ or other gas-state or gasifiable silicon hydrides (silanes) are mentioned as being effectively used. Particularly, it is easy to handle the layer formation work, and the Si supply efficiency is good. In this respect, SiH ₄ and Si ₂ H ₆ are preferable.

As the raw material gas for supplying halogen atoms used in the present invention, many halogen compounds can be cited, for example, halogen gas, halides, interhalogen compounds, silane derivatives substituted with halogen, etc. Preference is given to halogenated compounds or those which can be gasified.

Furthermore, a silicon compound containing a halogen atom, which has a silicon atom and a halogen atom as constituent elements and is in a gas state or which can be gasified, can be mentioned as an effective one in the present invention.

Halogen compounds that can be preferably used in the present invention include, specifically, halogen gas of fluorine, chlorine, bromine and iodine, BrF, ClF, ClF ₃ and BrF.
_{5, BrF 3, IF 3,} IF 7, ICl, may be mentioned interhalogen compounds such as IBr.

As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom,
Specifically, for example, SiF ₄ , Si ₂ F ₆ , SiCl ₄ ,
Silicon halides such as SiBr ₄ can be mentioned as preferable ones.

In the present invention, for supplying halogen atoms
The halogen compounds or halogens described above as the source gas
Silicon compounds containing nitrogen atoms are effectively used
In addition to these, HF, HCl, HBr, HI
Hydrogen halide such as SiH ₃F, SiH₂F₂, Si
HF₃, SiH₂I₂, SiH₂Cl₂, SiHC
l ₃, SiH₂Br₂, SiHBr₃Halogen substitution
Water in gas state or gasifiable such as silicon hydride
Halides containing elementary atoms as one of the constituent elements are also effective sources.
It can be mentioned as a charge gas.

Halides containing a hydrogen atom such as these are
At the same time as the supply of halogen atoms into the layer formed during layer formation, hydrogen atoms that are extremely effective in controlling electrical or photoelectric properties are also supplied. Used as raw material gas.

In the present invention, as the raw material gas for supplying hydrogen atoms, in addition to the above, H ₂ or SiH ₄ , Si
There may be mentioned silicon hydrides such as ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ .

In the present invention, for supplying germanium atoms
As gas, GeH_Four, Ge₂H ₆, Ge₃H₈, G
e_FourH_Ten, Ge_FiveH₁₂, Ge₆H₁₄, Ge₇H₁₆, Ge
₈H ₁₈, Ge₉H₂₀Such as germanium hydride and GeH
F₃, GeH₂F₂, GeH ₃F, GeHCl, GeH
₂Cl₂, GeH₃Cl, GeHBr₃, GeH₂Br
₂, GeH₃Br, GeHI₃, GeH₂I₂, GeH
₃Hydrogen atom such as hydrogenated germanium halide such as I
GeF as one of the constituents, GeF_Four,GeCl
_Four, GeBr_Four, GeI_Four, GeF₂, GeCl₂, G
eBr₂, GeI₂Such as germanium halide
Mention may be made of rumanium compounds.

Examples of the carbon atom-containing compound as a raw material for supplying carbon atoms include saturated hydrocarbons having 1 to 4 carbon atoms,
Examples thereof include ethylene hydrocarbons having 2 to 4 carbon atoms and acetylene hydrocarbons having 2 to 3 carbon atoms.

Specifically, as the saturated hydrocarbon,
(CH_Four), Ethane (C₂H₆), Propane (C₃H
₈), N-butane (n-C_FourH_Ten), Pentane (C_FiveH
₁₂), Ethylene-based hydrocarbons include ethylene (C₂H
_Four), Propylene (C₃H₆), Butene-1 (C
_FourH₈), Butene-2 (C_FourH₈), Isobutylene (C
_FourH ₈), Penten (C_FiveH_Ten), Acetylene-based carbonized water
As an element, acetylene (C ₂H₂), Methyl acetyl
(C₃H_Four), Butin (C_FourH₆) And so on
it can.

Examples of the raw material gas containing Si, C and H as constituent atoms include alkylsilicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₄ ) ₄ .

When glow discharge is used to form a layer containing a group III atom or a group V atom, the starting material used as a source gas for forming the layer is a starting material for the silicon atom described above. A starting material for supplying a Group III atom or a Group V atom is added to an appropriately selected substance. The starting material for supplying the group III atom or the group V atom may be a gas state substance containing the group III atom or the group V atom as a constituent atom or a gasified substance capable of being gasified. Any of them may be used.

Starting for Supplying Group III Atoms in the Present Invention
Specifically, what is effectively used as a substance is
B for supplying boron atoms₂H₆, B_FourH_Ten, B
_FiveH₉, B _FiveH₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄Etc.
Boron hydride, BF₃, BCl₃, BBR₃Halogen etc.
Boron bromide and the like can be mentioned, but in addition to this, AlCl₃，
GaCl₃, InCl₃, TlCl₃And so on
You can do it.

Starting Material for Supplying Group V Atoms in the Present Invention
In terms of quality, what is effectively used is
PH for supplying phosphorus atoms₃, P₂H_FourSuch as phosphorus hydride,
PH _FourI, PF₃, PF_Five, PCl₃, PCl_Five, PB
r₃, PBr_Five, PI₃, AsH₃, AsF₃, AsC
l₃, AsBr₃, AsF_Five, SbH₃, SbF₃, S
bF_Five, SbCl₃, SbCl_Five, BiH₃, BiCl
₃, BiBr₃, N₂, NH₃, H₂NNH₂, H
N₃, NH_FourN₃, F₃N, F_FourN₂And so on
it can.

In the present invention, the oxygen atom supply gas is oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (N
O), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N)
₂ O), nitrogen trioxide (N ₂ O ₃ ), trinitrogen trioxide (N
₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitric oxide (N
O ₃ ), silicon atom (Si), oxygen atom (O) and hydrogen atom (H) as constituent atoms, for example, disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ SiO 2).
Lower siloxanes such as SiH ₂ OSiH ₃ ) and the like can be mentioned.

In the present invention, a gas for supplying nitrogen atoms is used.
The nitrogen (N₂), Ammonia (NH₃), Hydraji
(H₂NNH₂), Hydrogen azide (HN₃), Ammoni
Umm (NH_FourN₃) Etc. gaseous or gasifiable nitrogen
Nitrogen compounds such as oxygen, nitrogen compounds and azides can be mentioned.
it can. In addition to the supply of nitrogen atoms, halogen
Nitrogen trifluoride (F
₃N), nitrogen tetrafluoride (F_FourN ₂) Etc.
We can mention compound.

In the present invention, a II-VI group compound semiconductor is formed.
A compound containing a group II atom of the periodic table, which is used to
As the compound, specifically, Zn (CH₃)₂, Zn (C
₂H _Five)₂, Zn (OCH₃)₂, Zn (OC₂H_Five)
₂, Cd (CH₃)₂, Cd (C₂H_Five)₂, Cd (C
H₃)₂, Cd (C₂H_Five)₂, Cd (C₃H₇)₂,
Cd (C_FourH₉)₂, Hg (CH₃)₂, Hg (C₂H
_Five)₂, Hg (C₆H _Five)₂, Hg [(C = (C
₆H_Five)]₂Etc. can be mentioned. Periodic table VI
Specific examples of the compound containing a group atom include NO and N
₂O, CO₂, CO, H₂S, SCl₂, S₂Cl₂,
SOCl₂, SeH₂, SeCl₂, Se₂Br₂, S
e (CH₃)₂, Se (C₂H_Five)₂, TeH, Te
(CH₃)₂, Te (C₂H_Five)₂Etc.
Wear. Of course, these raw materials are not only one type, but two or more types.
It can also be used as a mixture.

The valence electron control agent used for controlling the valence electrons of the II-VI group compound semiconductor formed in the present invention includes compounds containing an atom of group I, III, IV or V of the periodic table. Can be listed as valid. Specifically, as those containing a group I atom, LiCHLi
(Sec-CHg), SLiN, etc. can be mentioned as a suitable thing.

Compounds containing a group III atom include B
X₃, B₂H₆, B_FourH_Ten, B_FiveH ₉, B_FiveH₁₁, B₆
H_Ten, B (CH₃)₃, B (C₂H_Five)₃, B₆H₁₂,
AlX₃, Al (CH₃)₂Cl, Al (CH₃)₃,
Al (OCH₃)₃, Al (CH₃) Cl₂, Al (C
₂H_Five)₃, Al (OC₂H_Five)₃, Al (CH₃) ₃
Cl₂, Al (i-C_FourH₉)₃, Al (i-C
₃H₇)₃, Al (C₃H₇)₃, Al (OC_FourH₉)
₃, GaX₃Ga (OCH₃)₃, Ga (OC₂H_Five)
₃, Ga (OC₃H₇), Ga (OC_FourH₉)₃, Ga
(CH₃)₃, Ga₂H₆, GaH (C₂H_Five)₂, G
a (OC₂H_Five), (C₂H_Five)₂, In (C
H₃)₃, In (C_FourH₇)₃, In (C_FourH₉)₃,
NH as a compound containing a group V atom₃, HN₃, N₂H
_FiveN₃, N₂H_Four, NH_FourN₃, PX₃, P (OC
H₃)₃, P (OC₂H_Five)₃, P (C₃H₇)₃, P
(OC_FourH₉)₃, P (CH₃)₃, P (C
₂H_Five)₃, P (C_FourH₉)₃, P (OCH₃)₃, P
(OC₂H_Five)₃, P (OC₂H_Five)₃, P (OC₃H
₇)₃, P (OC_FourH₉) ₃, P (SCN)₃, P₂H
_Four, PH₃, AsH, AsH₃, As (OCH₃) ₃,
As (OC₂H_Five)₃, As (OC₃H₇)₃, As
(OC_FourH₉)₃, As (CH₃)₃, As (C
₆H_Five)₃, SbX₃, Sb (OCH₃)₃, Sb (O
C₂H_Five)₃, Sb (OC₃H₇)₃, Sb (OC_FourH
₉)₃, Sb (CH₃)₃, Sb (C₃H₇)₃, Sb
(C_FourH₉)₃Etc. can be mentioned. [However, X is
Halogen atom, specifically selected from F, Cl, Br, I
Represents at least one ] Of course, these raw materials
It is possible to use not only one type of quality but also a mixture of two or more types.
Wear.

As the valence electron controlling agent used for controlling the valence electrons of the III-V group compound semiconductor formed in the present invention, compounds containing an atom of group II, IV or VI of the periodic table are effective. Can be listed as

Specifically, as the compound containing a group II atom, Zn (CH ₃ ) ₂ , Zn (C ₂ H ₅ ) ₂ , Zn (O
CH ₃ ) ₂ , Zn (C ₂ H ₅ ) ₂ , Cd (CH ₃ ) ₂ ,
Cd (C ₂ H ₅ ) ₂ , Cd (C ₃ H ₇ ) ₂ , Cd (C _{4
H 9) 2, Hg (CH} 3) 2, Hg (C 2 H 5) 2, H
_{g (C 6 H 5) 2} , Hg [C≡C (C ₆ H _5)] can be mentioned ₂ such as valid. Compounds containing a group VI atom include NO, N ₂ O, CO ₂ , CO and H.
₂ S, SCl ₂ , S ₂ Cl ₂ , SOCl ₂ , SeH ₂ ,
SeCl ₂ , Se ₂ Br ₂ , Se (CH ₃ ) ₂ , Se
(C ₂ H ₅ ) ₂ , TeH, Te (CH ₃ ) ₂ , Te (C
₂ H ₅ ) _{2 and the} like can be mentioned. Of course, these raw materials may be used alone or in combination of two or more. Furthermore, examples of the compound containing a group IV atom include the compounds described above.

In the present invention, the raw material compounds described above are H
It may be introduced by mixing with a rare gas such as e, Ne, Ar, Kr, Xe, or Rn, and a diluent gas such as H ₂ , HF, or HCl.

As a material forming the gas introducing means arranged in the present invention, a material which is not damaged in microwave plasma is preferably used. In particular,
Heat-resistant metals such as stainless steel, nickel, titanium, niobium, tantalum, tungsten, vanadium, molybdenum, and those obtained by performing thermal spraying treatment on ceramics such as alumina, silicon nitride and quartz, and alumina, silicon nitride and quartz. Examples include ceramics alone and composites.

By forming a photovoltaic element by using the above-mentioned apparatus for continuously producing the photovoltaic element of the present invention, the above-mentioned various problems are solved and the above-mentioned various elements are satisfied. It is possible to form a photovoltaic element having high quality, excellent uniformity, and few defects on the moving strip-shaped member.

[0300]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 An a-Si: H photovoltaic element having the structure shown in FIG. 2A was manufactured as described below.

In this embodiment, as the substrate 201, a stainless steel (SUS304) plate having a 10 cm square and a thickness of 0.1 mm whose surface is mirror-polished is used, and a light reflection layer 202 is formed thereon.
Was formed into a thickness of 0.3 μm by a known vacuum deposition method.

On this, a zinc oxide layer as the reflection increasing layer 203 was formed as follows using the DC sputtering apparatus shown in FIG.

A substrate on which silver has been vapor-deposited on the heater 303 in advance.
After attaching the plate 302, the inside of the deposition chamber 301 is not shown.
Pump down. The degree of vacuum in the deposition chamber 301
10 ^-FiveConfirmed that it became below Torr with vacuum gauge 312
After that, the heater 303 is energized to change the temperature of the substrate 302 to 4
It was heated and held at 00 ° C.

In this example, the target 304 used was zinc oxide powder sintered. Argon gas as a sputter gas is supplied through the gas introduction valve 314 while being adjusted by the mass flow controller 316 so that the flow rate is 25 sccm, and after the flow rate is stabilized, a DC voltage is supplied from the sputter power source 306 to the target 304 and a sputter current. Was set and applied so as to be 0.8 A. The internal pressure during sputtering was kept at 7 mTorr.

As described above, the formation of the zinc oxide layer was started, and after the layer thickness of the zinc oxide layer reached 1.0 μm, power was supplied from the sputtering power source, sputtering gas was supplied, and the heater 303 was supplied. After de-energizing and cooling the substrate, the deposition chamber 30
The inside of 1 was leaked to the atmosphere, and the substrate on which the zinc oxide layer was formed was taken out.

Subsequently, an n-type layer 204, an i-type layer 205 and a p-type layer 206 each made of a-Si: H are formed thereon.
It was formed using the microwave plasma CVD apparatus shown in FIG.

Gas cylinders 1071 to 1076 in FIG.
The raw material gas for forming each semiconductor layer is sealed in. 1071 is SiH ₄ (purity 99.999
%) Gas cylinder, 1072 is GeH ₄ (purity 99.99)
9%) gas cylinder, 1073 is H ₂ (purity 99.999)
9%) gas cylinder, 1074 abbreviated as PH ₃ gas diluted to 10% with H ₂ gas (hereinafter "PH ₃ / H ₂ gas") cylinder, 1075 BF ₃ diluted to 10% with H ₂ gas Gas (hereinafter abbreviated as “BF ₃ / H ₂ gas”) cylinders and 1076 are Ar gas cylinders. When the gas cylinders 1071 to 1076 are attached, SiH ₄ gas is supplied from the gas cylinder 1071 and G is supplied from the gas cylinder 1072.
eH ₄ gas, H ₃ gas from gas cylinder 1073, PH ₃ / H ₂ gas from gas cylinder 1074, gas cylinder 107
BF ₃ / H ₂ gas from No. 5 and Ar gas from the gas cylinder 1076 are introduced into the gas pipes of the valves 1031 to 1036 by opening the valves 1051 to 1056, and the respective pipes are adjusted by the pressure regulators 1061 to 1066. The gas pressure inside was adjusted to ² kg / cm ² .

Valves 1031 to 1036 and deposition chamber 1
It is confirmed that the leak valve 109 of 01 is closed, and that the valves 1041 to 1046 are opened, the conductance (butterfly type) valve 107 is fully opened, and a vacuum pump (not shown) is used. The deposition chamber 101 and the gas pipe are exhausted. When the reading of the vacuum gauge 106 is preferably 1 × 10 ⁻⁴ Torr or less, more preferably 1 × 10 ⁻⁵ Torr or less, the valve 104 is reached.
1 to 1046 are closed.

Next, the valves 1031 to 1036 are gradually opened to let each gas flow through the mass flow controller 10.
21 to 1026.

After the preparation for forming the semiconductor layer is completed as described above, the heater 105 is energized to remove the substrate 104 from the substrate 3 for 3 hours.
It was heated and kept at 80 ° C.

Next, the introduction valves 1041, 1043, 1
Open 044 gradually to prevent dust from scattering
H ₄ gas, H ₂ gas, and PH ₃ / H ₂ gas were caused to flow into the deposition chamber 101 through the auxiliary valve 108 and the gas introduction pipe 103. At this time, the SiH ₄ gas flow rate is 10 sccm,
The mass flow controllers 1021, 1023, and 1024 were adjusted so that the H ₂ gas flow rate was 100 sccm and the PH ₃ / H ₂ gas flow rate was 1.0 sccm.

It is preferable to gradually introduce the gas into the deposition chamber 101 and to perform the operation with the shutter 115 closed to prevent dust from adhering to the substrate surface.

When the gas flow rate became stable, the deposition chamber 10
The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that the pressure in 1 became 5 mTorr. Next, the power of the microwave power source (not shown) is set to 400 W, and the waveguide, the waveguide section 110, and the conductor window 1 (not shown) are set.
Microwave power was introduced into the deposition chamber 101 via 02 to cause microwave glow discharge. DC and rf bias voltages can be applied after the plasma has stabilized,
60 by bias power supply 111 having sufficient power supply capacity
An rf bias of 0 W and a DC bias voltage of +100 V was applied to the bias rod 112. The shutter 115 was opened when the parameters of the plasma and the bias current became constant, and the formation of the n-type layer on the substrate 104 was started. The mesh 113 is removed from the vicinity of the substrate 104.

When the layer thickness of the n-type layer 204 reaches about 20 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the output of the bias power source 111 is cut off, and the introduction valves 1041, 1043, 1044 are closed. Deposition chamber 1
The introduction of gas into the inside of No. 01 was stopped, and the formation of the n-type layer 204 was completed.

Next, the i-type layer 205 was formed as follows. First, the mesh 113 was moved and installed so as to cover the substrate 104. Subsequently, the deposition chamber 101 and the piping were once evacuated to a high vacuum of 10 ⁻⁵ Torr or less, and then the substrate 104 was heated and held at 370 ° C. by the heater 105, and the introduction valve 1041 was opened to supplement 150 sccm of SiH ₄ gas. Valve 108 and gas introduction pipe 1
It was introduced into the deposition chamber 101 through 03. Deposition chamber 101
The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that the internal pressure became 5 mTorr.
Next, the power of the microwave power source (not shown) is set to 450 W, and the waveguide, the waveguide section 110, and the dielectric window 102 (not shown) are set.
Microwave power was introduced into the deposition chamber 101 through the to generate microwave glow discharge. After plasma is stabilized, rf bias 750 W by the bias power supply 111
Was supplied to the bias rod 112. Further, a DC bias voltage +60 V from the mesh bias power source 114 was applied to the mesh 113. When the parameters such as the state of plasma and the bias current become constant, the shutter 11
5 was opened to start forming an i-type layer on the n-type layer. In addition,
It has been previously confirmed by the above-described method that the microwave energy value is in a microwave energy rate-determining state.

When the layer thickness of the i-type layer 205 reaches about 270 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the outputs of the bias power sources 111 and 114 are cut off, and the gas is introduced into the deposition chamber 101. Stop the i-type layer 2
The formation of 05 is finished. The deposition rate of the i-type layer is about 10 nm
/ Sec.

Next, the p-type layer 206 was formed as follows. First, the mesh 113 was moved and removed from the vicinity of the substrate 104. Subsequently, the substrate 104 is heated and held at 350 ° C. by the heater 105, and Si is heated.
Auxiliary valve 1 for H ₄ gas, H ₂ gas, and BF ₃ / H ₂ gas
It was introduced into the deposition chamber 101 through 08 and the gas introduction pipe 103. At this time, the SiH ₄ gas flow rate is 10 sccm, H
The mass flow controllers were adjusted so that the ₂ gas flow rate was 100 sccm and the BF ₃ / H ₂ gas flow rate was 1 sccm. The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that the pressure in the deposition chamber 101 was 5 mTorr. Next, the power of a microwave power source (not shown) is set to 400 W, microwave energy is introduced into the deposition chamber 101 through a waveguide, a waveguide section 110, and a dielectric window 102 (not shown) to perform microwave glow discharge. Caused. After the plasma was stabilized, the bias power supply 111 applied a DC bias voltage of +100 V to the bias rod 112. When the parameters such as the state of plasma and the bias current become constant, the shutter 11
5 was opened to start forming a p-type layer on the i-type layer.

When the layer thickness of the p-type layer 206 becomes about 10 nm, the shutter 115 is closed to stop the introduction of microwave power, turn off the output of the bias power source 111, and stop the introduction of gas into the deposition chamber 101. The formation of the p-type layer 206 is completed.

Next, after argon purge inside the deposition chamber 101 and the gas introduction pipe and the like is repeated three times, the gas introduction valve is closed, and when the substrate temperature drops to an appropriate value, the leak valve 109 is opened to deposit. The inside of the chamber 101 was leaked to the atmosphere, and the substrate 104 having the n-type layer, the i-type layer and the p-type layer formed on the surface thereof was taken out from the deposition chamber 101.

In the next step, ITO (In ₂ O ₃ + SnO ₂ ) was formed as a transparent electrode 207 on the p-type layer 206 of the a-Si: H photovoltaic element formed as described above.
It was formed as follows.

The apparatus shown in FIG. 4 was used as a reactive vacuum vapor deposition apparatus.

The substrate 402 on which the p-type layer has been formed is attached to the heater 403, and as the evaporation source 404, metal tin and metal indium (both having a purity of 99.999%) are used.
%: 50% After replenishing the mixture, a vacuum pump (not shown) is operated to fully open the conductance valve and the deposition chamber 401.
The inside was evacuated.

After the degree of vacuum in the deposition chamber became 10 ⁻⁵ Torr or less, the heater 403 was energized to maintain the temperature of the substrate 402 at 150 ° C.

Subsequently, oxygen gas (O ₂ ) was adjusted by the mass flow controller 411 so that the flow rate was 8 sccm, and was introduced into the deposition chamber 401 via the gas introduction valve 410. After the flow rate becomes constant, the conductance valve 409 is adjusted while watching the vacuum gauge 408 to adjust the deposition chamber 4
The degree of vacuum inside 01 was set to 3 × 10 ⁻⁴ Torr.

After the internal pressure became constant, the heater 405 for the vapor deposition source was energized to start heating the vapor deposition source 404.

When the temperature of the vapor deposition source rises and metal tin and indium begin to vaporize, the vaporized metal atoms react with oxygen gas in the deposition chamber, and the pressure in the deposition chamber slightly decreases. When the fluctuation value of the pressure became 3 × 10 ⁻⁵ Torr, the shutter 407 was opened and the formation of the ITO film on the substrate 402 was started.

While watching the value of the deposition rate by the film thickness monitor 413, the output of the AC power source 406 is adjusted so that the deposition rate becomes substantially constant at about 0.07 nm / sec.
A TO film was formed.

When the film thickness reaches 75 nm, the shutter 407 is closed, the heaters 403 and 405 are deenergized, the gas introduction valve 410 is closed, and the transparent electrode 20 is closed.
The formation of 7 is completed. When the substrate temperature decreased, the leak valve 412 was opened, the inside of the deposition chamber 401 was leaked, and the substrate 402 on which the transparent electrode 207 was formed was taken out.

Next, as the collecting electrode 208, Al having a layer thickness of 2 μm was vapor-deposited by a resistance heating vacuum vapor deposition method using a mask.
Then, an a-Si: H photovoltaic element (No. Ex-1) was obtained.

As a comparative example, it is the same as the photovoltaic element (No. real-1) under other conditions except that a semiconductor layer was deposited without applying a DC bias voltage to the mesh 113 in the i-type layer forming step. Then, an a-Si: H photovoltaic element (No. ratio -1) was produced.

Pseudo sunlight was produced by using a solar simulator (Yamashita Denso Co., Ltd., YSS-150) for the photovoltaic elements (No. Ex-1) and (No. Ratio-1) produced as described above. (AM-1.5, 100 mW / cm ² )
The current-voltage characteristics were measured under irradiation to determine the photoelectric conversion efficiency. As a result, the photovoltaic element of the comparative example (No.
When the value of 1) is set to 1, the photoelectric conversion efficiency of the photovoltaic element (No. Ex-1) formed using the deposited film forming method of the present invention is dramatically improved to 1.25. I understood it. That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, the ionic species that contribute to the improvement of the film characteristics are effectively selected, In addition, the uniformity and characteristics of the deposited film were improved by applying an appropriate acceleration by the electric field between the mesh and the substrate, and as a result, the photoelectric conversion efficiency of the photovoltaic device was dramatically improved. It is considered to be a thing.

Further, 25 small-area photovoltaic elements having the same shape were formed on one substrate, and the variation in photoelectric conversion efficiency of the photovoltaic elements was examined. As a result, it was found that the variation width in the photovoltaic element formed by using the deposited film forming method of the present invention was 0.43 when the variation width in the photovoltaic element of the comparative example was 1. .
That is, i that most affects the characteristics of the photovoltaic element
In the photovoltaic element using the deposited film forming method of the present invention in forming the mold layer, the uniformity of the deposited film is improved by uniformizing the plasma, and as a result, the uniformity of the photovoltaic element is improved. It is considered that the dramatic improvement has been achieved.

Further, the following durability test was conducted in order to investigate the reliability of these photovoltaic elements under actual use conditions.

Photovoltaic device (No. Ex-1) and (N
o. Each of the ratio-1) is polyvinylidene fluoride (VDF)
It is vacuum-sealed with a protective film consisting of 1 and it is used under actual use conditions (installed outdoors, connecting a fixed resistance of 50 ohms to both electrodes).
After leaving for a year, the photoelectric conversion efficiency is evaluated again, and the deterioration rate due to light irradiation, temperature difference, wind and rain, etc. (The value of the photoelectric conversion efficiency damaged by the deterioration is divided by the initial value of the photoelectric conversion efficiency. ) Was investigated. As a result, the photovoltaic element (No.
The actual deterioration rate of -1) was dramatically improved to 0.71 when the deterioration rate of the photovoltaic element (No. ratio -1) was set to 1. That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, the activity having energy that contributes to the structural relaxation of the film being deposited is With the presence of species, it is possible to effectively reduce the effects of unnecessary electrons and ions that cause harmful damage to the deposited film, which reduces the disturbance of the network in the deposited film, and as a result, It is considered that the reliability of the electromotive force element has been dramatically improved.

Example 2 An a-SiGe: H photovoltaic element having the structure shown in FIG. 2A was produced as described below.

In this embodiment, as the substrate 201, a stainless steel (SUS304) plate having a 10 cm square and a thickness of 0.1 mm whose surface is mirror-polished is used, and the light reflecting layer 202 is formed thereon.
Was formed into a thickness of 0.5 μm by a known vacuum deposition method. At that time, the substrate temperature was set at 350 ° C. to deposit silver to form an uneven structure with a period of about 1 μm and a height difference of about 0.3 μm on the surface of the silver layer.

On this, a zinc oxide layer was formed as the reflection increasing layer 203 in the same manner as in Example 1.

Next, the n-type layer 204 was formed in the same manner as in Example 1, and subsequently, an a-SiGe: H film was formed as the i-type layer 205 as follows.

First, the deposition chamber 101 and the inside of the pipe are temporarily set to 10
After evacuating to a high vacuum of ^-5 Torr or less, the substrate 104 is heated and held at 380 ° C. by the heater 105, the introduction valves 1041 and 1042 are opened, and the SiH ₄ gas 11
0 sccm, GeH ₄ gas 40 sccm auxiliary valve 1
It was introduced into the deposition chamber 101 through 08 and the gas introduction pipe 103. Conductance valve 10 while watching vacuum gauge 106 so that the pressure in deposition chamber 101 becomes 5 mTorr.
The opening of 7 was adjusted. Next, the power of the microwave power source (not shown) is set to 400 W, and the waveguide and the waveguide 11 (not shown) are set.
0 and the dielectric window 102, microwave power was introduced into the deposition chamber 101 to cause microwave glow discharge. After the plasma was stabilized, rf energy of 600 W from the bias power supply 111 was applied to the bias rod 112. A DC bias of +120 V from the mesh bias power source 114 was applied to the mesh 113. When each parameter such as the state of plasma and the bias current became constant, the shutter 115 was opened, and the formation of the i-type layer on the n-type layer was started. It has been previously confirmed that the microwave energy value is in a microwave energy rate-determining state.

When the layer thickness of the i-type layer 205 reaches approximately 200 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the outputs of the bias power sources 111 and 114 are cut off, and the gas is introduced into the deposition chamber 101. Stop the i-type layer 2
The formation of 05 is finished. The deposition rate of the i-type layer is about 10 nm
/ Sec.

Subsequently, a p-type layer 206, a transparent electrode 207, and a collector electrode 208 were formed in the same manner as in Example 1 to obtain a photovoltaic element (No. Ex-2).

On the other hand, two types of comparative examples were manufactured. One is that, in the i-type layer forming step, the rf energy is set to 300 W, which is smaller than the microwave energy, and the semiconductor layer is deposited. A-SiG manufactured in the same manner as
e: H photovoltaic element (No. ratio 2-1), and the second one is more than microwave energy required to decompose microwave energy of 500 W and 100% of raw material gas in the i-type layer forming step. Except for the fact that the semiconductor layer is deposited with a large value, the other conditions are the photovoltaic device (N
o. This is an a-SiGe: H photovoltaic element (No. ratio -2-2) manufactured in the same manner as in Example-2).

Photovoltaic devices (No. Ex-2), (No. Ratio 2-1) and (No.
The current-voltage characteristics were measured for the ratio -2-2) in the same manner as in Example 1 to obtain the photoelectric conversion efficiency. As a result, when the value of the photovoltaic device (No. ratio 2-1) of the comparative example is 1, the photovoltaic device (No. real-2) manufactured by using the deposited film forming method of the present invention. It was found that the photoelectric conversion efficiency of 1) was dramatically improved to 1.27. Further, when the same evaluation is performed on the photovoltaic element (No. ratio -2-2), the photoelectric conversion efficiency is 0.93, and the photovoltaic element (No. ratio -2) is
It was inferior to -1).

From the above results, in the photovoltaic element using the deposited film forming method of the present invention in forming the i-type layer that most greatly affects the characteristics of the photovoltaic element, it contributes to the improvement of the characteristics of the deposited film. A large amount of ionic species is generated and is effectively selected, and the uniformity and stability of the plasma are improved, so that the uniformity and characteristics of the deposited film are improved, and as a result, the photovoltaic device is improved. It is considered that the dramatic improvement in the photoelectric conversion efficiency of 1 was achieved.

Example 3 a-Si: H / a-Si having the structure shown in FIG. 2 (b)
A Ge: H double type photovoltaic element was produced as described below. In the photovoltaic device, the first i-type layer is a
-SiGe: H, the second i-type layer is a-
It is composed of Si: H.

In this embodiment, as the substrate 211, a 10 cm square stainless steel (SUS304) plate having a mirror-polished surface is used, and a light reflecting layer 212 is formed thereon.
Was formed by a known vacuum deposition method to have an average thickness of 0.5 μm. At that time, the substrate temperature is set to 400 ° C. to deposit silver, and thereby a period of about 1.1 is formed on the surface of the silver layer.
A concavo-convex structure with a height difference of about 0.3 μm was formed.

On this, a zinc oxide layer was formed as the reflection increasing layer 213 in the same manner as in Example 1.

Subsequently, the first n-type layer 214, the a-SiGe: H film as the first i-type layer 215, and the first p-type layer 2 are formed.
16 was formed in the same manner as in Example 2.

Furthermore, the second n-type layer 217, the a-Si: H film as the second i-type layer 218, and the second p-type layer 219.
Was formed in the same manner as in Example 1.

After the above steps are completed, the transparent electrode 220,
The collector electrode 221 was formed in the same manner as in Example 1 to obtain a photovoltaic element (No. Ex-3).

As a comparative example, except that the semiconductor layer was deposited without applying a bias voltage to the mesh 113 in the steps of forming the first and second i-type layers, the other conditions were the photovoltaic element (No. -3) and a-Si: H /
a-SiGe: H double type photovoltaic element (No. ratio-
3) was produced.

With respect to the photovoltaic elements (No. Ex-3) and (No. Ratio-3) produced as described above, the current-voltage characteristics were measured in the same manner as in Example 1 to perform photoelectric conversion. I asked for efficiency. As a result, when the value of the photovoltaic element (No. ratio -3) of the comparative example is 1, the photovoltaic element (No. Ex-3) produced by using the deposited film forming method of the present invention is used. It was found that the photoelectric conversion efficiency was dramatically improved to 1.24. That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, the ionic species that contribute to the improvement of the deposited film characteristics are effectively selected. And that the uniformity and characteristics of the deposited film have been improved by improving the uniformity and stability of the plasma, and as a result, a dramatic improvement in the photoelectric conversion efficiency of the photovoltaic device has been achieved. Conceivable.

Further, the same experiment was repeated 10 times to examine the variation in the photoelectric conversion efficiency of the photovoltaic element.
As a result, it was found that the variation width in the photovoltaic element formed by using the deposited film forming method of the present invention was 0.49 when the variation width in the photovoltaic element of the comparative example was 1. It was That is, in the photovoltaic element using the deposited film forming method of the present invention in forming the i-type layer that most greatly affects the characteristics of the photovoltaic element, it is possible to improve the reproducibility of the deposited film by stabilizing the plasma. As a result, it is considered that the reproducibility of the photovoltaic element is dramatically improved.

Example 4 An a-Si: H photovoltaic device having the structure shown in FIG. 2 (a) was produced as described below.

In this example, as the substrate 201, a 10 cm square stainless steel (SUS304) plate having a mirror-polished surface was used, and a light reflecting layer 202 was formed thereon.
Was formed into a thickness of 0.3 μm by a known vacuum deposition method.

On this, a zinc oxide layer as the reflection increasing layer 203 was formed as follows using the DC sputtering apparatus shown in FIG.

A substrate on which silver has been vapor-deposited in advance on the heater 303.
After attaching the plate 302, the inside of the deposition chamber 301 is not shown.
Pump down. The degree of vacuum in the deposition chamber 301
10 ^-FiveConfirmed that it became below Torr with vacuum gauge 312
After that, the heater 303 is energized to change the temperature of the substrate 302 to 4
It was heated and held at 00 ° C.

In this example, the target 304 used was a sintered zinc oxide powder. Argon gas as a sputter gas is supplied through the gas introduction valve 314 while being adjusted by the mass flow controller 316 so that the flow rate is 25 sccm, and after the flow rate is stabilized, a DC voltage is supplied from the sputter power source 306 to the target 304 and a sputter current. Was set and applied so as to be 0.8 A. The internal pressure during sputtering was kept at 7 mTorr.

The formation of the zinc oxide layer was started as described above, and after the layer thickness of the zinc oxide layer reached 1.0 μm, power was supplied from the sputtering power source, sputtering gas was supplied to the heater 303. Power to the deposition chamber 3 is stopped and the substrate is cooled.
The inside of 01 was leaked to the atmosphere to take out the substrate on which the zinc oxide layer was formed.

Subsequently, an n-type layer 204, an i-type layer 205 and a p-type layer 206 each made of a-Si: H are formed thereon.
It was formed using the microwave plasma CVD apparatus shown in FIG.

Gas cylinders 1071 to 1076 in FIG.
The raw material gas for forming each semiconductor layer is sealed in. 1071 is SiH ₄ (purity 99.999
%) Gas cylinder, 1072 is GeH ₄ (purity 99.99)
9%) gas cylinder, 1073 is H ₂ (purity 99.999)
9%) gas cylinder, 1074 abbreviated as PH ₃ gas diluted to 10% with H ₂ gas (hereinafter "PH ₃ / H ₂ gas") cylinder, 1075 BF ₃ diluted to 10% with H ₂ gas Gas (hereinafter abbreviated as “BF ₃ / H ₂ gas”) cylinders and 1076 are Ar gas cylinders. When the gas cylinders 1071 to 1076 are attached, SiH ₄ gas from the gas cylinder 1071 and G from the gas cylinder 1072
eH ₄ gas, H ₂ gas from gas cylinder 1073, PH ₃ / H ₂ gas from gas cylinder 1074, gas cylinder 107
BF ₃ / H ₂ gas from No. 5 and Ar gas from the gas cylinder 1076 are introduced into the gas pipes of the valves 1031 to 1036 by opening the valves 1051 to 1056, and the respective pipes are adjusted by the pressure regulators 1061 to 1066. The gas pressure inside was adjusted to ² kg / cm ² .

Valves 1031 to 1036 and deposition chamber 1
It is confirmed that the leak valve 109 of 01 is closed, and that the valves 1041 to 1046 are opened, the conductance (butterfly type) valve 107 is fully opened, and a vacuum pump (not shown) is used. The deposition chamber 101 and the gas pipe are exhausted. When the reading of the vacuum gauge 106 is preferably 1 × 10 ⁻⁴ Torr or less, more preferably 1 × 10 ⁻⁵ Torr or less, the valve 104 is reached.
1 to 1046 are closed.

Next, the valves 1031 to 1036 are gradually opened to let each gas flow through the mass flow controller 10.
21 to 1026.

After the preparation for forming the semiconductor layer is completed as described above, the heater 105 is energized to set the substrate 104 to 3
Heated and held at 80 ° C.

Next, the introduction valves 1041, 1043, 1
Open 044 gradually to prevent dust from scattering
H ₄ gas, H ₂ gas, and PH ₃ / H ₂ gas were caused to flow into the deposition chamber 101 through the auxiliary valve 108 and the gas introduction pipe 103. At this time, the SiH ₄ gas flow rate is 10 sccm,
The mass flow controllers 1021, 1023, and 1024 were adjusted so that the H ₂ gas flow rate was 100 sccm and the PH ₃ / H ₂ gas flow rate was 1.0 sccm.

It is preferable to gradually introduce the gas into the deposition chamber 101 and to perform the operation with the shutter 115 closed, in order to prevent dust from adhering to the substrate surface.

The mesh 113 has been removed from the vicinity of the substrate by moving in advance.

When the gas flow rate becomes stable, the deposition chamber 10
The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that the pressure in 1 became 5 mTorr. Next, the power of the microwave power source (not shown) is set to 350 W, and the waveguide, the waveguide section 110, and the dielectric window 1 (not shown) are set.
Microwave power was introduced into the deposition chamber 101 via 02 to cause microwave glow discharge. After the plasma is stabilized, 500 W rf bias and +80 by the bias power supply 111 capable of supplying DC and rf bias voltages.
A DC bias voltage of V was applied to bias rod 112.
The shutter 115 is opened when each parameter such as the state of plasma and the bias current becomes constant, and the substrate 104 is opened.
The formation of the n-type layer on top was started.

When the thickness of the n-type layer 204 reaches about 20 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the output of rf and the DC power supply 111 is cut off, and
The introduction valves 1041, 1043, and 1044 were closed to stop the gas introduction into the deposition chamber 101, and the formation of the n-type layer 204 was completed.

Next, the i-type layer 205 is formed by using the method of the present invention.
Was formed as follows.

First, the mesh 113 is moved to move the substrate 1
The temperature of the mesh 113 is heated and maintained at 200 ° C. by installing it so as to cover 04 and operating the temperature controller 116 for the mesh 113. The material of the mesh 113 used in this example is A.
1 and has a substantially square opening having a side of 0.5 mm and an opening ratio of 50%.

Next, the deposition chamber 101 and the inside of the pipe are temporarily set to 10
After evacuating to a high vacuum of ^-4 Torr or less, the substrate 104 is heated and held at 370 ° C. by the heater 105, the introduction valve 1041 is opened, and 150 sccm of SiH ₄ gas is deposited through the auxiliary valve 108 and the gas introduction pipe 103. It was introduced into the chamber 101. The pressure in the deposition chamber 101 is 7 mTo
The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that it would be rr. Next, the power of the microwave power source (not shown) is set to 400 W, and the deposition chamber 1 is passed through the waveguide (not shown), the waveguide section 110 and the dielectric window 102.
Microwave power is introduced into 01 to generate microwave glow discharge, and then rf is generated by the bias power supply 111.
A bias of 650 W was supplied to the bias rod 112.

When the parameters of the plasma state, bias current, etc. became constant, the shutter 115 was opened, and the formation of the i-type layer on the n-type layer was started. It has been previously confirmed by the above-described method that the microwave energy value is in a microwave energy rate-determining state.

When the thickness of the i-type layer 205 reaches about 250 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the output of the bias power supply 111 is cut off, and the introduction of gas into the deposition chamber 101 is stopped. The formation of the i-type layer 205 is completed. The deposition rate of the i-type layer was about 9 nm / sec.

Next, the p-type layer 206 was formed as follows. First, the mesh 113 was moved and removed from the vicinity of the substrate 104. Subsequently, the substrate 104 is heated and held at 350 ° C. by the heater 105, and Si is heated.
Auxiliary valve 1 for H ₄ gas, H ₂ gas, and BF ₃ / H ₂ gas
It was introduced into the deposition chamber 101 through 08 and the gas introduction pipe 103. At this time, the SiH ₄ gas flow rate is 10 sccm, H
The mass flow controllers were adjusted so that the ₂ gas flow rate was 100 sccm and the BF ₃ / H ₂ gas flow rate was 1 sccm. The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that the pressure in the deposition chamber 101 was 5 mTorr. Next, the power of a microwave power source (not shown) is set to 400 W, microwave energy is introduced into the deposition chamber 101 through a waveguide, a waveguide section 110, and a dielectric window 102 (not shown) to perform microwave glow discharge. And then +10 by the bias power supply 111.
A DC bias voltage of 0V was applied to the bias rod 112. When the parameters of the plasma, the bias current, etc. became constant, the shutter 115 was opened, and the formation of the p-type layer on the i-type layer was started.

When the layer thickness of the p-type layer 206 reaches about 10 nm, the shutter 115 is closed to stop the introduction of microwave power, turn off the output of the bias power source 111, and stop the introduction of gas into the deposition chamber 101. The formation of the p-type layer 206 is completed.

Next, after the argon purge inside the deposition chamber 101 and the gas introduction pipe and the like is repeated three times, the gas introduction valve is closed, and when the substrate temperature drops to an appropriate value, the leak valve 109 is opened to deposit. The inside of the chamber 101 was leaked to the atmosphere, and the substrate 104 having the n-type layer, the i-type layer and the p-type layer formed on the surface thereof was taken out from the deposition chamber 101.

In the next step, ITO (In ₂ O ₃ + SnO) was formed as a transparent electrode 207 on the p-type layer 206 of the a-Si: H photovoltaic element formed as described above.
It was formed as follows.

The apparatus shown in FIG. 4 was used as a reactive vacuum vapor deposition apparatus.

The substrate 402 on which the p-type layer is formed is attached to the heater 403, and as the vapor deposition source 404, metal tin and metal indium (both having a purity of 99.999%) are used.
%: 50% After replenishing the mixture, a vacuum pump (not shown) is operated to fully open the conductance valve and the deposition chamber 401.
Evacuate the inside.

After the degree of vacuum in the deposition chamber became 10 ⁻⁶ Torr or less, the heater 403 was energized to maintain the temperature of the substrate 402 at 150 ° C.

Subsequently, oxygen gas (O ₂ ) was adjusted by the mass flow controller 411 so that the flow rate was 8 sccm, and was introduced into the deposition chamber 401 via the gas introduction valve 410. After the flow rate becomes constant, the conductance valve 409 is adjusted while watching the vacuum gauge 408 to adjust the deposition chamber 4
The degree of vacuum inside 01 was set to 3 × 10 ⁻⁴ Torr.

After the internal pressure became constant, the heater 405 for the vapor deposition source was energized to start heating the vapor deposition source 404.

When the temperature of the vapor deposition source rises and tin and indium start to vaporize, the vaporized metal atoms react with oxygen gas in the deposition chamber, so that the pressure in the deposition chamber slightly decreases. When the fluctuation value of this pressure reaches 3 × 10 ⁻⁶ Torr, the shutter 407 is opened and the ITO on the substrate 402 is opened.
The film formation started.

While watching the value of the deposition rate by the film thickness monitor 413, the output of the AC power source 406 is adjusted so that the deposition rate becomes substantially constant at about 0.07 nm / sec.
A TO film was formed.

When the thickness of the ITO film reaches 75 nm, the shutter 407 is closed and the heaters 403 and 4 are used.
The energization of 05 is stopped, the gas introduction valve 410 is closed, and the formation of the transparent electrode 207 is completed. When the substrate temperature decreased, the leak valve 412 was opened, the inside of the deposition chamber 401 was leaked, and the substrate 402 on which the transparent electrode 207 was formed was taken out.

Next, as the collecting electrode 208, Al having a layer thickness of 2 μm is vapor-deposited by a resistance heating vacuum vapor deposition method using a mask.
Then, an a-Si: H photovoltaic element (No. Ex-4) was obtained.

As a comparative example, a photovoltaic element (No. Ex-4) was used under the other conditions except that the preset temperature of the mesh 113 was changed to deposit the semiconductor layer in the i-type layer forming step.
And a-Si: H photovoltaic element (No. ratio -4
-1) to (No. ratio -4-10) were manufactured.

Photovoltaic devices (No. Ex-4) and (No. Ratio-4-1) to (N) produced as described above.
o. For the ratio -4-10), using a solar simulator (Yamashita Denso, YSS-150), the simulated sunlight (A
The current-voltage characteristics were measured under irradiation with M-1.5 and 100 mW / cm ² ) to examine the relationship between the preset temperature of the mesh and the photoelectric conversion efficiency during the formation of the i-type layer. The results are standardized and shown in FIG. As is clear from this result, the photoelectric conversion efficiency of the photovoltaic element formed by using the deposited film forming method of the present invention is as high as that of the photovoltaic element formed by not using the method of the present invention. It turns out that it has improved dramatically from the efficiency. That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, active species that contribute to the improvement of the film characteristics are effectively selected, It is also considered that the characteristics of the deposited film were improved due to the abundant supply to the surface of the deposited film, and as a result, the photoelectric conversion efficiency of the photovoltaic device was dramatically improved.

Further, the following durability test was conducted in order to investigate the reliability of these photovoltaic elements under actual use conditions.

Photovoltaic device (No. Ex-4) and (N
o. Each of the ratios 4-1) to (No. ratio -4-10) is vacuum-sealed with a protective film made of polyvinylidene fluoride (VDF), and under actual use conditions (installed outdoors, 50 on both electrodes).
After placing it for 1 year in a fixed resistance of ohms, the photoelectric conversion efficiency is evaluated again, and the deterioration rate due to light irradiation, temperature difference, wind and rain, etc. The value obtained by dividing by the value of photoelectric conversion efficiency) was obtained, and the relationship between the set temperature of the mesh and the deterioration rate during the formation of the i-type layer was investigated.
The results are standardized and shown in FIG. As is clear from this result, the reliability of the photovoltaic element formed by using the deposited film forming method of the present invention is as high as that of the photovoltaic element formed by not using the deposited film forming method of the present invention. It turned out that it has improved dramatically from the reliability. That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that largely affects the reliability of the photovoltaic element, active species that contribute to the improvement of the deterioration resistance of the deposited film are effective. It is considered that the deterioration of the deposited film is improved by the above selection and the abundant supply to the surface of the deposited film, and as a result, the reliability of the photovoltaic element is dramatically improved.

Example 5 An a-SiGe: H photovoltaic device having the structure shown in FIG. 2A was produced as described below.

In this embodiment, a stainless steel (SUS304) plate having a 10 cm square and a thickness of 0.1 mm whose surface is mirror-polished is used as the substrate 201, and the light reflecting layer 202 is formed thereon.
Was formed into a thickness of 0.5 μm by a known vacuum deposition method. At that time, the substrate temperature was set at 350 ° C. to deposit silver to form an uneven structure with a period of about 1 μm and a height difference of about 0.3 μm on the surface of the silver layer.

On this, a zinc oxide layer was formed as the reflection increasing layer 203 in the same manner as in Example 1.

Next, the n-type layer 204 was formed in the same manner as in Example 1, and subsequently, an a-SiGe: H film was formed as the i-type layer 205 as follows.

First, the deposition chamber 101 and the inside of the pipe are temporarily set to 10
After evacuating to a high vacuum of ^-5 Torr or less, the substrate 104 is heated and held at 380 ° C. by the heater 105, the introduction valves 1041 and 1042 are opened, and the SiH ₄ gas 12
0 sccm, GeH ₄ gas 30 sccm auxiliary valve 1
It was introduced into the deposition chamber 101 through 08 and the gas introduction pipe 103. Conductance valve 10 while watching vacuum gauge 106 so that the pressure in deposition chamber 101 becomes 5 mTorr.
The opening of 7 was adjusted. Next, the power of the microwave power source (not shown) is set to 350 W, and the waveguide and the waveguide section 11 (not shown) are set.
0 and the dielectric window 102 to introduce microwave power into the deposition chamber 101 to cause microwave glow discharge,
After the plasma is stabilized, the bias power supply 111 causes r
F energy of 550 W was applied to the bias rod 112.
In addition, by operating the temperature controller 114 for the mesh 113, the temperature of the mesh 113 is increased to 200 ° C.
Heat and store. When parameters such as plasma state and bias current became constant, the shutter 115 was opened, and formation of the i-type layer on the n-type layer was started. It has been previously confirmed that the microwave energy value is in a microwave energy rate-determining state. The mesh 113 used in this embodiment is made of SUS.
And has a substantially square opening with a side of 0.75 mm and an opening ratio of 70%.

When the layer thickness of the i-type layer 205 reaches approximately 230 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the outputs of the bias power sources 111 and 114 are cut off, and the gas is introduced into the deposition chamber 101. Stop the i-type layer 2
The formation of 05 is finished. The deposition rate of the i-type layer is about 9 nm /
It was sec.

Subsequently, the p-type layer 206, the transparent electrode 207, and the collector electrode 208 were formed in the same manner as in Example 4 to obtain a photovoltaic element (No. Ex-5).

On the other hand, two types of comparative examples were manufactured. One is that in the i-type layer forming step, the rf energy supplied from the bias rod is set to 300 W, which is a value smaller than the microwave energy, and the semiconductor layer is deposited. The actual a-5) is an a-SiGe: H photovoltaic element (No. ratio -5-1) manufactured by the same method as the actual -5), and another one is 500 W of microwave energy and source gas in the i-type layer forming step. Was prepared under the same conditions as the photovoltaic element (No. Ex-5), except that the semiconductor layer was deposited at a value larger than the microwave energy required for 100% decomposition of a. -SiGe: H photovoltaic element (No. ratio-5-
2).

Photovoltaic devices (No. Ex-5), (No. Ratio-5-1) and (No.
The current-voltage characteristics were measured for the ratio -5-2) in the same manner as in Example 4 to obtain the photoelectric conversion efficiency. As a result, when the value of the photovoltaic element (No. ratio -5-1) of the comparative example is set to 1, the photovoltaic element (No. real-number) formed by using the deposited film forming method of the present invention. It was found that the photoelectric conversion efficiency of 5) was dramatically improved to 1.31. Further, when the same evaluation is performed on the photovoltaic element (No. ratio -5-2), the photoelectric conversion efficiency is 0.93, and the photovoltaic element (No. ratio -5).
It was inferior to -1).

From the above results, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, the electrical characteristics and deterioration resistance of the deposited film are obtained. The ion species that contribute to the improvement of the plasma property are effectively selected and are abundantly supplied to the surface of the deposited film, and the uniformity and stability of the deposited film are improved by improving the plasma uniformity and stability. As a result, it is considered that the photoelectric conversion efficiency of the photovoltaic element has been dramatically improved.

Example 6 a-Si: H / a-Si having the structure shown in FIG. 2 (b)
A Ge: H double type photovoltaic element was produced as described below. In the photovoltaic device, the first i-type layer is a
-SiGe: H, the second i-type layer is a-
It is composed of Si: H.

In this example, as the substrate 211, a 10 cm square stainless steel (SUS304) plate having a mirror-polished surface is used, and a light reflection layer 212 is formed thereon.
Was formed by a known vacuum deposition method to have an average thickness of 0.5 μm. At that time, the substrate temperature is set to 400 ° C. to deposit silver, and thereby a period of about 1.1 is formed on the surface of the silver layer.
A concavo-convex structure with a height difference of about 0.3 μm was formed.

On this, a zinc oxide layer was formed as the reflection increasing layer 213 in the same manner as in Example 1.

Subsequently, the first n-type layer 214, the a-SiGe: H film as the first i-type layer 215, and the first p-type layer 2 are formed.
16 was formed in the same manner as in Example 2.

Further, a second n-type layer 217, an a-Si: H film as the second i-type layer 218, and a second p-type layer 219.
Was formed in the same manner as in Example 1.

After completing the above steps, the transparent electrode 220,
The collector electrode 221 was formed in the same manner as in Example 4 to obtain a photovoltaic element (No. Ex-6).

As a comparative example, except for the point that the semiconductor layer was deposited without placing the mesh 113 in the vicinity of the substrate 104 in the first and second i-type layer forming steps, the photovoltaic element ( No. Ex.-6) and a-Si: H
/ A-SiGe: H double type photovoltaic element (No. ratio-
6) was produced.

Current-voltage characteristics were measured in the same manner as in Example 1 with respect to the photovoltaic elements (No. Ex-6) and (No. Ratio-6) produced as described above, and photoelectric conversion was performed. I asked for efficiency. As a result, when the value of the photovoltaic element (No. ratio-6) of the comparative example is 1, the photovoltaic element (No. Ex-6) formed by using the deposited film forming method of the present invention. It was found that the photoelectric conversion efficiency of was dramatically improved to 1.35. That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, the ionic species that contribute to the improvement of the deposited film characteristics are effectively selected. And that the uniformity and characteristics of the deposited film have been improved by improving the uniformity and stability of the plasma, and as a result, a dramatic improvement in the photoelectric conversion efficiency of the photovoltaic device has been achieved. Conceivable.

Further, the same experiment was repeated 10 times to examine the variation in the photoelectric conversion efficiency of the photovoltaic element.
As a result, it was found that the variation width in the photovoltaic element formed by using the deposited film forming method of the present invention is 0.46 when the variation width in the photovoltaic element of the comparative example is 1. It was That is, in the photovoltaic device using the deposition forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic device, the reproducibility of the deposited film is improved by stabilizing the plasma. As a result, it is considered that the reproducibility of the photovoltaic element has been dramatically improved.

Example 7 An a-Si: H photovoltaic device having the structure shown in FIG. 2A was manufactured as described below.

In this example, as the substrate 201, a stainless steel (SUS304) plate having a 10 cm square and a thickness of 0.1 mm whose surface was mirror-polished was used, and a light reflecting layer 202 was formed thereon.
Was formed into a thickness of 0.3 μm by a known vacuum deposition method.

On this, a zinc oxide layer as the reflection increasing layer 203 was formed as follows using the DC sputtering apparatus shown in FIG.

A substrate on which silver has been vapor-deposited in advance on the heater 303.
After attaching the plate 302, the inside of the deposition chamber 301 is not shown.
Pump down. The degree of vacuum in the deposition chamber 301
10 ^-FiveConfirmed that it became below Torr with vacuum gauge 312
After that, the heater 303 is energized to change the temperature of the substrate 302 to 4
It was heated and held at 00 ° C.

In this example, the target 304 used was a sintered zinc oxide powder. Argon gas as a sputter gas is supplied through the gas introduction valve 314 while being adjusted by the mass flow controller 316 so that the flow rate is 25 sccm, and after the flow rate is stabilized, a DC voltage is supplied from the sputter power source 306 to the target 304 and a sputter current. Was set and applied so as to be 0.8 A. The internal pressure during sputtering was kept at 7 mTorr.

The formation of the zinc oxide layer was started as described above, and after the layer thickness of the zinc oxide layer reached 1.0 μm, power was supplied from the sputtering power source, sputtering gas was supplied, and the heater 303 was supplied. After de-energizing and cooling the substrate, the deposition chamber 30
The inside of 1 was leaked to the atmosphere, and the substrate on which the zinc oxide layer was formed was taken out.

Subsequently, an n-type layer 204, an i-type layer 205 and a p-type layer 206 each made of a-Si: H are formed thereon.
It was formed using the microwave plasma CVD apparatus shown in FIG.

Gas cylinders 1071 to 1076 in FIG.
The raw material gas for forming each semiconductor layer is sealed in. 1071 is SiH ₄ (purity 99.999
%) Gas cylinder, 1072 is GeH ₄ (purity 99.99)
9%) gas cylinder, 1073 is H ₂ (purity 99.999)
9%) gas cylinder, 1074 abbreviated as PH ₃ gas diluted to 10% with H ₂ gas (hereinafter "PH ₃ / H ₂ gas") cylinder, 1075 BF ₃ diluted to 10% with H ₂ gas Gas (hereinafter abbreviated as “BF ₃ / H ₂ gas”) cylinders and 1076 are Ar gas cylinders. When the gas cylinders 1071 to 1076 are attached, SiH ₄ gas from the gas cylinder 1071 and G from the gas cylinder 1072
eH ₄ gas, H ₂ gas from gas cylinder 1073, PH ₃ / H ₂ gas from gas cylinder 1074, gas cylinder 107
BF ₃ / H ₂ gas from No. 5 and Ar gas from the gas cylinder 1076 are introduced into the gas pipes of the valves 1031 to 1036 by opening the valves 1051 to 1056, and the respective pipes are adjusted by the pressure regulators 1061 to 1066. The gas pressure inside was adjusted to ² kg / cm ² .

Valves 1031 to 1036 and deposition chamber 1
It is confirmed that the leak valve 109 of 01 is closed, and that the valves 1041 to 1046 are opened, the conductance (butterfly type) valve 107 is fully opened, and a vacuum pump (not shown) is used. The deposition chamber 101 and the gas pipe are exhausted. When the reading of the vacuum gauge 106 is preferably 1 × 10 ⁻⁴ Torr or less, more preferably 1 × 10 ⁻⁵ Torr or less, the valve 104 is reached.
1 to 1046 are closed.

Next, the valves 1031 to 1036 are gradually opened to let each gas flow through the mass flow controller 10.
21 to 1026.

After the semiconductor layer was prepared for preparation as described above, the heater 105 was energized to heat and hold the substrate 104 at 380 ° C.

Next, the introduction valves 1041, 1043, 1
Open 044 gradually to prevent dust from scattering
H ₄ gas, H ₂ gas, and PH ₃ / H ₂ gas were caused to flow into the deposition chamber 101 through the auxiliary valve 108 and the gas introduction pipe 103. At this time, the SiH ₄ gas flow rate is 10 sccm,
The mass flow controllers 1021, 1023, and 1024 were adjusted so that the H ₂ gas flow rate was 100 sccm and the PH ₃ / H ₂ gas flow rate was 1.0 sccm.

It is preferable to gradually introduce the gas into the deposition chamber 101 and to perform this with the shutter 115 closed to prevent dust from adhering to the substrate surface.

When the gas flow rate is stable, the deposition chamber 10
The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that the pressure in 1 became 5 mTorr. Next, the power of the microwave power source (not shown) is set to 400 W, and the waveguide, the waveguide section 110, and the dielectric window 1 (not shown) are set.
Microwave power was introduced into the deposition chamber 101 via 02 to cause microwave glow discharge. After the plasma is stabilized, 600 W rf bias and +10 by a bias power supply 111 capable of supplying DC and rf bias voltages.
A DC bias voltage of 0V was applied to the bias rod 112. When each parameter such as the state of plasma and the bias current becomes constant, the shutter 115 is opened and the substrate 1
The formation of an n-type layer on 04 was started. The mesh 11
It has been removed from near substrate 104 by moving 3.

When the layer thickness of the n-type layer 204 becomes about 20 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the output of rf and the DC power supply 111 is cut off, and
The introduction valves 1041, 1043, and 1044 were closed to stop the gas introduction into the deposition chamber 101, and the formation of the n-type layer 204 was completed.

Next, the i-type layer 205 was formed as follows. First, the mesh 113 was moved and installed so as to cover the substrate 104. Subsequently, the deposition chamber 101 and the piping were once evacuated to a high vacuum of 10 ⁻⁵ Torr or less, and then the substrate 104 was heated and held at 370 ° C. by the heater 105, and the introduction valve 1041 was opened to supplement 150 sccm of SiH ₄ gas. Valve 108 and gas introduction pipe 1
It was introduced into the deposition chamber 101 through 03. Deposition chamber 101
The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that the internal pressure became 5 mTorr.
Next, the power of the microwave power source (not shown) is set to 450 W, and the waveguide, the waveguide section 110, and the dielectric window 102 (not shown) are set.
Microwave power is introduced into the deposition chamber 101 through a microwave glow discharge to generate a microwave glow discharge, and then an rf bias 750 W from a bias power source 111 is applied to the bias rod 112.
Supplied to. Also, the rf bias voltage from the mesh rf bias power source 114 is applied to the rf energy 100
W was supplied from the mesh 113. When each parameter such as the state of plasma and the bias current became constant, the shutter 115 was opened, and the formation of the i-type layer on the n-type layer was started. It has been previously confirmed by the above-described method that the microwave energy value is in a microwave energy rate-determining state.

When the thickness of the i-type layer 205 reaches about 270 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the outputs of the bias power sources 111 and 114 are cut off, and the gas is introduced into the deposition chamber 101. Stop the i-type layer 2
The formation of 05 is finished. The deposition rate of the i-type layer is about 10 nm
/ Sec.

Next, the p-type layer 206 was formed as follows. First, the mesh 113 was moved and removed from the vicinity of the substrate 104. Subsequently, the substrate 104 is heated and held at 350 ° C. by the heater 105, and Si is heated.
Auxiliary valve 1 for H ₄ gas, H ₂ gas, and BF ₃ / H ₂ gas
It was introduced into the deposition chamber 101 through 08 and the gas introduction pipe 103. At this time, the SiH ₄ gas flow rate is 10 sccm, H
The mass flow controllers were adjusted so that the ₂ gas flow rate was 100 sccm and the BF ₃ / H ₂ gas flow rate was 1 sccm. The opening of the conductance valve 107 was adjusted while observing the vacuum gauge 106 so that the pressure in the deposition chamber 101 was 5 mTorr. Next, the power of a microwave power source (not shown) is set to 400 W, microwave energy is introduced into the deposition chamber 101 through a waveguide, a waveguide section 110, and a dielectric window 102 (not shown) to perform microwave glow discharge. And then +10 by the bias power supply 111.
A DC bias voltage of 0V was applied to the bias rod 112. When the parameters of the plasma, the bias current, etc. became constant, the shutter 115 was opened, and the formation of the p-type layer on the i-type layer was started.

When the layer thickness of the p-type layer 206 becomes about 10 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the output of the bias power supply 111 is cut off, and the introduction of gas into the deposition chamber 101 is stopped. The formation of the p-type layer 206 is completed.

Next, after the argon purging of the inside of the deposition chamber 101 and the gas introduction pipe and the like is repeated three times, the gas introduction valve is closed, and when the substrate temperature drops to an appropriate value, the leak valve 106 is opened and deposition is performed. The inside of the chamber 101 was leaked to the atmosphere, and the substrate 104 having the n-type layer, the i-type layer and the p-type layer formed on the surface thereof was taken out from the deposition chamber 101.

In the next step, ITO (In ₂ O ₃ + SnO ₂ ) was formed as a transparent electrode 207 on the p-type layer 206 of the a-Si: H photovoltaic element formed as described above.
It was formed as follows.

The apparatus shown in FIG. 4 was used as a reactive vacuum vapor deposition apparatus.

The substrate 402 on which the p-type layer has been formed is attached to the heater 403, and as the vapor deposition source 404, metal tin and metal indium (both having a purity of 99.999%) are used.
%: 50% After replenishing the mixture, a vacuum pump (not shown) is operated to fully open the conductance valve and the deposition chamber 401.
Evacuate the inside.

After the degree of vacuum in the deposition chamber became 10 ⁻⁶ Torr or less, the heater 403 was energized to maintain the temperature of the substrate 402 at 150 ° C.

Subsequently, oxygen gas (O ₂ ) was adjusted by the mass flow controller 411 so that the flow rate was 8 sccm, and introduced into the deposition chamber 401 through the gas introduction valve 410. After the flow rate becomes constant, the conductance valve 409 is adjusted while watching the vacuum gauge 408 to adjust the deposition chamber 4
The degree of vacuum inside 01 was set to 3 × 10 ⁻⁴ Torr.

After the internal pressure became constant, the heater 405 for the vapor deposition source was energized to start heating the vapor deposition source 404.

When the temperature of the vapor deposition source rises and metal tin and indium begin to vaporize, the vaporized metal atoms react with oxygen gas in the deposition chamber, so that the pressure in the deposition chamber slightly decreases. When the fluctuation value of the pressure became 3 × 10 ⁻⁵ Torr, the shutter 407 was opened and the formation of the ITO film on the substrate 402 was started.

While watching the value of the deposition rate by the film thickness monitor 413, the output of the AC power source 406 is adjusted so that the deposition rate becomes substantially constant at about 0.07 nm / sec.
A TO film was formed.

When the film thickness reaches 75 nm, the shutter 407 is closed, the heaters 403 and 405 are deenergized, the gas introduction valve 410 is closed, and the transparent electrode 20 is closed.
The formation of 7 is completed. When the substrate temperature decreased, the leak valve 412 was opened, the inside of the deposition chamber 401 was leaked, and the substrate 402 on which the transparent electrode 207 was formed was taken out.

Next, as the collector electrode 208, Al having a layer thickness of 2 μm was vapor-deposited by a resistance heating vacuum vapor deposition method using a mask.
Then, an a-Si: H photovoltaic element (No. Ex-7) was obtained.

As a comparative example, the other conditions are the same as those of the photovoltaic element (No. real-7) except that the semiconductor layer is deposited without applying the rf bias voltage to the mesh 113 in the i-type layer forming step. Then, an a-Si: H photovoltaic element (No. ratio -7) was produced.

The solar cells (Yamashita Denso Co., Ltd., YSS-150) for the photovoltaic elements (No. Ex-7) and (No. Ratio-7) produced as described above were used for pseudo sunlight. (AM-1.5, 100 mW / cm ² )
The current-voltage characteristics were measured under irradiation to determine the photoelectric conversion efficiency. As a result, the photovoltaic element of the comparative example (No.
When the value of 7) is set to 1, the photoelectric conversion efficiency of the photovoltaic element (No. Ex-7) formed by using the deposited film forming method of the present invention is dramatically improved to 1.22. I found out that That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, the ionic species that contribute to the improvement of the film characteristics are effectively selected, Moreover, the uniformity and characteristics of the deposited film have been improved by being appropriately accelerated by the electric field between the mesh and the substrate, and as a result, the photoelectric conversion efficiency of the photovoltaic device has been dramatically improved. it is conceivable that.

Further, the same experiment was repeated 10 times to examine the variation in the photoelectric conversion efficiency of the photovoltaic element.
As a result, it was found that the variation width in the photovoltaic element formed by using the deposited film forming method of the present invention is 0.47 when the variation width in the photovoltaic element of the comparative example is 1. It was That is, in the photovoltaic element using the deposited film forming method of the present invention in forming the i-type layer that most greatly affects the characteristics of the photovoltaic element, it is possible to improve the reproducibility of the deposited film by stabilizing the plasma. As a result, it is considered that the reproducibility of the photovoltaic element is dramatically improved.

Further, in order to investigate the reliability of these photovoltaic elements under actual use conditions, the following durability test was conducted.

Photovoltaic device (No. Ex-7) and (N
o. Each of the ratio -7) is polyvinylidene fluoride (VDF)
It is vacuum-sealed with a protective film consisting of 1 and it is used under actual use conditions (installed outdoors, connecting a fixed resistance of 50 ohms to both electrodes).
After leaving for a year, the photoelectric conversion efficiency is evaluated again, and the deterioration rate due to light irradiation, temperature difference, wind and rain, etc. (The value of the photoelectric conversion efficiency damaged by the deterioration is divided by the initial value of the photoelectric conversion efficiency. ) Was investigated. As a result, the photovoltaic element (No.
The actual deterioration rate of -7) was dramatically improved to 0.66 when the deterioration rate of the photovoltaic element (No. ratio -7) was set to 1. That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, the activity having energy that contributes to the structural relaxation of the film being deposited is With the presence of species, it is possible to effectively reduce the effects of unnecessary electrons and ions that cause harmful damage to the deposited film, which reduces the disturbance of the network in the deposited film, and as a result, It is considered that the reliability of the electromotive force element has been dramatically improved.

Example 8 An a-SiGe: H photovoltaic device having the structure shown in FIG. 2A was produced as described below.

In this example, as the substrate 201, a stainless steel (SUS304) plate having a 10 cm square and a thickness of 0.1 mm, the surface of which was mirror-polished, was used, and the light reflection layer 202 was formed thereon.
Was formed into a thickness of 0.5 μm by a known vacuum deposition method. At that time, the substrate temperature was set at 350 ° C. to deposit silver to form an uneven structure with a period of about 1 μm and a height difference of about 0.3 μm on the surface of the silver layer.

On this, a zinc oxide layer was formed as the reflection increasing layer 203 in the same manner as in Example 7.

Next, the n-type layer 204 was formed in the same manner as in Example 7, and subsequently, an a-SiGe: H film was formed as the i-type layer 205 as follows.

First, the deposition chamber 101 and the inside of the pipe are once
After evacuating to a high vacuum of ^-5 Torr or less, the substrate 104 is heated and held at 380 ° C. by the heater 105, the introduction valves 1041 and 1042 are opened, and the SiH ₄ gas 12
0 sccm, GeH ₄ gas 30 sccm auxiliary valve 1
It was introduced into the deposition chamber 101 through 08 and the gas introduction pipe 103. Conductance valve 10 while watching vacuum gauge 106 so that the pressure in deposition chamber 101 becomes 5 mTorr.
The opening of 7 was adjusted. Next, the power of the microwave power source (not shown) is set to 400 W, and the waveguide and the waveguide 11 (not shown) are set.
0 and the dielectric window 102 to introduce microwave power into the deposition chamber 101 to cause microwave glow discharge,
After the plasma is stabilized, the bias power supply 111 causes r
F energy of 600 W was applied to the bias rod 112.
Further, the rf bias voltage from the mesh bias power source 114 is applied to the mesh 113, and the rf energy is 80 W.
Was supplied from the mesh. When each parameter such as the state of plasma and the bias current became constant, the shutter 115 was opened, and the formation of the i-type layer on the n-type layer was started. It has been previously confirmed that the microwave energy value is in a microwave energy rate-determining state.

When the layer thickness of the i-type layer 205 reaches approximately 230 nm, the shutter 115 is closed, the introduction of microwave power is stopped, the outputs of the bias power sources 111 and 114 are cut off, and the gas is introduced into the deposition chamber 101. Stop the i-type layer 2
The formation of 05 is finished. The deposition rate of the i-type layer is about 10 nm
/ Sec.

Subsequently, a p-type layer 206, a transparent electrode 207, and a current collecting electrode 208 were formed in the same manner as in Example 7 to obtain a photovoltaic element (No. Ex-8).

On the other hand, two types of comparative examples were manufactured. One is that in the i-type layer forming step, the rf energy supplied from the bias rod is set to 300 W, which is a value smaller than the microwave energy, and the semiconductor layer is deposited. Example 8) An a-SiGe: H photovoltaic element (No. ratio -8-1) manufactured in the same manner as Example 8), and another one is 500 W of microwave energy and source gas in the i-type layer forming step. Was prepared under the same conditions as the photovoltaic element (No. real-8) except that the semiconductor layer was deposited at a value higher than the microwave energy required for 100% decomposition. -SiGe: H photovoltaic element (No. ratio -8-
2).

Photovoltaic devices (No. Ex-8), (No. Ratio-8-1) and (No.
The current-voltage characteristics were measured for the ratio -8-2) in the same manner as in Example 7 to obtain the photoelectric conversion efficiency. As a result, when the value of the photovoltaic element (No. ratio −8-1) of the comparative example is 1, the photovoltaic element (No. actual −) formed by using the deposited film forming method of the present invention. It was found that the photoelectric conversion efficiency of 8) was dramatically improved to 1.23. Further, when the same evaluation is performed on the photovoltaic element (No. ratio -8-2), the photoelectric conversion efficiency is 0.89, and the photovoltaic element (No. ratio -8).
It was inferior to -1).

From the above results, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, it contributes to the improvement of the characteristics of the deposited film. The uniformity and characteristics of the deposited film are improved by the effective selection of ion species and the improvement of plasma uniformity and stability. As a result, the photoelectric conversion efficiency of the photovoltaic device is dramatically improved. Is considered to have been achieved.

Example 9 a-Si: H / a-Si having the structure shown in FIG. 2 (b)
A Ge: H double type photovoltaic element was produced as described below. In the photovoltaic device, the first i-type layer is a
-SiGe: H, the second i-type layer is a-
It is composed of Si: H.

In this example, as the substrate 211, a 10 cm square stainless steel (SUS304) plate having a mirror-polished surface was used, and a light reflection layer 212 was formed thereon.
Was formed by a known vacuum deposition method to have an average thickness of 0.5 μm. At that time, the substrate temperature is set to 400 ° C. to deposit silver, and thereby a period of about 1.1 is formed on the surface of the silver layer.
A concavo-convex structure with a height difference of about 0.3 μm was formed.

On this, a zinc oxide layer was formed as the reflection increasing layer 213 in the same manner as in Example 7.

Subsequently, the first n-type layer 214, the a-SiGe: H film as the first i-type layer 215, and the first p-type layer 2 are formed.
16 was formed in the same manner as in Example 8.

Furthermore, the second n-type layer 217, the a-Si: H film as the second i-type layer 218, and the second p-type layer 219.
Was formed in the same manner as in Example 7.

After the above steps are completed, the transparent electrode 220,
The collector electrode 221 was formed in the same manner as in Example 7 to obtain a photovoltaic element (No. Ex-9).

As a comparative example, except that the semiconductor layer was deposited without applying an rf bias voltage to the mesh 113 in the steps of forming the first and second i-type layers, the photovoltaic element (No. Equal to the actual −9) and a-Si:
An H / a-SiGe: H double photovoltaic element (No. ratio -9) was produced.

Current-voltage characteristics were measured in the same manner as in Example 7 with respect to the photovoltaic elements (No. Ex-9) and (No. Ratio-9) produced as described above, and photoelectric conversion was performed. I asked for efficiency. As a result, when the value of the photovoltaic element (No. ratio-9) of the comparative example is 1, the photovoltaic element (No. Ex-9) formed by using the deposited film forming method of the present invention. It was found that the photoelectric conversion efficiency of 1. was dramatically improved to 1.20. That is, in the photovoltaic element using the deposited film forming method of the present invention in the formation of the i-type layer that most greatly affects the characteristics of the photovoltaic element, the ionic species that contribute to the improvement of the deposited film characteristics are effectively selected. And that the uniformity and characteristics of the deposited film have been improved by improving the uniformity and stability of the plasma, and as a result, a dramatic improvement in the photoelectric conversion efficiency of the photovoltaic device has been achieved. Conceivable.

Further, the same experiment was repeated 10 times to examine the variation in the photoelectric conversion efficiency of the photovoltaic element.
As a result, it was found that the variation width of the photovoltaic element formed by using the deposited film forming method of the present invention was 0.39 when the variation width of the photovoltaic element of the comparative example was 1. It was That is, in the photovoltaic element using the deposited film forming method of the present invention in forming the i-type layer that most greatly affects the characteristics of the photovoltaic element, it is possible to improve the reproducibility of the deposited film by stabilizing the plasma. As a result, it is considered that the reproducibility of the photovoltaic element is dramatically improved.

Example 10 Photovoltaic devices were continuously manufactured using the manufacturing apparatus shown in FIG.

First, a vacuum container 2301 having a substrate delivery mechanism was thoroughly degreased and washed, and a silver thin film of 100 nm and Z was formed as a lower electrode by a sputtering method.
SUS430BA band-shaped member 2150 (width 120 mm x length 200 m x thickness 0.
13 mm) wound bobbin 2303 is set, the band-shaped member 2150 is a gas gate, a vacuum container 2100n for forming a first conductivity type layer, a vacuum container 2100 for forming an i-type layer, and a second conductivity type. Vacuum container 2100p for layer formation
Via a vacuum container 23 having a belt-shaped member winding mechanism
The tension was adjusted to such an extent that there was no slack in the sample until 02.

Therefore, each vacuum container 2301, 2100
n, 2100, 2100p, and 2302 were evacuated to 1 × 10 ⁻⁶ Torr or less with a vacuum pump (not shown).

Next, the gas gates 2129n, 2129,
2130 and 2129p are provided with gate gas introduction pipes 2131n,
H ₂ as a gate gas was made to flow at 700 sccm from 2131, 2132, and 2131p to heat the infrared lamp 2 for heating.
The belt-shaped member 21 is formed by 124n, 2124, and 2124p.
50 are heated to 350 ° C. each. Then, SiH ₄ gas is supplied at 20 sccm and PH by the gas introducing means 2114n.
₃ / H ₂ (1%) gas at 200 sccm, H ₂ gas at 2
00 sccm, gas introduction means 2114, 2115, 21
16 from 200 sccm of SiH ₄ gas, H
₂ gas of 200 sccm, SiH ₄ gas of 30 sccm, BF ₃ / H ₂ (1
%) Gas and H ₂ gas at 250 sccm were introduced. The pressure in the vacuum container 2100n is 30 mTorr
The opening of the throttle valve 2127n was adjusted while observing the pressure gauge (not shown) so as to be r. Vacuum container 2100
The opening of the throttle valve 2127 was adjusted while observing the pressure gauge (not shown) so that the internal pressure became 6 mTorr. The pressure in the vacuum container 2100p is 30 mTorr
The opening of the throttle valve 2127p was adjusted while observing the pressure gauge (not shown) so that

Thereafter, the microwave power is applied to the applicator 2
105n, 2105, 2106, 2107, 2105p
Power is applied to each of the microwave transparent members 210
8n, 2108, 2109, 2110, 2108p, and microwave power of 1000W, 300W, 300
Introduced W, 300W, 1000W, then strip 21
50 is conveyed in the direction of the arrow in the figure, and the first member is placed on the belt-shaped member.
Of the conductivity type, the i-type layer, and the second conductivity type layer were formed.

When forming the i-type layer, meshes 2135 and 2136 were placed in the vacuum container 2100 as shown in FIG.

Next, ITO (In ₂ O ₃ + SnO ₂ ) was formed as a transparent electrode on the second conductive type layer by vacuum evaporation to a thickness of 2
70 nm was vapor-deposited, and Al was further vapor-deposited by vacuum vapor-depositing to a thickness of 2 μm to obtain a photovoltaic element (element No.
Actual 10).

Table 1 shows the manufacturing conditions of the photovoltaic element.

[0474]

[Table 1] Comparative Example 10 When forming the i-type layer, a vacuum container 21 as shown in FIG.
The meshes 2135 and 2136 in 00 were removed, and other manufacturing conditions were the same as in Example 10 (element N
o. Ratio 10).

Example 11 When an i-type layer was formed in the same manner as in Example 10, FIG.
As shown in, except that the mesh 2135 and 2136 are arranged in the vacuum container 2100 and the mesh and the strip-shaped member are held at the same potential by a conductive member (not shown),
Under the same manufacturing conditions as in Example 10, a lower electrode, a first conductivity type layer, an i-type layer, a second conductivity type layer, a transparent electrode, and a collector electrode were formed on a strip-shaped member to form a photovoltaic element. Obtained (element N
o. Fruit 11).

Example 10 (element No. Ex. 10), Example 11 (element No. Ex. 11) and Comparative Example 10 (element No. Ex.
The photoelectric conversion efficiency, the characteristic uniformity, and the defect density of the photovoltaic element manufactured in the ratio 10) were evaluated.

The photoelectric conversion efficiency and the characteristic uniformity are the same as those in Example 10.
(Element No. Ex. 10), Example 11 (Element No. Ex. 1)
1) and the photovoltaic element on the belt-shaped member prepared in Comparative Example 10 (element No. ratio 10) were cut out every 10 m in a 5 cm square area, and irradiated with AM-1.5 (100 mW / cm ² ) light. The photoelectric conversion efficiency was measured, and the average value and its variation were evaluated. Example 10 (Element No.
Ex. 10), the photoelectric conversion efficiency of the photovoltaic elements of Example 11 (element No. Ex 11) is comparative example 10 (element No. ratio 10).
1.05 times, respectively, based on the photovoltaic element of 1.
It turned out that it was excellent with 06 times. Table 2 shows the results of characteristic evaluation in which the reciprocal of the magnitude of variation was obtained with the photovoltaic element of Comparative Example 10 (element No. ratio 10) as a reference.

The defect density is as shown in Example 10 (Element No. Ex. 1).
0), Example 11 (element No. Ex 11) and Comparative Example 10
Defects of each photovoltaic element were measured by cutting out 100 5 cm square areas in the range of the central portion 5 m of the photovoltaic element on the strip-shaped member prepared with (element No. ratio 10) and measuring the reverse current. The presence or absence of the defect was detected to evaluate the defect density. Table 2 shows the results of the characteristic evaluation in which the reciprocal of the number of defects was obtained with the photovoltaic device of Comparative Example 10 (device No. ratio 10) as a reference.

[0479]

[Table 2] As shown in Table 2, as compared with the photovoltaic element of Comparative Example 10 (element No. ratio 10), Example 10 (element No. Ex 1) was used.
0) and the photovoltaic elements of Example 11 (element No. Ex. 11) are excellent in conversion efficiency, characteristic uniformity, and defect density, and are photovoltaic elements formed by the manufacturing apparatus of the present invention. However, it was found that they have excellent characteristics, and the effect of the present invention was verified.

Example 12 As shown in FIG. 17, a first conductivity type layer, an i-type layer, a second conductivity type layer, a first conductivity type layer, an i-type layer, and a second conductivity layer were formed on the lower electrode. A tandem-type solar cell in which two mold layers were laminated with two pin junctions was formed. In order to stack two sets of pin junctions, a first conductive type layer forming vacuum is provided between the second conductive type layer forming vacuum container 2100p and the vacuum container 2302 of the deposited film forming apparatus shown in FIG. The container 2100n ′, the i-type layer film forming vacuum container 2100 ′, and the second conductivity type layer film forming vacuum container 2100p ′ are connected via gas gates.

The first pin junction is made of amorphous silicon germanium, and the second pin junction is made of amorphous silicon to form the i layer. The manufacturing conditions are summarized in Table 3.

The meshes are the vacuum containers 2100 and 2100 ′ for forming the i-type layer, as shown in FIG.
6'was arranged as shown (element No. Ex. 12).

[0483]

[Table 3] Comparative Example 11 When forming each layer, a tandem photovoltaic element was prepared under the same manufacturing conditions as in Example 12 without disposing the mesh shown in FIGS. It was created (element No. ratio 11).

Photovoltaic devices produced in Example 12 (element No. Ex. 12) and Comparative Example 11 (element No. ratio 11) were subjected to photoelectric conversion efficiency, characteristic uniformity and The defect density was measured. The results are shown in Table 4.

[0485]

[Table 4] The photoelectric conversion efficiency of the photovoltaic element of Example 12 (element No. Ex. 12) is 1.07 times that of the photovoltaic element of Comparative Example 11 (element No. ratio 11), which is excellent. I understood. In addition, as a result of the measurement of the characteristic uniformity and the defect density, the photovoltaic element of Example 12 (element No. Ex. 12) was compared with the photovoltaic element of Comparative Example 11 (element No. ratio 11). It was found that the characteristic uniformity was 1.22 times and the defect density was 1.25 times better, and that the photovoltaic device formed according to the present invention had excellent characteristics, and the effect of the present invention was verified.

Example 13 A triple-type photovoltaic element shown in FIG. 18 in which three sets of pin junctions of a first conductivity type layer, an i-type layer, and a second conductivity type layer were laminated on a lower electrode was obtained. It was made. In order to stack three sets of pin junctions, the first conductivity type layer formation is performed between the vacuum container 2100p ′ and the vacuum container 2302 for forming the second conductivity type layer of the deposited film forming apparatus shown in the twelfth embodiment. Vacuum container for membrane 21
00n ", vacuum container 2100p" for forming i-type layer, second
Of the vacuum chamber 2100p ″ for forming the conductive type layer is connected via each gas gate. First p
The in-junction is amorphous silicon germanium, the second pin-junction is amorphous silicon, and the third p-junction is
The in-junction is made of amorphous silicon to form each i-layer. The production conditions are summarized in Table 5.

The meshes 2135 and 2136 are provided in the i-type layer film forming vacuum container 2100, and the meshes 2135 ′ and 213 are provided in the i-type layer film forming vacuum container 2100 ′.
6'into the i-type layer deposition vacuum container 2100 '' mesh 2
135 ″ and 2136 ″ are arranged respectively.

[0488]

[Table 5] Comparative Example 12 When each layer was formed, the mesh shown in Example 13 was not placed in each i-type layer film forming vacuum container, and the other manufacturing conditions were the same as in Example 12, and the triple-type light was used. An electromotive force element was produced (element No. ratio 12).

Photovoltaic devices produced in Example 13 (element No. Ex. 13) and Comparative Example 12 (element No. ratio 12) were processed in the same manner as in Example 10 to obtain photoelectric conversion efficiency, characteristic uniformity and The defect density was measured. The results are shown in Table 6.

[0490]

[Table 6] The photoelectric conversion efficiency of the photovoltaic element of Example 13 (element No. Ex. 13) is 1.08 times that of the photovoltaic element of Comparative Example 12 (element No. ratio 12), which is excellent. all right. Further, as a result of the measurement of the characteristic uniformity and the defect density, the photovoltaic element of Example 13 (element No. Ex. 13) was compared with the photovoltaic element of Comparative Example 12 (element No. ratio 12). It was found that the characteristic uniformity was 1.25 times better and the defect density was 1.35 times better, and the photovoltaic device formed according to the present invention had excellent characteristics, and the effect of the present invention was verified.

Example 14 Next, film formation of a functional deposition film for forming a film formation space by bending a belt-shaped member in the carrying direction will be described.

In FIG. 13, reference numeral 2210 (2150) is a belt-shaped member, and is used for supporting / conveying rollers 2202, 220.
3 and the supporting and transporting rings 2204, 2205, while maintaining a cylindrically curved shape, an arrow (→) in the figure
And the film forming space 2216 is continuously formed. 2206a to 2206e are strip members 2201 (2
150) is a temperature control mechanism for heating or cooling, and temperature control is independently performed for each. In this device, a pair of applicators 2207 and 2208 are provided so as to face each other, and a microwave transparent member 220 is provided at the tip portion thereof.
9 and 2210 are provided, and the rectangular waveguides 2211 and 2212 do not have their long sides perpendicular to the plane containing the central axis of the supporting / conveying roller, and The surfaces including the long sides are arranged so as not to be parallel. Note that, in FIG. 13, the applicator 2207 is shown as the support / transport ring 2 for the sake of explanation.
Although it is shown separated from 204, it is arranged in the direction of the arrow in the drawing when the deposited film is formed.

Reference numerals 2213a, 2213b, 2213c are gas introducing means, and the source gas is introduced into the film forming space by a gas supply facility (not shown). The support / conveyance rollers 2202 and 2203 have a conveyance speed detection mechanism and a tension detection adjustment mechanism (not shown) built therein, and the belt-shaped member 2201.
The conveyance speed of (2150) is kept constant and its curved shape is kept constant.

FIG. 15 shows the film formation space described in FIG.
To the vacuum container 2200n for forming the conductive type layer, the vacuum container 2200 for forming the i-type layer, and the vacuum container 2200p for forming the second conductive type layer, respectively, to continuously deposit the functional deposited film. This is a device for film formation. Band-shaped member 2201 (2150)
Vacuum containers 2301 and 2 for feeding and winding
302, a bobbin for sending out the band-shaped member 2150 of 2303 and a bobbin for winding the band-shaped member 2150 of 2304 are arranged. Then, the belt-shaped member is conveyed in the direction of the arrow in the figure. Of course, this can also be reversed and conveyed. Further, the vacuum containers 2303 and 2304 may be provided with winding and feeding means for the interleaving paper used for surface protection of the belt-shaped member 2201 (2150). The material of the interleaving paper, a polyimide-based heat-resistant resin,
Teflon type and glass wool are preferably used. Two
Reference numerals 305 and 2306 denote transport rollers that also adjust the tension and position the belt-shaped member. 2314 and 2315 are pressure gauges, 2309n, 2309, 2309p, 2307,
2308 is a throttle valve for adjusting conductance,
2320n, 2320, 2320b, 2310, 231
Reference numeral 1 denotes an exhaust pipe, which is connected to an exhaust pump (not shown). 2217 and 2218 are meshes, respectively.

The microwave applicator is the same as that described above with reference to FIG.

FIG. 14 is a view of the film forming space viewed from the width direction of the strip-shaped member. In FIG. 14, meshes 2217 and 2218 are shown.
Is the film forming space 2 of the strip member 2150 (2201).
It is arranged so as to be close to the carry-in side and the carry-out side of 216.

Photovoltaic devices were continuously manufactured using the apparatus shown in FIG.

First, a vacuum container 2301 having a substrate feeding mechanism is thoroughly degreased and washed, and a silver thin film of 100 nm and Z is formed as a lower electrode by a sputtering method.
SUS430BA band-shaped member 2150 (width 120 mm x length 200 m x thickness 0.
(13 mm) wound bobbin 2303 is set and passed through the belt-shaped member 2201, the gas gate, and the vacuum containers 2200n, 2200, 2200p for film formation of each layer to the vacuum container 2302 having a belt-shaped member winding mechanism,
The tension was adjusted so that there was no slack.

Therefore, the respective vacuum vessels 2301, 2302,
2200n, 2200, and 2200p were evacuated to 1 × 10 ⁻⁶ Torr or less by a vacuum pump (not shown).

Next, a gate gas introducing pipe 21 is attached to the gas gate.
H ₂ as a gate gas is caused to flow at 700 sccm from 31n, 2131, 2132, and 2131p, and the belt-shaped member 2150 is moved by the temperature adjusting mechanisms 2206a to 2206e.
Heated to 350 ° C., 350 ° C. and 300 ° C., respectively, and 40 sccc of SiH ₄ gas from the gas introduction means 2213n.
m, PH ₃ / H ₂ (1%) gas at 200 sccm, H ₂
Gas is 400 sccm, gas introducing means pipes 2213a, 2
From 213b and 2213c, the total SiH ₄ gas is 400 sccm, the H ₂ gas is 200 sccm, and the SiH ₄ gas is 20 sccm from the gas introducing means 2213p.
F ₃ (1%) gas 100 sccm, H ₂ gas 500
sccm was introduced.

The pressure in the vacuum container 2200n is 40 mT.
The opening of the conductance adjusting throttle valve 2309n was adjusted while observing the pressure gauge (not shown) so as to be orr. The pressure inside the vacuum container 2200 is 5 mTorr.
The opening of the conductance valve 2305 was adjusted while observing the pressure gauge (not shown) so that Vacuum container 2200
The opening of the throttle valve 2309p was adjusted while observing the pressure gauge (not shown) so that the pressure in p was 40 mTorr. And the applicator 2207n, 2208n, 220 which connected the microwave electric power to each vacuum container
7, 2, 208, 2207p, 2208p, through the microwave transparent member, microwave power 800
W, 800W, 500W, 500W, 800W, 800
W was introduced.

Next, the strip-shaped member 2150 is conveyed in the direction of the arrow in the figure, and the first conductivity type layer, i-type layer, and
A second conductivity type layer was formed.

Next, ITO (In ₂ O ₃ + SnO ₂ ) was formed as a transparent electrode on the second conductivity type layer by vacuum evaporation.
0 nm was vapor-deposited, and Al was further vapor-deposited by 2 μm as a collector electrode by vacuum vapor deposition to obtain a photovoltaic element (Element No. Ex 14).

Table 7 shows the conditions for producing the photovoltaic element described above.

[0505]

[Table 7] Comparative Example 13 When forming the i-type layer, the meshes 2217 and 2218 in the vacuum container 2200 as shown in FIGS. 13 and 14 were removed, and the other manufacturing conditions were the same as in Example 14 (Element No. Ratio 13).

Example 15 In the case of forming an i-type layer in Comparative Example 13, as shown in FIGS.
As shown in FIG. 4, a mesh 221 is placed inside the vacuum container 2200.
No. 7, 2218 was provided, and these meshes were made to have the same electric potential by a conductive member (not shown).
A lower electrode, a first conductivity type layer, an i-type layer, a second conductivity type layer, a transparent electrode, and a collector electrode are formed on the strip-shaped member under the same film forming conditions as in No. 4 to obtain a photovoltaic element. (Element No. Ex 1
5).

Example 14 (Element No. Ex. 14), Example 15 (Element No. Ex. 15) and Comparative Example 13 (Element No. Ex.
The photoelectric conversion efficiency, the characteristic uniformity, and the defect density of the photovoltaic element manufactured in the ratio 13) were evaluated.

The characteristic uniformity is shown in Example 14 (element No.
14), Example 15 (element No. Ex. 15) and Comparative Example 1
Photovoltaic on the strip-shaped member manufactured with No. 3 (element No. ratio 13)
A force element is cut out every 10 m in an area of 5 cm square, and AM
-1.5 (100 mW / cm ²) Installed under light irradiation,
The photoelectric conversion efficiency is measured and the average is calculated, and the photoelectric conversion efficiency is calculated.
The variation in the rate was evaluated.

The photoelectric conversion efficiencies of the photovoltaic elements of Example 14 (element No. Ex 14) and Example 15 (element No. Ex 15) were the same as those of Comparative Example 13 (element No. ratio 13). It was found to be excellent, being 1.06 times and 1.07 times, respectively, as a reference.

Table 8 shows the results of the characteristic evaluation in which the characteristic uniformity, which is the reciprocal of the variation, was obtained with the photovoltaic element of Comparative Example 13 (element No. ratio 13) as a reference.

The defect density is as shown in Example 14 (Element No. Ex. 1).
4), Example 15 (element No. Ex. 15) and Comparative Example 13
Defects of each photovoltaic element were measured by cutting out 100 5 cm square areas in the range of the central portion 5 m of the photovoltaic element formed on the strip-shaped member (element No. ratio 13) and measuring the reverse current. The presence or absence of the defect was detected to evaluate the defect density. Table 8 shows the results of the characteristic evaluation in which the reciprocal of the number of defects was obtained with the photovoltaic device of Comparative Example 13 (device No. ratio 13) as a reference.

[0512]

[Table 8] As shown in Table 8, as compared with the photovoltaic element of Comparative Example 13 (element No. ratio 13), Example 14 (element No. Ex. 1) was used.
4) and the photovoltaic element of Example 15 (element No. Ex. 15) are excellent in both characteristic uniformity and defect density, and the photovoltaic element formed according to the present invention has excellent characteristics. It has been proved to have the effect, and the effect of the present invention has been proved.

Example 16 A photovoltaic element was continuously manufactured by the manufacturing apparatus of the present invention shown in FIG.

First, a vacuum container 3310 having a substrate feeding mechanism is thoroughly degreased and washed, and a silver thin film of 100 nm and Z is formed as a lower electrode by a sputtering method.
SUS430BA band-shaped member 3150 (width 120 mm x length 200 m x thickness 0.
13 mm) wound bobbin 3303 is set, the belt-shaped member 3150 is a gas gate, a vacuum container 3100n ′ for forming a first conductive type layer, a vacuum container 3100 for forming an i-type layer, and a second conductive layer. Vacuum container 3100 for forming mold layer
Vacuum container 3 having a belt-shaped member winding mechanism via p
The tension was adjusted to the extent that there was no slack through the wire up to 302.

Therefore, each vacuum container 3301, 3100
n, 3100, 3100p and 3302 were evacuated to 1 × 10 ⁻⁶ Torr or less by a vacuum pump (not shown).

Next, the gas gates 3129n, 3129,
3130, 3129p to the gate gas introduction pipe 3131n,
700 sccm of H ₂ was made to flow from 3131, 3132, and 3131p as a gate gas, and the infrared lamp 3 for heating was used.
The belt-shaped member 31 is formed by 124n, 3124, and 3124p.
50 are heated to 350 ° C. each. Then, SiH ₄ gas is supplied at 20 sccm and PH by the gas introducing means 3114n.
₃ / H ₂ (1%) gas at 200 sccm, H ₂ gas at 2
00 sccm, gas introducing means 3114, 3115, 31
16 from 200 sccm of SiH ₄ gas, H
₂ gas at 200 sccm, SiH ₄ gas at 30 sccm, and BF ₃ / H ₂ (1
%) Gas and H ₂ gas at 250 sccm were introduced. The pressure in the vacuum container 3100n is 30 mTorr
The opening of the throttle valve 3127n was adjusted while observing the pressure gauge (not shown) so as to be r. Vacuum container 3100
The opening of the throttle valve 3127 was adjusted while observing the pressure gauge (not shown) so that the internal pressure became 6 mTorr. The pressure in the vacuum container 3100p is 30 mTorr.
The opening of the throttle valve 3127p was adjusted while observing the pressure gauge (not shown) so that

Thereafter, the microwave power is applied to the applicator 3
105n, 3105, 3106, 3107, 3105p
Power is applied to each of the microwave transparent members 310.
8n, 3108, 3109, 3110, 3108p, microwave power 1000W, 300W, 300
W, 300W, 1000W is introduced, and then the strip-shaped member 31
50 is conveyed in the direction of the arrow in the figure, and the first member is placed on the belt-shaped member.
Of the conductivity type, the i-type layer, and the second conductivity type layer were formed.

When forming the n-type layer, a mesh 3133n was placed in a vacuum container 3100n as shown in FIG.

Next, ITO (In ₂ O ₃ + SnO ₂ ) was formed as a transparent electrode on the second conductivity type layer by vacuum evaporation.
0 nm was vapor-deposited, and Al was further vapor-deposited by 2 μm as a collector electrode by vacuum vapor deposition to form a photovoltaic element (element N
o. Actual 16).

Table 9 shows the manufacturing conditions of the above photovoltaic element.

[0521]

[Table 9] Comparative Example 14 When forming the n-type layer, the vacuum container 3 as shown in FIG.
The mesh 3133n in 100n was removed, and the other film forming conditions were the same as in Example 16 (element No. ratio 14).

Example 17 A strip-shaped member was produced under the same manufacturing conditions as in Comparative Example 14 except that a mesh 3133 was provided in a vacuum container 3100 as shown in FIG. 19 when forming an i-type layer in Comparative Example 14. A lower electrode, a first conductivity type layer, an i-type layer, a second conductivity type layer, a transparent electrode, and a collector electrode were formed on the above to obtain a photovoltaic element (Element No. Example 17).

Example 18 A strip-shaped member was produced under the same manufacturing conditions as in Comparative Example 14 except that when a p-type layer was formed in Comparative Example 14, a mesh 3133p was arranged in a vacuum container 3100p as shown in FIG. A lower electrode, a first conductivity type layer, an i-type layer, a second conductivity type layer, a transparent electrode, and a collector electrode were formed on the above to obtain a photovoltaic element (Element No. Example 18).

Example 19 In forming the n, i, p-type layers in Comparative Example 14, vacuum vessels 3100n, 310 as shown in FIGS.
Meshes 3133n and 31 in 0 and 3100p respectively
33, 3133p were provided, and under the same manufacturing conditions as in Comparative Example 14, the lower electrode, the first conductivity type layer, the i-type layer, the second conductivity type layer, the transparent electrode, and the current collector were formed on the belt-shaped member. Electrodes were formed to obtain a photovoltaic element (Element No. Ex. 19).

Example 16 (Element No. Ex 16) to Example 19 (Element No. Ex 19) and Comparative Example 14 (Element N)
o. The uniformity of characteristics and the defect density of the photovoltaic element manufactured according to the ratio 14) were evaluated.

The characteristic uniformity is shown in Example 16 (element No.
16) to Example 19 (Element No. Ex. 19) and Comparative Example 1
Photovoltaic on a strip-shaped member prepared in No. 4 (element No. ratio 14)
A force element is cut out every 10 m in an area of 5 cm square, and AM
-1.5 (100 mW / cm ²) Installed under light irradiation,
Measure the photoelectric conversion efficiency and measure the variation in the photoelectric conversion efficiency.
evaluated. Photovoltaic power of Comparative Example 14 (element No. ratio 14)
Calculate the reciprocal of the magnitude of variation based on the element
Table 10 shows the results of evaluation of uniformity of properties.

The defect density is as shown in Example 16 (element No. Ex. 1).
6) to Example 19 (Element No. Ex. 19) and Comparative Example 14
Defects of each photovoltaic element were measured by cutting out 100 5 cm square areas in the range of the central portion 5 m of the photovoltaic element on the strip-shaped member prepared in (Element No. ratio 14) and measuring the reverse current. The presence or absence of the defect was detected to evaluate the defect density. Table 10 shows the results of the characteristic evaluation in which the reciprocal of the number of defects was obtained with the photovoltaic device of Comparative Example 14 (device No. ratio 14) as a reference.

[0528]

[Table 10] As shown in Table 10, Comparative Example 14 (element No. ratio 14)
Example 16 (element No. Ex. 1)
The photovoltaic elements of 6) to Example 19 (element No. 19) are excellent in both property uniformity and defect density, and the photovoltaic elements formed by the manufacturing apparatus of the present invention are excellent. It was found to have mass productivity, and the effect of the present invention was verified.

Example 20 As shown in FIG. 27, a first conductivity type layer, an i-type layer, a second conductivity type layer, a first conductivity type layer, an i-type layer, and a second conductivity layer were formed on the lower electrode. A tandem-type solar cell in which two mold layers were laminated with two pin junctions was formed. In order to stack two sets of pin junctions, the first conductivity type layer deposition vacuum is provided between the second conductivity type layer deposition vacuum container 3100p and the vacuum container 3302 of the deposited film forming apparatus shown in FIG. The container 3100n ′, the i-type layer film forming vacuum container 3100 ′, and the second conductivity type layer film forming vacuum container 3100p ′ are connected to each other through respective gas gates.

The first pin junction is made of amorphous silicon germanium, and the second pin junction is made of amorphous silicon to form the i layer. The production conditions are summarized in Table 11.

[0531] The mesh is composed of a vacuum container 3100n for forming the first conductivity type layer and a vacuum container 310 for forming the i-type layer.
0, the vacuum container 3100p for forming the second conductivity type layer, the first
Of the vacuum container 3100n ′ for forming the conductive type layer, the vacuum container 3100 ′ for forming the i-type layer, and the vacuum container 3100p ′ for forming the second conductive type layer (element No. ．
Actual 20).

[0532]

[Table 11] Comparative Example 15 A tandem photovoltaic element was prepared under the same manufacturing conditions as in Example 20, without disposing the mesh shown in FIGS. 19 and 20 in the vacuum container for forming each layer when forming each layer. It was manufactured (element No. ratio 15).

The photovoltaic elements manufactured in Example 20 (element No. Ex. 20) and Comparative Example 15 (element No. ratio 15) were measured for characteristic uniformity and defect density in the same manner as in Example 16. Was done. As a result of the measurement, Comparative Example 15 (element N
o. Compared with the photovoltaic element having a ratio of 15), the photovoltaic element of Example 20 (element No. Ex. 20) has a characteristic uniformity of 1.
34 times, the defect density was 1.49 times better, and it was found that the photovoltaic element manufactured according to the present invention had excellent mass productivity, and the effect of the present invention was verified.

Example 21 A triple type photovoltaic device shown in FIG. 28, in which three sets of pin junctions of a first conductivity type layer, an i type layer and a second conductivity type layer are laminated on a lower electrode is shown. It was made. In order to stack three sets of pin junctions, between the vacuum vessel 3100p ′ for producing the second conductivity type layer and the vacuum vessel 3302 of the deposited film forming apparatus shown in the embodiment 20, for producing the first conductivity type layer. Vacuum container 31
00n ″, a vacuum container 3100 ″ for forming an i-type layer, and a vacuum container 3100p ″ for forming a second conductivity type layer are connected to each other through respective gas gates. First pi
The n-junction is amorphous silicon germanium, the second pin junction is amorphous silicon, and the third pi is
Each of the n-junctions is made of amorphous silicon to form an i-layer. The production conditions are summarized in Table 12.

The mesh is composed of the first conductive type layer film forming vacuum containers 3100n, 3100n ′, 3100n ″, the i type layer film forming vacuum containers 3100, 3100 ′, 3100 ″,
Second conductivity type layer forming vacuum container 3100p, 3100
All of p ′ and 3100p ″ were arranged.

[0536]

[Table 12] Comparative Example 16 In forming each layer, the mesh shown in Example 20 was not arranged in the vacuum container for forming each layer, and other production conditions were the same as in Example 20, and the triple photovoltaic element was used. Was produced (element No. ratio 16).

The photovoltaic elements manufactured in Example 21 (element No. Ex. 21) and Comparative Example 16 (element No. ratio 16) were measured for uniformity of characteristics and defect density in the same manner as in Example 16. Was done. As a result of the measurement, Comparative Example 16 (element N
o. Compared with the photovoltaic element having a ratio of 16), the photovoltaic element of Example 21 (element No. Ex. 21) has a characteristic uniformity of 1.
It was found that the photovoltaic element manufactured according to the present invention had excellent mass productivity, with 40 times better defect density and 1.55 times better defect density, demonstrating the effect of the present invention.

Example 22 Next, the production of a functional deposition film in which a film formation space is formed by bending a belt-shaped member in the carrying direction will be described.

In FIG. 23, 3210 (3150) is a belt-shaped member, and is used for supporting / conveying rollers 3202, 320.
3 and the supporting and carrying rings 3204, 3205 while maintaining a cylindrically curved shape, an arrow (→) in the figure
And the film forming space 3216 is continuously formed. 3206a to 3206e are strip members 3201 (3
150) is a temperature control mechanism for heating or cooling, and temperature control is independently performed for each. In this device, a pair of applicators 3207 and 3208 are provided so as to face each other, and a microwave permeable member 320 is provided at a tip portion thereof.
9, 3210 are provided respectively, and the rectangular waveguides 3211, 3212 are so arranged that their long sides are not perpendicular to the plane containing the central axis of the supporting / conveying roller, and The surfaces including the long sides are arranged so as not to be parallel. In FIG. 23, the applicator 3207 is shown as a support / transport ring 32 for the sake of explanation.
Although it is shown as separated from 04, it is arranged in the direction of the arrow in the drawing when the deposited film is formed.

Reference numerals 3213a, 3213b, and 3213c are gas introducing means, and the source gas is introduced into the film forming space by a gas supply facility (not shown). The support / conveyance rollers 3202 and 3203 have a conveyance speed detection mechanism and a tension detection adjustment mechanism (not shown) built therein.
The conveyance speed of (3150) is kept constant, and its curved shape is kept constant. FIG. 25 shows that the film formation space of FIG. 23 is applied to a vacuum container 3200n for forming a first conductivity type layer, a vacuum container 3200 for forming an i-type layer, and a vacuum container 3200p for forming a second conductivity type layer. It is a device for continuously producing a functional deposited film. Vacuum containers 3301 and 3302 for feeding and winding the belt-shaped member 3201 (3150)
Is a bobbin for feeding the band member 3150 of 3303,
A bobbin for winding the band-shaped member 3150 of 3304 is arranged. Then, the belt-shaped member is conveyed in the direction of the arrow in the figure. Of course, this can also be reversed and conveyed. Further, in the vacuum containers 3303 and 3304, the strip-shaped member 3 is
The interleaving paper winding and feeding means used for surface protection of 201 (3150) may be provided. As the material of the interleaving paper, polyimide, Teflon, glass wool and the like which are heat resistant resins are preferably used. 330
Numerals 5 and 3306 are conveying rollers that also adjust the tension and position the belt-shaped member. 3314 and 3315 are pressure gauges, 3309n, 3309, 3309p, 3307 and 3
308 is a throttle valve for adjusting conductance, 3
320n, 3320, 3320b, 3310, 3311
Are exhaust pipes, each connected to an exhaust pump (not shown). 3217 is a mesh.

The microwave applicator is the same as that described above with reference to FIG.

FIG. 24 is a view of the film forming space viewed from the width direction of the strip-shaped member. In FIG. 24, meshes 3217 and 3217 are shown.
n and 3217p are strip members 315 in the film formation space, respectively.
They are arranged so as to be close to each other over the entire 0 deposition surface.

Photovoltaic devices were continuously manufactured using the apparatus shown in FIG.

First, a vacuum container 3301 having a substrate feeding mechanism is thoroughly degreased and washed, and a silver thin film of 100 nm and Z is formed as a lower electrode by a sputtering method.
SUS430BA belt-shaped member 3150 (3201) (width 120 mm x length 200) on which an nO thin film is deposited by 1 μm
m × thickness 0.13 mm) wound bobbin 330
3 is set, and a vacuum container 3302 having a belt-shaped member winding mechanism is provided via the belt-shaped member 3201, the gas gate, and the vacuum containers 3200n, 3200, and 3200p for forming each layer.
The tension was adjusted so that there was no slack.

Therefore, each vacuum container 3301, 3302,
The 3200n, 3200, and 3200p were evacuated to 1 × 10 ⁻⁶ Torr or less by a vacuum pump (not shown).

Next, the gate gas introduction pipe 31 is attached to the gas gate.
H ₂ as a gate gas was made to flow at 700 sccm from 31n, 3131, 3132, and 3131p, and the belt-shaped member 3150 was set by the temperature adjusting mechanisms 3206a to 3206e.
Heated to 350 ° C., 350 ° C. and 300 ° C., respectively, and 40 sccc of SiH ₄ gas from the gas introducing means 3213n.
m, PH ₃ / H ₂ (1%) gas at 200 sccm, H ₂
Gas is 400 sccm, gas introducing means pipes 3213a, 3
213b and 3213c, 400 sccm of SiH ₄ gas in total, 200 sccm of H ₂ gas, 20 sccm of SiH ₄ gas from the gas introducing means 3213p, B
F ₃ (1%) gas 100 sccm, H ₂ gas 500
sccm was introduced.

The pressure in the vacuum container 3200n is 40 mT.
The opening of the conductance adjusting throttle valve 3309n was adjusted while looking at the pressure gauge (not shown) so as to be orr. The pressure inside the vacuum container 2200 is 5 mTorr.
The opening of the conductance valve 3305 was adjusted while observing the pressure gauge (not shown) so that Vacuum container 3200
The opening of the throttle valve 3309p was adjusted while observing the pressure gauge (not shown) so that the pressure in p was 40 mTorr. Then, the applicators 3207n, 3208n, 320 connected to the respective vacuum vessels with microwave power.
A microwave power of 800 is applied to each of 7, 3208, 3207p, and 3208p through a microwave transparent member.
W, 800W, 500W, 500W, 800W, 800
W was introduced.

Next, the strip-shaped member 3150 is conveyed in the direction of the arrow in the drawing, and the first conductivity type layer, the i-type layer, and
A second conductivity type layer was produced.

Next, ITO (In ₂ O ₃ + SnO ₂ ) was formed as a transparent electrode on the second conductivity type layer by vacuum evaporation.
0 nm was vapor-deposited, and Al was further vapor-deposited by vacuum vapor-depositing to a thickness of 2 μm as a collector electrode to fabricate a photovoltaic element (element N
o. Actual 22).

Table 13 shows the above-mentioned conditions for manufacturing the photovoltaic element.
Shown in.

When forming the n-type layer, a mesh 3217n was placed in a vacuum container 3200n as shown in FIGS.

[0552]

[Table 13] Comparative Example 17 When forming the n-type layer, the mesh 3217n in the vacuum container 3200n as shown in FIGS.
Other manufacturing conditions were the same as in Example 22 (element N
o. Ratio 17).

Example 23 When the i-type layer was formed in Comparative Example 17, as shown in FIGS.
As shown in FIG. 4, a mesh 3217 is placed in the vacuum container 3200.
Except that, under the same manufacturing conditions as in Comparative Example 17, the lower electrode, the first conductivity type layer, the i-type layer, the second conductivity type layer, the transparent electrode, and the current collecting electrode were formed on the belt-shaped member, and light was formed. An electromotive force element was produced (element No. Ex. 23).

Example 24 When a p-type layer was formed in Comparative Example 17, the results shown in FIGS.
4, the mesh 321 is placed in the vacuum container 3200p.
Under the same manufacturing conditions as in Comparative Example 17, except that 7p was provided,
A lower electrode, a first conductivity type layer, an i-type layer, a second conductivity type layer, a transparent electrode, and a collector electrode were formed on the strip-shaped member to fabricate a photovoltaic element (Element No. Example 24). .

Example 25 In forming the n, i, p-type layers in Comparative Example 17, vacuum vessels 3200n, 320 as shown in FIGS.
Meshes 3217n, 3217, 3 in 0, 3200p
Under the same manufacturing conditions as in Comparative Example 17, except that 217p were provided, the lower electrode, the first conductivity type layer, the i-type layer, the second conductivity type layer, the transparent electrode, and the current collecting electrode were formed on the strip-shaped member. To form a photovoltaic element (Element No. Ex. 25).

The uniformity of characteristics and the defect density of the photovoltaic elements produced in Example 22 (element No. Ex. 22) to Example 25 and Comparative Example 17 (element No. ratio 17) were evaluated.

The characteristic uniformity is shown in Example 22 (element No.
22) to Example 25 (element No. Ex. 25) and Comparative Example 1
Photovoltaic on a strip-shaped member manufactured with No. 7 (element No. ratio 17)
A force element is cut out every 10 m in an area of 5 cm square, and AM
-1.5 (100 mW / cm ²) Installed under light irradiation,
Measure the photoelectric conversion efficiency and measure the variation in the photoelectric conversion efficiency.
evaluated. Photovoltaic power of Comparative Example 14 (element No. ratio 14)
Calculate the reciprocal of the magnitude of variation based on the element
Table 14 shows the results of evaluation of uniformity of property.

The defect density is as shown in Example 22 (Element No. Ex. 2).
2), Example 25 (element No. Ex. 25) and Comparative Example 17
Defects of each photovoltaic element were measured by cutting out 100 areas of 5 cm square in the area of the central portion 5 m of the photovoltaic element on the strip-shaped member produced in (Element No. ratio 17) and measuring the reverse current. The presence or absence of the defect was detected to evaluate the defect density. Table 14 shows the results of evaluating the defect density by obtaining the reciprocal of the number of defects with reference to the photovoltaic device of Comparative Example 17 (device No. ratio 17).

[0559]

[Table 14] As shown in Table 14, Comparative Example 17 (element No. ratio 17)
Example 22 (element No. Ex. 2)
The photovoltaic elements of 2) to Example 25 (element No. 25) are excellent in both property uniformity and defect density, and the photovoltaic element manufactured according to the present invention has excellent mass productivity. It was found that the effect of the present invention was demonstrated.

[0560]

INDUSTRIAL APPLICABILITY In a microwave plasma CVD method in which a raw material gas for forming a deposited film is decomposed by microwave energy under a low pressure to form a deposited film on a substrate, an internal pressure of 50 mTorr
At a vacuum degree of r or less, the microwave energy smaller than the microwave energy required for 100% decomposition of the raw material gas is applied to the raw material gas, and the rf energy larger than the microwave energy to be applied is applied to the raw material gas. And applying a DC bias voltage to the mesh by interposing a mesh made of a conductive metal between the substrate and the space where the source gas is mainly decomposed by the microwave energy to act on the mesh. The following effects were obtained by using the deposited film forming method of the present invention characterized by:

(1) It has become possible to form a deposited film of a non-single-crystal semiconductor film, which has excellent electrical characteristics and little photodegradation even when the deposition rate is increased to several nm / sec or more.

(2) By increasing the uniformity and stability of plasma, unevenness in the thickness and characteristics of the deposited film formed is reduced, and as a result, for photovoltaic devices, thin film transistors, sensors, electrophotography. The device characteristics such as the light receiving member and the yield have been improved, and it has become possible to reduce the manufacturing cost of these electronic devices.

(3) Active species having energy that effectively contributes to structural relaxation of the film are uniformly supplied over a large area during formation of the deposited film while suppressing the occurrence of abnormal discharge that adversely affects the properties of the deposited film. It is possible to reduce the damage to the surface of the deposited film by unnecessary ions and electrons that adversely affect the characteristics of the deposited film, and it is possible to uniformly form a deposited film having desired characteristics.

In the microwave plasma CVD method of decomposing the raw material gas for depositing a deposited film with microwave energy under a low pressure to form a deposited film on the substrate, an internal pressure of 50 mTo
A microwave energy smaller than the microwave energy required for 100% decomposition of the source gas at a vacuum degree of rr or less is applied to the source gas, and at the same time, an rf energy larger than the microwave energy to be applied is applied to the source gas. And a mesh made of a conductive metal is interposed between the substrate and the space in which the source gas is mainly decomposed by the applied microwave energy, and the mesh is kept at a temperature of 100 ° C. or higher during formation of the deposited film. The same effect as described above was obtained by using the deposited film forming method of the present invention, which is characterized by heating and holding the film.

In the microwave plasma CVD method of decomposing the raw material gas for depositing the deposited film with microwave energy under a low pressure to form the deposited film on the substrate, the internal pressure is 50 mTo
A microwave energy smaller than the microwave energy required for 100% decomposition of the source gas at a vacuum degree of rr or less is applied to the source gas, and at the same time, an rf energy larger than the microwave energy to be applied is applied to the source gas. A mesh made of a conductive metal is interposed between the substrate and the space where the source gas is mainly decomposed by the applied microwave energy, and an rf bias voltage is applied to the mesh. The same effect as above can be obtained by using the deposited film forming method of the present invention.

On the other hand, a film forming space is provided in a vacuum container capable of being evacuated, and the belt-shaped member is continuously conveyed in the longitudinal direction thereof to penetrate the film forming space, and the belt-shaped member in the film forming space is moved. In a device for producing a functional deposited film that decomposes a raw material gas by microwave plasma on a surface to form a deposited film, one or both of a carry-in side and a carry-out side of the strip-shaped member in the film formation space, a predetermined range By using the deposited film forming apparatus of the present invention, characterized in that the porous conductive member is disposed so as to be close to the deposition surface of the strip-shaped member, In continuous production,
In addition to achieving high photoelectric conversion efficiency over a large area, it has become possible to reproducibly produce a large number of photovoltaic devices with excellent uniformity and few defects.

In the above tenth to fifteenth embodiments, i
Although the description has been mainly given to the production of the buffer layer of the mold layer, a mesh made of a conductive metal is arranged in each film formation space when the first and second conductive type layers are prepared to prevent ion bombardment. It is also possible to reduce and improve the device characteristics.

[0568] Further, a film forming space is provided in a vacuum container capable of being evacuated, and the belt-shaped member is continuously conveyed in the longitudinal direction thereof and penetrates the film forming space, and the belt-shaped member in the film forming space is In a device for producing a functional deposited film that decomposes a raw material gas by microwave plasma to form a deposited film on the surface, a porous conductive member is provided over the entire deposition surface of the strip-shaped member in the film formation space. By using the deposited film production apparatus of the present invention, which is arranged so as to be close to the deposition surface, it is possible to maintain stable microwave plasma for a long time, particularly in the continuous production of photovoltaic elements. As a result, it is possible to reproducibly produce a large number of photovoltaic elements with high quality and excellent uniformity over a large area and with few defects.
It was further promoted as compared with the above-mentioned device provided with a mesh in one part.

Also, the impact of high-energy ion species in microwave plasma on the surface of the substrate and the surface of the deposited film can be suppressed, which not only improves the characteristics of the photovoltaic element but also reduces film peeling from the strip-shaped member. , It has become possible to improve the photodegradation characteristics.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view of a film forming apparatus system suitable for applying a deposited film forming method of the present invention.

FIG. 2 is a schematic explanatory view showing a mode example of a photovoltaic element that is preferably formed by the deposited film forming method of the present invention.

FIG. 3 is a schematic explanatory view showing an example of a DC magnetron sputtering apparatus.

FIG. 4 is a schematic explanatory view showing an example of a resistance heating vacuum vapor deposition apparatus.

FIG. 5 is a schematic explanatory view of a film forming apparatus system suitable for applying the deposited film forming method of the present invention.

FIG. 6 is a graph showing the relationship between the preset temperature of the mesh and the photoelectric conversion efficiency when forming the i-type layer.

FIG. 7 is a graph showing the relationship between the set temperature of the mesh and the deterioration rate of the deposited film when forming the i-type layer.

FIG. 8 is a schematic explanatory view of a film forming apparatus system suitable for applying the deposited film forming method of the present invention.

FIG. 9 is a conceptual schematic diagram showing an example of an i-type layer forming film forming container in the deposited film manufacturing apparatus of the present invention.

FIG. 10 is a graph conceptually showing a pressure gradient in the vicinity of a gas gate that is preferably used in the device of the present invention.

FIG. 11 is a schematic explanatory view showing one mode of a film forming apparatus of the present invention suitable for continuously forming a film of photovoltaic elements.

FIG. 12 is a partial cross-sectional view showing one structural example of a microwave applicator suitable for the device of the present invention.

FIG. 13 is a partial cutaway perspective view schematically showing a configuration example of a film forming space portion in the i-type layer film forming vacuum container of the device of the present invention.

14 is a cross-sectional view of a film forming space portion in the i-type layer film forming vacuum container shown in FIG.

FIG. 15 is a schematic explanatory view showing another aspect of the film forming apparatus of the present invention, which is suitable for continuously forming a film of photovoltaic elements.

FIG. 16 is a cross-sectional view showing several aspects of a photovoltaic element that is preferably manufactured by the film forming apparatus of the present invention.

FIG. 17 is a cross-sectional view showing several aspects of a photovoltaic element that is preferably manufactured by the film forming apparatus of the present invention.

FIG. 18 is a cross-sectional view showing several aspects of a photovoltaic element that is preferably manufactured by the film forming apparatus of the present invention.

FIG. 19 is a conceptual schematic diagram showing one embodiment of an i-type layer forming film forming container in the second film forming apparatus of the present invention.

FIG. 20 is a conceptual schematic diagram showing one embodiment of an n, p-type layer forming film forming container in the second film forming apparatus of the present invention.

FIG. 21 is a schematic explanatory view showing one mode of a second film forming apparatus of the present invention, which is suitable for continuously forming a photovoltaic element.

FIG. 22 is a microwave applicator suitable for the present invention.
It is a fragmentary sectional view showing a mode.

FIG. 23 is a partially broken perspective view schematically showing one mode of a film forming space portion in the vacuum container for forming n, i and p type layers of the device of the present invention.

FIG. 24 is a transverse cross-sectional view of a film forming space in the vacuum container for forming n, i and p type layers shown in FIG. 23.

FIG. 25 is a schematic explanatory view showing another aspect of the second film-forming apparatus of the present invention, which is suitable for continuously forming a photovoltaic element.

FIG. 26 is a cross-sectional view showing several aspects of a photovoltaic element preferably manufactured by the second device of the present invention.

FIG. 27 is a cross-sectional view showing several aspects of a photovoltaic device that is suitably manufactured by the second device of the present invention.

FIG. 28 is a cross-sectional view showing several aspects of a photovoltaic device preferably manufactured by the second device of the present invention.

[Explanation of symbols]

100 film forming apparatus 101 deposition chamber 102 dielectric window 103 gas introduction tube 104 substrate 105 heating heater 106 vacuum gauge 107 conductance valve 108 auxiliary valve 109 leak valve 110 waveguide section 112 bias rod 113 mesh 114 mesh bias power supply 115 shutter 116 mesh Temperature controller 117 rf power supply for mesh 1020 raw material gas supply device 1041 to 1046 introduction valve 1021 to 1026 mass flow controller 1031 to 1036 mass flow controller 1
Next valve 1061-1066 Pressure regulator 1051-1056 Valve 1071-1076 Cylinder 200, 210 Photovoltaic element 201, 211 Conductive substrate 202, 212 Light reflection layer 203, 213 Reflection increasing layer 204, 214 Conductivity type layer 205, 215 218 i-type layer 206, 216, 217, 219 conductive type layer 207, 220 transparent electrode 208, 221 current collecting electrode 209, 222 irradiation light 301 deposition chamber 302 substrate 303 heating heater 304, 308 target 305, 309 insulating support 306, 310 DC power source 307, 311 Shutter 312 Vacuum gauge 313 Conductance valve 314, 315 Gas introduction valve 316, 317 Mass flow controller 401 Deposition chamber 402 Substrate 403 Heating heater 404 Deposition source 40 Heater 406 AC power 407 shutter 408 vacuum gauge 409 a conductance valve 410 gas introduction valve 411 mass flow controllers 412 leak valve 413 film thickness monitor 2100,2100n, 2100p, 2301,230
2 Vacuum container 2101 i-type layer forming film forming container 2101n First conductivity type layer forming film forming container 2101p Second conductivity type layer forming film forming container 2102, 2102n, 2102p, 2103, 210
4 film forming spaces 2105, 2105n, 2105p, 2106, 210
7 Applicators 2108, 2108n, 2108p, 2109, 211
0 microwave transparent member 2111, 2111n, 2111p, 2112, 211
3 Waveguides 2114, 2114n, 2114p, 2115, 211
6 Gas introduction means 2117, 2117n, 2117p, 2118, 211
9 gas supply pipes 2120, 2120n, 2120p, 2121, 212
2 Exhaust punching board 2123, 2123n, 2123p Lamp house 2124, 2124n, 2124p Infrared lamp heater 2125, 2125n, 2125p, 2126 Exhaust pipe 2127, 2127n, 2127p, 2128 Exhaust throttle valve 2129, 2129n, 2129p, 2130, 231
1, 2312 gas gates 2131, 2131n, 2131p, 2132n, 21
32p, 2132 Gate gas supply pipe 2133, 2133n, 2133p Exhaust pipe 2134, 2134n, 2134p Thermocouple 2135, 2136 Mesh 2150 Band member 2220 i-type layer film forming vacuum container 2220n First conductive type layer film forming vacuum container 2220p No. 2 vacuum container 2201 for forming a conductive type layer 2202n, 2202p, 2202, 2203, 220
2p, 2203p Transport rollers 2204n, 2205n, 2204, 2205, 220
4p, 2205p Transport ring 2206na, 2206nb, 2206a to e, 220
6pa, 2206pb temperature adjustment mechanism 2207n, 2208n, 2207, 2208, 220
7p, 2208p applicator 2209n, 2210n, 2209, 2210, 220
9p, 2210p microwave permeable member 2211n, 2212n, 2211, 2122, 221
1p, 2212p Square waveguide 2213a, b, c, 2213n, 2213p Gas introduction means 2214 Exhaust pipe 2215a, b Isolation passageway 2216 Film forming space 2217, 2218 Mesh 2303 Sending bobbin 2304 Winding bobbin 2305, 2306 Transfer roller 2307, 2308, 2309, 2309a, 2309
b Throttle valve 2310, 2311 Exhaust pipe 2312, 2313 Temperature adjustment mechanism 2314, 2315 Pressure gauge 2400 Microwave applicator 2401,402 Microwave permeable member 2403a, 2403b Microwave matching disk 2404 Inner cylinder 2405 Outer cylinder 2406 For fixing Ring 2407 Choke flange 2408 Rectangular waveguide 2409 Cooling medium 2410 O-ring 2411 Groove 2412 Metal seal 2413, 2414 Cooling air introduction / exhaust hole 2501 Band member 2502 Lower electrode 2503 First conductive type layer (n-type semiconductor layer) 2504 i Type semiconductor layer 2504b buffer layer 2505 second conductivity type layer (p type semiconductor layer) 2506 upper electrode 2507 current collecting electrode 2508 first pin junction photovoltaic element 2509 second pin junction Photovoltaic element 2510 third pin junction photovoltaic element 2511 tandem photovoltaic device 2512 triple type photovoltaic device 3100,3100n, 3100p, 3301,330
2 vacuum container 3101 i-type layer film forming container 3101n film forming container for forming first conductivity type layer 3101p film forming container for forming second conductivity type layer 3102, 3102n, 3102p, 3103, 310
4 film forming spaces 3105, 3105n, 3105p, 3106, 310
7 Applicators 3108, 3108n, 3108p, 3109, 311
0 microwave permeable member 3111, 3111n, 3111p, 3112, 311
3 Waveguides 3114, 3114n, 3114p, 3115, 311
6 Gas introduction means 3117, 3117n, 3117p, 3118, 311
9 gas supply pipes 3120, 3120n, 3120p, 3121, 312
2 Exhaust punching board 3123, 3123n, 3123p Lamp house 3124, 3124n, 3124p Infrared lamp heater 2125, 3125n, 3125p, 3126 Exhaust pipe 3127, 3127n, 3127p, 3128 Exhaust throttle valve 3129, 3129n, 3129p, 3130, 331
1,3312 Gas gate 3131, 3131n, 3131p, 3132n, 31
32p, 3132 Gate gas supply pipe 3133, 3133n, 3133p Mesh 3134, 3134n, 3134p Thermocouple 3150 Band member 3200 i-type layer film forming vacuum container 3200n First conductivity type layer film forming vacuum container 3200p Second conductivity type layer Film forming vacuum container 3201 Band-shaped members 3202n, 3202p, 3202, 3203, 320
2p, 3203p Transport rollers 3204n, 3205n, 3204, 3205, 320
4p, 3205p Transport ring 3206na, 3206nb, 3206a to e, 320
6pa, 3206pb temperature adjusting mechanism 3207n, 3208n, 3207, 3208, 320
7p, 3208p applicator 3209n, 3210n, 3209, 3210, 320
9p, 3210p microwave permeable member 3211n, 3212n, 3211, 3212, 321
1p, 3212p Rectangular waveguide 3213a, b, c, 3213n, 3213p Gas introduction means 3214 Exhaust pipe 3215a, b Isolation passageway 3216 Film forming space 3217, 3218 Mesh 3303 Sending bobbin 3304 Winding bobbin 3305, 3306 Transfer roller 3307, 3308, 3309, 3309a, 3309
b Throttle valve 3310, 3311 Exhaust pipe 3312, 3313 Temperature adjustment mechanism 3314, 3315 Pressure gauge 3400 Microwave applicator 3401, 3402 Microwave transmissive member 3403a, 3403b Microwave matching disk 3404 Inner cylinder 3405 Outer cylinder 3406 For fixing Ring 3407 Choke flange 3408 Rectangular waveguide 3409 Cooling medium 3410 O-ring 3411 Groove 3412 Metal seal 3413, 3414 Cooling air introducing / exhausting hole 3501 Band member 3502 Lower electrode 3503 First conductive type layer (n-type semiconductor layer) 3504 i -Type semiconductor layer 3505 Second conductivity type layer (p-type semiconductor layer) 3506 Upper electrode 3507 Current collecting electrode 3508 First pin-junction photovoltaic element 3509 Second pin-junction photovoltaic element 3510 Third pin junction photovoltaic element 3511 Tandem photovoltaic element 3512 Triple photovoltaic element

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Masafumi Sano 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Ryo Hayashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Akira Sakai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasushi Fujioka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. ( 72) Inventor Shotaro Okabe 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Naoshi Yoshiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Invention Person Masahiro Kanai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (8)

[Claims] 1. A microwave plasma CVD method in which a raw material gas for forming a deposited film is decomposed by microwave energy under a low pressure to form a deposited film on a substrate, and the raw material gas is supplied at a vacuum degree of 50 mTorr or less in internal pressure.
Microwave energy smaller than that required for 0% decomposition is applied to the source gas, and at the same time, rf is larger than the applied microwave energy.
Energy is applied to the raw material gas, and a mesh made of a conductive metal is interposed between the substrate and the space where the raw material gas is mainly decomposed by the acting microwave energy, and a DC bias is applied to the mesh. A method for forming a deposited film by a microwave plasma CVD method, characterized in that a voltage is applied. 2. In a microwave plasma CVD method in which a raw material gas for forming a deposited film is decomposed by microwave energy under a low pressure to form a deposited film on a substrate, the raw material gas is 10 at a vacuum degree of 50 mTorr or less.
Microwave energy smaller than that required for 0% decomposition is applied to the source gas, and at the same time, rf is larger than the applied microwave energy.
Energy is applied to the raw material gas, and a mesh made of a conductive metal is interposed between the substrate and the space where the raw material gas is mainly decomposed by the microwave energy to act, and at the time of forming the deposited film. A method for forming a deposited film by a microwave plasma CVD method, which comprises heating and holding the mesh at a temperature of 100 ° C. or higher. 3. In a microwave plasma CVD method for decomposing a raw material gas for forming a deposited film with microwave energy under a low pressure to form a deposited film on a substrate, the raw material gas is 10 at a vacuum degree of 50 mTorr or less.
Microwave energy smaller than that required for 0% decomposition is applied to the source gas, and at the same time, rf is larger than the applied microwave energy.
Energy is applied to the raw material gas, and a mesh made of a conductive metal is interposed between the substrate and the space where the raw material gas is mainly decomposed by the microwave energy to act, and an rf bias is applied to the mesh. A method for forming a deposited film by a microwave plasma CVD method, characterized in that a voltage is applied. 4. A film forming space is provided in a vacuum container capable of being evacuated, and the belt-shaped member is continuously conveyed in its longitudinal direction to penetrate the film forming space, In a device for producing a functional deposited film that decomposes a raw material gas by microwave plasma on a surface to form a deposited film, one or both of a carry-in side and a carry-out side of the strip-shaped member in the film formation space, a predetermined range The deposited film forming apparatus, wherein a porous conductive member is provided so as to be close to the deposition surface of the strip-shaped member. 5. A film forming space is provided in a vacuum container capable of being evacuated, and the belt-shaped member is continuously conveyed in its longitudinal direction to penetrate the film forming space, In the apparatus for producing a functional deposited film, which decomposes a raw material gas by microwave plasma to form a deposited film on the surface, a porous conductive member is provided over the entire deposition surface of the strip-shaped member in the film formation space. An apparatus for producing a deposited film, which is arranged so as to be close to the deposition surface. 6. The deposited film forming apparatus according to claim 4, wherein the porous conductive member is a mesh made of a conductive metal. 7. A porous conductive member and the belt-shaped member,
The deposited film forming apparatus according to claim 4, wherein the deposited film is electrically connected by a conductive material. 8. The deposited film forming apparatus according to claim 4, wherein the pressure in the film forming space is 50 mTorr or less.