JPH0372083A - Method and device for continuously forming large-area functional deposited film by microwave plasma cvd method - Google Patents

Abstract

PURPOSE:To continuously obtain the functional deposited film having high quality uniformly over a wide area at a high speed by confining microwave plasma into a film forming space and controlling the plasma potential. CONSTITUTION:A band-shaped member 101 which constitutes the side wall of the film forming space is continuously moved in the longitudinal direction. A microwave antenna means is so plunged into the above-mentioned film forming space as to parallel with the transverse direction of the member 101. Microwave electric power is radiated in the entire direction perpendicular to the progressing direction of the microwaves from the above-mentioned antenna means to generate plasma and to continuously form the large-area functional deposited film with good uniformity. The high-quality functional deposited film which has desired characteristics and has less defects is continuously and efficiently formed at a high yield by properly controlling the plasma potential according to the above-mentioned method.

Description

Detailed Description of the Invention [Technical field to which the invention pertains] The present invention uses a novel microwave energy supply device capable of generating uniform microwave plasma over a large area, and the plasma reaction caused thereby. The present invention describes a method and apparatus for continuously forming a large-area functional deposited film by decomposing and exciting a source gas.

More specifically, it is a method and apparatus capable of dramatically increasing the utilization efficiency of the raw material gas and continuously forming a highly uniform functional deposited film over a large area at high speed. Accordingly, large-area thin film semiconductor devices such as photovoltaic elements can be mass-produced at low cost.

[Description of prior art]

The demand for electricity continues to increase worldwide, and how to produce electricity to meet such demand is being considered as a global issue. Electricity production is currently performed by hydroelectric power, thermal power generation, and nuclear power generation. Among these power generation methods, hydroelectric power generation uses rainfall, but cannot consistently produce a predetermined amount of electricity.

Thermal power generation uses so-called fossil fuels such as oil and coal, and most of the electricity demand is met by this power generation method, but fossil fuels are finite and there are unavoidable problems when generating electricity. The necessity of switching to other power generation methods is being debated because the carbon dioxide emitted by the power generation system has an inherent IL'fff that will cause global warming in the future.

For these reasons, nuclear power generation is attracting a lot of attention, and the proportion of electricity produced by nuclear power generation is on the rise. However, with nuclear power generation, there is a risk of radioactive contamination, a serious problem affecting the survival of all living things, so it is essential to ensure safety.
This point is being considered on a global scale.

Against the above background, "solar power generation" has recently been attracting a lot of attention, and many proposals have already been made regarding this. However, none of the solar power generation methods that have been proposed are capable of producing electricity from the perspective of meeting electricity demand.By the way, the solar power generation methods that have been proposed so far can be broadly divided into the following two methods. can.

The method focuses two sunlight to heat water, boil it and generate steam (photothermal conversion), which generates electricity in a boiler (heat M, conversion).

Method B: Generates electricity by converting light N from solar cells.

The solar power generation method of method A is a method that generates electricity after two steps of energy conversion, and the conversion efficiency of the system is low, and although small plant experiments have been started, it has not been put into practical use.

On the other hand, many proposals have already been made regarding the solar power generation method of Method B, and some of them have been put into practical use as power sources for consumer products such as wristwatches and desk calculators; Although experiments are being conducted on small-scale power generation facilities, it is currently still in the research stage.

The reason for this is that there are several issues that need to be overcome in order to produce large-scale electricity on a regular basis. The biggest challenge is whether batteries can be produced on an industrial scale. By the way, the semiconductor layer, which is an important component of solar cells, is a so-called pn junction, a pir junction.
A semiconductor junction such as an l junction is formed. These semiconductor junctions are formed by stacking semiconductor layers of different conductivity types, implanting dopants of different conductivity types into semiconductor layers of -conductivity type by ion implantation, or diffusing them by thermal diffusion. be done. There are many proposals regarding the material constituting the semiconductor layer, but these proposals include single crystal or polycrystalline silicon (hereinafter '
) and amorphous silicon (hereinafter referred to as “a-
It is abbreviated as 3+1. ), and compound semiconductor materials.

However, when using any of these materials, there are manufacturing issues such as uniformity and reproducibility, photoelectric conversion efficiency issues, and manufacturing cost issues, which make it difficult to produce large quantities and large areas that can meet the enormous power demand. The manufacturing method for producing solar cells and the solar cell element structure itself have not yet been perfected.

In particular, solar cell panels using single-crystal Si are manufactured by lining up Si wafers cut from silicon ingots, implanting ions into them to form p-n junctions, and connecting them together with as few gaps as possible. , the manufacturing process for solar cell elements is not suitable for processing large quantities of large-area substrates, and large-diameter single-crystal silicon ingots are extremely expensive to begin with;
In the step of cutting out a Si wafer, a large amount of portion that cannot be used as a cutting allowance is discharged. These factors are also a cause of increasing the production cost of single-crystal Si solar cells. At present, there is no effective way to solve these problems.

Although the photoelectric conversion efficiency of solar cells using polycrystalline S1 is slightly higher than that of solar cells using A-3T, the technology for controlling crystal grain size, which is one of the characteristics determining factors, is still incomplete. Furthermore, the device manufacturing process is almost the same as that for single-crystal Si solar cells, so it is difficult to say that it is a method suitable for mass production.

In addition, due to the unique property of crystals, whether single crystal or polycrystalline, X-3T is easily broken, requiring strict protective materials for outdoor solar power generation. Solar panel units are quite heavy and are subject to restrictions on installation location and environment.

On the other hand, in the production of large-area solar cells using a-3i, phosphine (P) (3), diborane (BOH,
) and other dopant elements are mixed with silane, the main raw material gas, and subjected to glow discharge decomposition, a semiconductor film having a desired conductivity type can be obtained, and these semiconductor films can be deposited on a desired substrate. It is known that a semiconductor junction can be easily formed by sequentially laminating the above-mentioned x-3i, and can be manufactured at a considerably lower cost than when using the x-3i described above.

Then, in order to perform the above-mentioned glow discharge decomposition, RF (
The glow discharge decomposition method (radio frequency) was technically established,
It is becoming widely used. However, this method produces a relatively high quality semiconductor film when it is formed at a low deposition rate, so it is possible to form a semiconductor film of high quality enough to function as a solar cell over a large area at high speed. It is difficult to do so, and it is even more difficult to manufacture solar cells in an industrial scale to meet electricity demand.

On the other hand, as a method for forming high-quality deposited films at high speed,
Plasma processes using microwaves are attracting attention. Since microwaves have a short frequency band, it is possible to increase the power density within the film forming chamber compared to when conventional RF is used, allowing plasma to be generated and sustained efficiently.

For example, U.S. Pat. No. 4,517,223 and U.S. Pat. No. 4,504,518 each disclose a method of generating a glow discharge using microwave power and forming a deposited film on a substrate at low pressure. Disclosed.

According to these publications, since these deposited film formation methods perform film formation under low pressure, there is less recombination of radicals, which causes deterioration of the properties of the deposited film when high power is applied. It is understood that there are advantages such as less generation of fine powder made of polysilane or the like in plasma and improvement in film formation rate. However, plasma processes using microwaves have a problem in that non-uniformity in plasma density tends to occur because the wavelength of microwaves is extremely short, about 1/180 of that of conventional RF.

As an example of avoiding such problems, there has been an attempt to use a slow wave circuit as a microwave power supply means to equalize the microwave power within the deposition chamber, but the slow wave circuit has There is a particular problem in that the microwave power supplied to the plasma from the microwave power supply means rapidly attenuates as it moves away from the plasma. In order to solve this problem, attempts have been made to make the power density near the substrate constant by gradually increasing the distance between the substrate to be processed and the microwave power feeding means in the direction of propagation of the microwave.

For example, US Pat. No. 3,814,983 and US Pat. No. 4,521,717 disclose such methods. In the former, it is stated that it is necessary to incline the microwave power supply means at a certain angle with respect to the substrate.
The power transfer efficiency is not satisfactory. Further, in the latter case, it is disclosed that microwave power feeding means, which are two slow wave circuits, are provided non-parallelly in a plane parallel to the base body. That is, the central axis of the microwave power feeding means is
It is desirable that the microwaves be arranged in a plane parallel to the substrate and on a straight line perpendicular to the direction of movement of the substrate, and to avoid interference between the two microwave power feeding means. Each of these discloses disposing the power feeding means so as to be laterally shifted from each other by half the length of the long side of the waveguide with respect to the moving direction of the base body.

Furthermore, among microwave feeding means, antenna systems that are relatively easy to handle are shown in Figures 17 and 18, for example.
Japanese Patent Publication No. 57-53858 and Japanese Unexamined Patent Application Publication No. 1987-6 shown in the figure
There is a microwave plasma cvoHW described in Japanese Patent No. 1-283116.

In either case, the antenna is surrounded by a cylindrical body made of a material that is transparent to microwaves. By preventing film deposition on the antenna, the lifetime of the antenna can be improved, and high-density plasma can be generated over a wide pressure range. However, in the installation shown in FIG.
A microwave power supply means such as a group 183 placed on the 182 is disposed inside.

Reference numeral 184 denotes a coaxial line as the microwave power supply means, and the microwave power is passed through a microwave transparent cylinder 186 from a gap 185 provided by cutting out a part of the outer conductor of the coaxial line 184. It is put into the reaction container 181. However, with this apparatus, it is clearly difficult to uniformly form an a-3i film on a large-area substrate, and there is no specific disclosure.On the other hand, in the apparatus shown in FIG. Inside there is a Rondo antenna 172 which is a microwave power supply means, a gas supply port 173,
A gas exhaust port 175 connected to a vacuum pump 174 and a substrate 177 placed on a quartz cylinder 176 are provided. Microwave power generated by the microwave oscillator is transmitted through a waveguide 178 and is injected into a space surrounded by a quartz cylinder 176 via a rondo antenna 172 and a microwave transmission member 179 to generate plasma. Plasma treatment is performed. However, due to the inherent property of the antenna that the microwave power is sequentially radiated into space while propagating on the Rondo antenna, attenuation of the microwave power occurs in the length direction of the Rondo antenna, resulting in plasma This is difficult to make uniform in the longitudinal direction.

In addition, 1. In the cavity resonator method, which is known as another microwave power feeding means, several proposals have been made for maintaining plasma uniformity.

These proposals can be found, for example, in the Journal of Vacuum
Science and Technology (Journal of Va.
euus 5cieriee Technology)
B-4 (January-February 1986 >2'1) 5) Q-2
98 shells and B-4 of the same magazine (January-February 1986) 12
See the report on pages 6-130. According to these reports, a cylindrical cavity type microwave reactor called a microwave plasma disk source (abbreviated as MPDS) has been proposed. It is said that the Ilp plasma has a disk-like shape, is included in the resonator 2 as part of a cylindrical cavity resonator, and its diameter is a function of the microwave frequency. These reports indicate that a variable cavity length structure was added to the MPDS so that it could be tuned to the microwave frequency.

In an MPDS designed to operate at 2.45 GHz, the plasma confinement diameter is at most lo(2).
The plasma volume is at most 118 cm.
3, which cannot be said to be a large area. The report also states that in a system designed to operate at a frequency as low as 915 MHz, lowering the frequency provides a plasma diameter of about 40 and a plasma volume of 2000 cm3.

Also, the report further states that lower frequencies, e.g. 400
By operating with MH2, it is said that the discharge can be expanded to a diameter of more than 1 meter. However, in order to achieve this goal, a dedicated high-power microwave oscillator must be developed, and even if it is recharged, the frequencies that can be used industrially are restricted by the Radio Law in order to avoid communication problems. This makes it difficult to implement.

Furthermore, a method using electron cyclotron resonance (ECR) as another microwave power feeding means was disclosed in Japanese Patent Application Laid-Open No. 55-14.
This method has been proposed in Japanese Patent Application Laid-open No. 1729, Japanese Patent Application Laid-Open No. 57133636, and the like. That is, in this method, an electromagnet is placed coaxially around a cavity resonator that serves as a plasma generation chamber, and the electromagnet applies a magnetic field of 875 Gauss near the microwave introduction window to generate electron cyclotron resonance (F, CR). ) conditions to increase the absorption rate of microwaves into plasma,
This generates high-density plasma.

The high-density plasma is then transported along a diverging magnetic field formed by the electromagnet to form a desired deposited film on a desired substrate.

This method is similar to the previously mentioned microwave plasma disk source (MPDS) method in that it uses a cavity resonator, but in the MPDS method, only a part of the interior of the cavity is occupied by the plasma. On the other hand, the ECR mentioned above
The method differs in that the cavity is filled with plasma and that it utilizes the electron cyclotron resonance phenomenon.

Now, at academic conferences and the like, many examples of forming various semiconductor thin films using the high-density plasma produced by this ECR method have been reported. This type of microwave ECR plasma CVD apparatus is already commercially available.

However, in these methods using ECR, since a diverging magnetic field applied from outside the cavity resonator is used to control the plasma, the magnetic field distribution created by the electromagnet on the substrate surface is also uneven, and it is difficult to spread the magnetic field over a large area of the substrate. It is very difficult to form a uniform and homogeneous deposited film.

A method that partially overcomes this difficulty and improves the film thickness and film quality distribution is disclosed in JP-A-63-283018. That is, this means that magnetic field generating means (e.g., a second electromagnet) other than the electromagnets arranged around the cavity resonator are arranged around the substrate in order to generate a uniform magnetic field distribution,
Uniform IIl! ! This achieves a thickness/11iSff distribution. However, this second electromagnet is already huge, and the reality is that even if a device is constructed using this huge magnet, it is only possible to obtain uniformity in film quality and thickness of about 15 cmφ at most. be.

In addition to establishing a high-frequency power supply means such as RF or microwave as explained above, it is also possible to manufacture solar cell elements by sequentially laminating semiconductor films having a plurality of desired conductivity types to form semiconductor junctions. Continuous film deposition equipment must also be established.

As an example of such a continuous film-forming apparatus, a plurality of independent film-forming chambers for forming a plurality of semiconductor films are connected via a gate valve, and each film-forming chamber is equipped with 1&ll parallel plate type RF electrodes. and in each of the film forming chambers,
A continuous film forming apparatus has been proposed in which each semiconductor film is deposited by an RF glow discharge decomposition method in a state isolated from other film forming chambers. That is, a so-called three-chamber separation type continuous film forming apparatus has been proposed as a continuous film forming apparatus for stacked semiconductor devices having pin junctions, in which the gate valves are used to form a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer. The film forming chambers are separated and each layer is formed using the RF glow discharge decomposition method. However, in the process of stacking each layer, the cycle of film formation, exhaust, transport, and bottom film is repeated, which takes a long time. Moreover, since the width of the substrate is also limited by the gate valve, it is impossible to use a continuous film-forming apparatus that can produce large quantities of solar cell elements that can replace current power generation methods.

In contrast, the roll-to-roll technology disclosed in U.S. Pat.
The continuous reading film apparatus of the Roll type is practical because there are fewer restrictions on the film formation time and the width of the substrate as described above.

According to this device, a plurality of RF glow discharge regions are provided along a path along which a sufficiently long flexible strip substrate having a desired width is conveyed, and each RF glow discharge fiIJ! In step Ii, a semiconductor device mainly composed of a-3l is formed, and the strip-shaped substrate is continuously conveyed substantially horizontally in its longitudinal direction, thereby emitting RF glow. It is said that it is possible to continuously form elements having . In addition, in the specification,
A gas gate is used to prevent the dopant gas used when forming each semiconductor film from diffusing and mixing into other RF glow discharge regions. Specifically, the gas gate is
The RF glow discharge regions are separated from each other by a slit-shaped gas isolation passage, and a means is adopted for forming a flow of scavenging gas such as Ar or Hffi in the isolation passage.

However, since the formation of each of the semiconductor layers is performed by plasma CVD using RF (radio frequency), there is a natural limit to improving the film deposition rate while maintaining the characteristics of the continuously formed film. There is. That is, even when forming a semiconductor layer with a film thickness of at most 5000 Å, for example, the film deposition rate is slow, so a predetermined plasma is constantly generated over a fairly long and large area in the direction of conveyance of the strip-shaped substrate. It is necessary to maintain a uniform plasma.

However, doing so requires considerable skill, and it is therefore difficult to generalize the various plasma control parameters involved. Furthermore, the decomposition efficiency and utilization efficiency of the film-forming raw material gas used are not high, which is one of the factors that increases production costs.

In addition to this, Japanese Patent Application Laid-open No. 61-288074 states:
A deposited film forming apparatus using an improved roll-to-roll continuous film forming method is disclosed.

In this device, a curved part is formed in a part of a flexible continuous band-shaped member installed in a reaction vessel, and active species generated from a raw material gas are applied to this width in an activation space different from the reaction vessel. After being transported to the reaction vessel, it is introduced into the reaction vessel and chemical interaction is caused by thermal energy to form a deposited film on the inner surface of the band-shaped member forming the curved portion. By depositing on the inner surface of the curved portion in this manner, the device can be made more compact. Furthermore, since active species activated in advance are used, the film formation rate can be increased compared to the conventional fil#II film forming apparatus.

However, this device only utilizes a deposited film formation reaction due to chemical interaction in the presence of thermal energy, and the method of supplying thermal energy, the ease with which the reaction between active species and other molecules occurs, and the Depending on the lifespan of the species until deactivation, etc., the distance between the reaction vessel and the activation space of the deposited film forming apparatus and the film forming conditions are restricted, making it difficult to increase the area.

By the way, thin film semiconductors are used not only for the solar cells mentioned above, but also for large area or large area applications such as thin film transistors (TPT) for driving pixels of liquid crystal displays, photoelectric conversion elements and switching elements for contact image sensors, etc. It is also suitable for manufacturing thin film semiconductor devices that require long dimensions, and has been put into practical use as a key component for the above-mentioned image input/output devices. It is expected that the provision of a new method for forming a deposited film will lead to further widespread use.

[Purpose of the invention]

The present invention overcomes the problems in the conventional v1i film semiconductor device forming method and apparatus as described above, and provides a novel method and method for forming a high-quality functional deposited film uniformly over a large area and at high speed. The purpose is to provide a device.

Another object of the present invention is to provide a method and apparatus for continuously forming a high quality functional deposited film on a strip member.

A further object of the present invention is to provide a method and apparatus that can dramatically increase the utilization efficiency of raw material gas for forming deposited films and realize mass production of thin film semiconductor devices at low cost.

Still another object of the present invention is to provide a method and apparatus for generating substantially uniform plasma over a large area and large capacity.

Still another object of the present invention is to provide a method and apparatus for uniformly, reproducibly, and stably controlling the plasma potential of microwave plasma generated over a large area and large volume.

A further object of the present invention is to provide a novel method and apparatus for forming a functional deposited film of high quality and excellent uniformity of properties by controlling the plasma potential of microwave plasma.

Still another object of the present invention is to provide a novel method and apparatus for continuously forming a photovoltaic device with good stability, high efficiency, and high photoelectric conversion efficiency on a relatively wide and long substrate. It is something to do.

[Structure and effects of the invention]

The inventors of the present invention solved the above-mentioned problems in the conventional semiconductor deposited film type Ifi apparatus, and conducted intensive research to achieve the object of the present invention. A microwave antenna means is enclosed in a microwave-transparent member and inserted into the 18 chamber, and a raw material gas for film formation is introduced into the film formation chamber, and an appropriate method is used to easily cause gas diffusion. When the pressure was maintained, microwaves were supplied from the microwave power source to the microwave antenna means, and a bias voltage was applied to the bias application means arranged separately from the band-shaped member. It has been found that uniform microwave plasma can be generated in the longitudinal direction of the microwave antenna, and that the plasma potential can be controlled.

The present invention was completed as a result of further studies based on the above-mentioned findings, and is a method for continuously forming a large-area functional deposited film using a microwave plasma CVD method that mainly focuses on and equipment.

The method of the present invention is as follows.

That is, while continuously moving the strip member in the longitudinal direction, a columnar film forming space that can be maintained in a substantially vacuum state is formed with the moving strip member as a side wall in the middle of the movement. Introducing raw material gas for film formation via a gas supply means,
Simultaneously, radiating microwaves in all directions perpendicular to the direction of propagation of the microwaves via a microwave antenna and injecting microwave power into the film-forming space to generate microwave plasma within the film-forming space; A microwave plasma characterized in that, while controlling the plasma potential of the microwave plasma, a deposited film is formed on the surface of the continuously moving band-shaped member that constitutes the side wall exposed to the microwave plasma. This is a method of continuously forming a large-area functional deposited film using the CVD method.

In the method of the present invention, a curved start end forming means and a curved end forming means are used in the middle of the moving band-shaped member, and the curved end forming means is provided between the curved start end forming means and the curved end forming means. The strip member is curved leaving a gap in the longitudinal direction of the strip member to form a side wall of the film forming space.

Further, in the method of the present invention, the material of the strip-shaped member is a material whose linear expansion coefficient is larger than that of the deposited film to be formed, and the strip-shaped member is heated to a desired film-forming temperature higher than room temperature. A deposited film is formed on the concave curved surface that is formed by continuously curving the deposited film while maintaining the temperature, and when the belt-shaped member on which the deposited film is formed is cooled to room temperature outside the film-forming space, the belt-shaped member is flattened. It can be rolled out into a shape and cooled, or rolled up into a convex shape and cooled.

Then, the microwave antenna means is inserted into the film-forming space from either of the opposing end surfaces of the columnar film-forming space formed with the band-shaped member as a side wall, and the microwave antenna is transmitted into the film-forming space. Turn on the power.

Further, microwave power is introduced into the film forming space from the microwave antenna means via a microwave transparent member provided between the microwave antenna means and the film forming space, and , the microwave antenna means is separated from the plasma generated in the film forming chamber by the microwave transparent member.

In the method of the present invention, the plasma potential is controlled via bias application means separated from the strip member.

The bias applying means is disposed so that at least a portion thereof is in contact with the microwave plasma, and a bias voltage is applied to the bias applying means, but the bias applying means is arranged such that at least a portion thereof is in contact with the microwave plasma. At least a portion is subjected to conductive treatment.

Further, as the bias voltage, direct current, pulsating current and/or alternating current are suitably used.

In the method of the present invention, the bias applying means may also serve as the gas supply means, or may be arranged separately from the gas supply means.

The bias applying means may include one or more bias rods.

In the method of the present invention, the plasma potential may be controlled by a bias voltage applied to the band-shaped member, and the gas supply means is set to a ground potential, and at least a portion thereof is arranged to be in contact with the microwave plasma. be set up.

At least a portion of the gas supply means that is in contact with the microwave plasma is subjected to conductive treatment.

In the method of the present invention, the outer diameter of the microwave transparent member is adjusted and selected in advance according to the complex dielectric constant of the plasma.

Further, at least a surface of the band-shaped member on the side exposed to the microwave plasma is subjected to conductive treatment.

Furthermore, the apparatus of the present invention has the following contents.

That is, it is an apparatus that continuously forms a functional deposited film on a continuously moving strip-shaped member by microwave plasma CVD method, and while continuously moving the strip-shaped member in the longitudinal direction, A columnar film forming chamber is formed using the strip member as a side wall and can maintain a substantially vacuum inside thereof through a curved portion forming means for curving,
A microwave coaxial line for supplying microwave power for generating microwave plasma in the film forming chamber; a center conductor separating means for separating the center conductor of the wave coaxial line; a means for evacuating the film forming chamber; a gas supply means for introducing a raw material gas for film forming into the film forming chamber; Bias for controlling the plasma potential tTj of the plasma.

and a salinity ItI control means for heating and/or cooling the strip member, and the microwave plasma of the strip member forming the side wall of the film forming chamber while continuously moving. This is an apparatus for continuously forming a large area deposited film, characterized in that the deposited film is continuously formed on the surface exposed to the air.

In the apparatus of the present invention, the curved portion forming means includes a curved start end forming roller, a curved end end forming roller, and an opposing curved portion end surface support ring, and the curved start end forming roller and the curved end forming roller are , are arranged parallel to each other with a gap left in the longitudinal direction of the strip member.

In the device of the present invention, the bias applying means is arranged separately from the strip member.

The bias applying means is disposed such that at least a portion thereof is in contact with the microwave plasma, and a bias voltage is applied to the bias applying means. At least a portion of the contacting portion is subjected to conductive treatment.

Further, as the bias voltage, direct current, pulsating current and/or alternating current are suitably used.

In the apparatus of the present invention, the bias application means may also serve as the gas supply means, or may be arranged separately from the gas supply means.

The bias applying means is composed of one or more bias rods.

In the apparatus of the present invention, when the bias applying means is disposed also as the strip member, the gas supply means is grounded and at least a portion thereof is disposed so as to be in contact with the microwave plasma.

At least a portion of the gas supply means that is in contact with the microwave plasma is subjected to conductive treatment.

In the apparatus of the present invention, the center conductor of the microwave coaxial line is inserted into the film forming chamber from either one of the opposing end surfaces of the columnar film forming chamber, and It is arranged near the central axis and substantially parallel to the width direction of the band-shaped member.

In the apparatus of the present invention, the central conductor separating means constituted by the microwave 13i1J member is rotationally symmetrical, and its shape may be cylindrical, truncated conical, or conical.

Furthermore, in the apparatus of the present invention, at least two tuning means are disposed on the microwave coaxial line, one of which serves as an insertion length adjustment mechanism for the center conductor inserted into the film forming chamber. Ru.

Further, at least a surface of the band-shaped member on the side exposed to the microwave plasma is subjected to conductive treatment.

〔experiment〕

Various experiments were conducted using the apparatus of the present invention to investigate the conditions for generating microwave plasma in order to uniformly form a high-quality functional deposited film on a strip-shaped member. do.

In this experimental example, the plasma stability, film thickness distribution, and film quality distribution were investigated when the inner diameter of the cylindrical film forming chamber was changed.

Specifically, using the apparatus of Apparatus Example 1 to be described later, five types of samples were prepared according to the film forming conditions shown in Table 1 by changing only the inner diameter of the film forming chamber. Note that this study was conducted with the strip member stationary.

Table 2 shows the evaluation results regarding the plasma state etc. when the inner diameter of the film forming chamber was variously changed.

The inner diameter of the film forming chamber shown in Table 2 is 180mmφ, 120s
In the case of sφ, the microwave power is 25 (l O
When plasma was generated under the same conditions as shown in Table 1 except that W was used, the inner diameter of the film forming chamber was 120 mmφ.
In the case of , the discharge was stabilized, but the inner diameter of the deposition chamber was
In the case of 關φ, although discharge occurred, it was unstable and not worthy of practical use.

Next, the characteristics of samples 2-1 to 2-4 were evaluated using the evaluation method described below.

The thickness of the deposited film formed is MCPD manufactured by Union Giken Co., Ltd.
It was calculated from the peak position of the multiple interference fringe of the spectral reflectance curve measured using a -2O0 type spectral reflectance meter.

The film thickness measurement points for each sample were in the width direction of the substrate (X
) and in the longitudinal direction (y) at intervals of 79 m and 50 m, a Crl film was deposited on this a-8i; Then, in the dark, the Ohmisoku electrode and 5US430BA used as a strip member were used.
(0.2 mm thick) The dark conductivity (σ, ) was determined from the current value flowing by applying a voltage between the thin plate, and while applying the voltage in the same manner as described above, the He- Photoconductivity (σ,) is determined from the current value flowing when irradiated with N5 laser light.
were calculated, and the characteristic distribution of each was evaluated. In addition, H
The irradiation intensity of the e-Ne laser beam into the a-3i:)l film is 4X10" in terms of the number of photons, taking into account the absorption of the Cr electrode.
pieces/-・sec.

Figure 10 (al shows the film thickness distribution in the X direction of samples 2-1 to 2-3, the mountain in Figure 1O shows the film thickness distribution in the y direction, Figure 11 +8
+σ1. Distribution of σ in the X direction, Fig. 11 σ4 at +8+
．． The measurement results of the distribution of σ in the y direction are shown. Here, X=O represents the center in the width direction of the band-like member, and y=o represents the center when the band-like member is expanded in the longitudinal direction.

From these measurement results, the uniformity of both the film thickness and film quality is good in the width direction of the band-shaped member, but the deposited film thickness decreases as the internal pressure of the film-forming chamber increases, and the uniformity of the film in the longitudinal direction of the band-shaped member is good. Although the uniformity of the film thickness was maintained in Sample 2-1, the characteristics clearly deteriorated.

That is, as the inner diameter of the film forming chamber increases, the characteristics of the a-3i:H film that is formed tend to deteriorate.

In addition, in sample 2-4, since the strip members are coaxially very close to each other, the plasma density is considerably higher than in the case of other samples, and the substrate temperature is over 350°C. Therefore, peeling of the film occurred after film formation, and the film could not withstand evaluation.

In this experimental example, the apparatus of the present invention shown in Fig. 1 (see apparatus example 1 described later) and the conventional RF glow discharge decomposition apparatus shown in Fig. 9 were used under the conditions shown in Table 3. We investigated changes in compressive stress in the deposited film by forming a deposited film and measuring the amount of strain on the substrate before and after the deposited film was formed. Here, the Young's modulus of the stainless steel forming the band member is 2.04 x 10' [kf/llj
” ], linear expansion coefficient is 11.9 x 10” [”C
-'].

As a result, 'JJJ M' was not observed in the deposited film using either device, but the measurement results of the compressive stress actually accumulated in the deposited film were as follows using the conventional device shown in Figure 9. In contrast, when using the apparatus of the present invention shown in FIG.
/me'', and it was found that the stress relaxation was effective at about 1/3.5.

Large attack team 1 In this experimental example, a method of creating a pressure difference between the inside and outside of the film forming space was performed using the apparatus shown in FIG.
An experiment was conducted to deposit an a-3t:H film under the same manufacturing conditions as shown in the table except that the width of the slit opening was varied.

Table 4 shows the experimental results and evaluation.

In addition, the effective conductance Cat [1/sec] in the table
is the flow rate from [Esccm] to [Torr −1/se
The differential pressure ΔP between the inside and outside of the film-forming space in terms of e
It was calculated by dividing by [rr].

From the results in Table 4, it was found that in order to prevent plasma leakage, it is preferable to make the pressure difference between the inside and outside of the film forming space larger than 9 mTorr.

In this experimental example, the apparatus shown in Fig. 1 was used to learn how to suppress abnormal discharge by keeping the pressure outside the film forming space low, and the apparatus shown in Fig. 6 was installed at the vacuum exhaust port. The process was the same except that the pressure outside the film forming chamber was varied under the production conditions shown in Table 3 by interposing a throttle valve and connecting an oil diffusion pump so that the effective pumping speed could be varied. A discharge experiment was conducted under the following manufacturing conditions. The results are shown in Table 5.

From these results, tcJI! When the pressure in the isolation container outside the space became high and almost equal to the pressure inside the film forming space, abnormal discharge or discharge concentration occurred and a film with poor adhesion was deposited. Therefore, it has been found that in order to prevent film quality deterioration due to abnormal discharge, it is preferable to maintain the pressure outside the film forming space at 5 m Torr or less.

In this experimental example, the apparatus shown in Device Example 1 (Fig. 1), which will be described later, was equipped with a bias applying means having the configuration shown in Fig. 19 (A), and a nickel gas introduction tube was used. We investigated the controllability of microwave plasma, the influence on plasma potential, film quality, etc. when changing the DC bias voltage applied to the bias application tube 1903, which also serves as a bias application tube 1903.

Bias applied voltage from -300V to +300V
Plasma was generated under the same microwave plasma discharge conditions as shown in Table 1, except that the conditions were changed in OV steps. Note that the inner diameter of the film forming chamber was 801 mφ. The surface temperature of the strip member was 250°C, and the conveyance speed was 48 cs.
/sin.

Furthermore, after each bias voltage was applied, discharge was maintained for 10 minutes.

FIG. 20 shows the results of determining the current-voltage characteristics between the bias application tube and the strip member during bias application, with the bias applied voltage plotted on the X-axis and the bias current value plotted on the Y-axis.

At the same time, the plasma potential V when bias was applied was measured by a probe method using a single probe using a tungsten wire with a diameter of 0.3 vs. and a length of 3 m (ft part). The results of determining the rate of change ΔVb (=Vb/V6) with respect to the potential v0 are shown in FIG. 21. The single probe was placed approximately at the center of the curved portion of the band-shaped member and approximately 5 cm from the inner surface. did.

Although these results vary depending on the type and flow rate of the raw material gas for discharge, in general, when the bias voltage is set to 19
If the voltage is below 0V or above +190V, abnormal discharge such as sparks will occur in the film forming chamber, making it difficult to maintain a stable discharge state. ◆ However, it was found that when the microwave plasma discharge conditions are constant, the current-voltage characteristics show a linear relationship with an almost increasing tendency as the bias voltage increases, and the plasma potential also shows an increasing tendency as the bias voltage increases. .

That is, by changing the bias voltage, the plasma potential could be controlled easily, stably, and with good reproducibility.

Subsequently, a 5 x 5 sample piece was cut out for the film deposited on the 5US430BA thin plate as a strip member, and its surface condition was examined using ultra-high resolution, low acceleration FB-3EM.
(Hitachi S-900 model) When the bias voltage ranged from 1300V to +IOV, several hundred people ~
Surface roughness was noticeable for several thousand people, but +10V to +1
In the range of 70 V, it was observed that the film surface tended to become smoother as the bias voltage increased. And +17
In the range exceeding 0V, the membrane surface begins to become rough again, especially at +1
Pinholes were also observed on the surface of the sample where abnormal discharges occurred frequently at voltages exceeding 90V.

Moreover, under the condition that the microwave power is constant, S r H4
etc.! As the flow rate ratio of the raw material gas with a large separation cross-sectional area increases, the slope of the current-voltage characteristics increases, while H
! It was found that as the flow rate ratio of the raw material gas with a small ionization cross section increases, the slope of the current-voltage characteristic becomes smaller.

The current-voltage characteristics were measured under the same conditions as in Comparative Experimental Example 5, except that the pre-bias application 1903, which also served as the gas introduction tube, was changed from nickel to aluminum. However, when the bias applied voltage was increased from Ov to approximately +55V, a phenomenon was observed in which the pre-bias application 1903 began to deform and eventually fused.

Furthermore, when the same measurement was performed by changing the pre-bias application 1903 to one made of copper or brass, the same phenomenon as described above was also observed. Before bias application, 1903 was sprayed with 800 ttm of nickel on the surface of high melting point metals such as stainless steel, titanium, vanadium, niobium, tantalum, molybdenum, and tungsten, and alumina ceramic tubes. When we performed similar measurements using the one made of stainless steel, we found that the applied bias voltage was +11
When using other materials, almost the same measurement results as those obtained in Experimental Example 5 were obtained, except that deformation was observed when the voltage exceeded 5V, and it finally fused. In particular, no phenomena such as deformation were observed.

Comparison basis 1 In Experimental Example 5, 5US430BA as a strip member
The current-voltage characteristics were measured under the same conditions except that the il1 sheet was replaced with a PET (polyethylene terephthalate) sheet (thickness: 0.8 mm). However, the current value that flows regardless of whether the bias voltage is applied to the positive or negative side is
Although it showed almost the same value as that obtained in Experimental Example 5,
Fti, the starting voltage of abnormal discharge in the membrane chamber was 195V or about 95V. When the state was visually observed, sparks were generated between the bias application tube and the rollers for supporting and conveying the strip member, and the strip member used exhibited a charge amplification phenomenon due to its insulating properties. rI
i. It was found that this was because an excessive current was flowing through the supporting/conveying roller, which was the only part of the membrane chamber other than before the bias was applied, which was made of a conductive member.

In addition, when the surface condition of the deposited film was observed and evaluated using the same method as in Experimental Example 6, it was found that the surface condition of the film was approximately several hundred to several thousand, regardless of the difference in the applied bias voltage. The surface remained rough.

Kitamoto 04 Motion 1 In Experimental Example 5, the position of the pre-bias application 1903, which also serves as a gas introduction pipe arranged in the film forming chamber, was changed from approximately above the central axis of the film forming chamber (position O in Fig. 4). The 1i current-voltage characteristics were measured under the same conditions except that the strip member was shifted in the 45°, 90°, and 135° directions along the curved surface of the strip member in Figure 4. Measurements were also made in the same way.

As a result, results exactly the same as in Experimental Example 5 were obtained when shifting in directions of 45°, 90°, and 135°. On the other hand, OH
If the film is shifted by 100 am or 120 m in the direction of However, almost no bias current flows, making it difficult to control the plasma potential.

In this experimental example, we used the apparatus with the configuration used in Experimental Example 5 to generate microwave plasma when bias voltages with various waveforms and frequency conditions shown in Table 8 were applied to the bias application tube 1903. We investigated the controllability of plasma potential, the effects on plasma potential, and film quality. Note that the microwave plasma discharge conditions and the like were the same as in Experimental Example 5.

Bias voltages can be obtained by amplifying various waveform outputs generated by a funxilane generator (HP8116A manufactured by Hewlett-Paracard) using a precision power amplifier (4500 series manufactured by NF Circuit Block Company and a custom-made product), or by using a homemade one. The output from the rectifier circuit device was applied to a bias application tube 1903 via a coaxial cable.

Table 8 shows the results of evaluating the controllability of the plasma potential based on discharge conditions, rate of change in plasma potential, observation of the film surface, etc. From these results, it was found that the effect of applying a bias voltage was observed in a relatively wide frequency range.

Furthermore, when the frequency of the bias voltage was fixed and the maximum amplitude voltage was varied, the same tendency as in Experimental Example 5 was observed.
That is, the same tendency as when changing the DC voltage was observed, and in particular, as the maximum amplitude voltage increased, the frequency of occurrence of abnormal discharges such as sparks increased.

These results show that even when various bias voltages other than DC voltage are applied to the bias tube, the plasma potential can be controlled easily, stably, and with good reproducibility by changing the bias voltage. Ta.

In this experimental example, the bias application means is shown in Fig. 19 (B
) The current-voltage characteristics were measured under the same conditions as in Experimental Example 5 except that the configuration was changed to that shown in ().

As a result, almost the same results as in Experimental Example 5 were obtained, and even though the gas introduction tube 1905 and the bias rod 19o4 were arranged independently, the plasma potential could be easily and stably changed by changing the bias voltage. It was found that it could be controlled with good reproducibility.

In this experimental example, the bias application means is shown in Figure 19 (C
) The current-voltage characteristics were measured under the same conditions as in Experimental Example 5 except that the configuration was changed to that shown in ().

As a result, the starting voltage of abnormal discharges such as sparks changed slightly, and at that time, there were no abnormal discharges except for the occurrence of abnormal discharges, especially at the contact area between the support/transport ring and the strip member in the deposition chamber. The same results as in Experimental Example 5 were obtained. however,
The bias voltage at which the film surface was smoothed had a polarity completely opposite to that in Experimental Example 5, that is, in the range of -10V to -170V.

Of course, the plasma was stable within this voltage range.

Therefore, it has been found that the plasma potential can be easily, stably, and reproducibly controlled by applying a bias voltage to the band-shaped member and arranging the ground rod 1905, which also serves as a gas introduction pipe, in the film forming chamber.

In this experimental example, the bias application means is shown in Fig. 19 (D
), a DC bias voltage was applied to the bias rod 1904 under the same conditions as in Experimental Example 7, and independently of this, 1/4 of the DC voltage applied to the bias rod 1904 was applied to the bias rod 1906. We investigated the controllability of microwave plasma, the influence on plasma potential and tilt, etc. when applying a voltage of . Note that the microwave plasma discharge conditions and the like were the same as in Experimental Example 5.

As a result, the frequency of abnormal discharges such as sparks is reduced,
Almost the same results as in Experimental Example 5 were obtained, except that the stability of the plasma was improved.

Therefore, it has been found that the plasma potential can be easily, stably, and reproducibly controlled by disposing a plurality of bias rods in the film forming chamber and applying bias voltages to each rod independently.

In the example of the Tsuchimoto experiment, the bias rod 1904 was used in experiment example 9.
Experimental Example 6 was carried out by changing the bias voltage applied to DC voltage to
Controllability of microwave plasma when applying bias voltages of various waves and frequencies similar to that carried out in
We investigated the effects on plasma potential and film quality. Note that the microwave plasma discharge conditions and the like were the same as in Experimental Example 5.

As a result, the frequency of abnormal discharges such as sparks is reduced,
In addition, almost the same results as in Experimental Example 5 were obtained, except that the starting voltage of abnormal discharge was slightly lowered and the stability of the plasma was improved.

Therefore, it has been found that the plasma potential can be easily, stably, and reproducibly controlled by disposing a plurality of bias rods in the film forming chamber and applying bias voltages to each rod independently.

In Experimental Examples 7 and 8, we conducted an experiment in which the same bias voltage as that in Experimental Example 6 was applied. Similar effects were observed.

In the method and apparatus of the present invention, the stability, uniformity, etc. of the microwave plasma are determined by, for example, the type and shape of the microwave applicator, the pressure inside the film forming chamber during film formation, and the microwave power. Since various parameters such as the degree of confinement of the microwave plasma, the volume and shape of the discharge space, etc. are intricately intertwined and maintained, it is difficult to determine the optimal conditions using only a single parameter. The results revealed roughly the following trends and condition ranges.

In the method of the present invention, the inner diameter of the film forming space is preferably 60 mm to 120 mm. The stress accumulated in the deposited film can be alleviated by forming the deposited film on a concave curved surface, expanding it into a flat shape, and cooling it.

Further, by changing the opening width of the slit to make the pressure difference between the inside and outside of the film forming space 9 m Torr or more, leakage of plasma from the film forming space can be prevented. Furthermore, it has been found that by setting the pressure outside the film-forming space to 6 mTorr or less, deterioration in the quality of the deposited film due to abnormal discharge can be prevented.

Furthermore, in the method and apparatus of the present invention, in order to control the plasma potential of the microwave plasma, a bias voltage applying means is provided in the film formation chamber in which the plasma is confined, and various DC voltages or pulses are applied to the bias applying means. It has been found that it is desirable to apply bias voltages of various waveforms, frequencies, and maximum amplitude voltages at current and alternating current voltages. Also,
It has been found that the bias voltage applying means may also serve as the gas introduction tube, or may be a bias rod provided separately from the gas introduction tube. It has also been found that the plasma potential can be controlled in substantially the same way even if a bias voltage is applied to the band-shaped member. When the bias voltage is a DC voltage, it has been found that it is desirable to set the voltage to +IOV to +200V as a guideline for improving membrane characteristics.

Hereinafter, the method and apparatus of the present invention will be explained in more detail based on the facts found through the above-mentioned [experiments].

The method of the present invention is objectively different from conventional deposited film forming methods. The point is that it also serves as a support for film formation.

Here, the function as a structural material is specifically the function of physically and chemically separating the atmosphere space for film formation, that is, the film formation space, and the atmosphere space that is not involved in film formation. This means, for example, the function of forming atmospheres with different gases and their states, restricting the direction of gas flow, and furthermore, forming atmospheres with different pressure differences.

That is, the band-like member is curved to form the side wall of the columnar film-forming space, and the raw material gas and microwave power for forming the deposited film are introduced into the film-forming space from either one of the opposing end faces. By supplying and exhausting through a gap left in a part of the side wall, plasma is confined in the film forming space and a functional deposited film is formed on a band-shaped member with the side wall at tR, The band-like member itself plays an important function as a structural member for isolating the film-forming space from an external atmospheric space that is not involved in film-forming, and can also be used as a support for forming a deposited film.

Therefore, the atmosphere outside the film-forming space, which has the band-shaped member as a side wall, is completely different from the atmosphere inside the film-forming space in terms of gas composition, its state, pressure, etc.

On the other hand, in the conventional method for forming a deposited film, a support for forming a deposited film is disposed in a film forming space for forming a deposited film, and is used exclusively for forming a deposited film, for example, formed in the film forming space. It functions only as a member for depositing the precursor, and does not function as a structural material constituting the film forming space as in the method of the present invention.

In addition, in conventional methods such as RF plasma CVD and sputtering, the support for forming the deposited film may also serve as an electrode for generating and maintaining discharge, but plasma confinement is insufficient. However, the isolation from the external atmospheric space that is not involved in film formation is insufficient, and it is difficult to say that it functions as a structural material.

In short, the method of the present invention uses a band-like member that can function as a support for forming a functional deposited film as a side wall of the film-forming space, and allows the band-like member to function as the structural material, and also allows the band-like member to function as a support for forming a functional deposited film. It also enables continuous formation of functional deposited films.

Based on the results of experiments conducted by the present inventors, it has been found that currently available plasma CVD equipment, whether using RF or microwave, can be formed within the TCLL chamber. The rate at which the film raw material gas is deposited on the substrate and becomes a deposited film that can actually be put to practical use is about 15% at most, and the recovery rate as a deposited film is actually quite low.

The present inventors conducted repeated studies based on the premise that this point largely depends on the shape and structure of the film-forming space, and found that the surrounding wall of the film-forming space is composed of a base body, and the surrounding wall of the film-forming space is It has been found that the recovery rate can be greatly improved by forming a deposited film on the inner surface. That is, the band-shaped member is used as a base, and the side wall of the film-forming chamber is formed by the band-shaped member while being continuously moved.

Then, a gap is provided in a part of the side wall for evacuating the inside of the film forming chamber. The shape of the film forming chamber is preferably columnar, more preferably cylindrical. In order to improve the recovery rate of the deposited film, it is preferable to increase the ratio of the area of the side wall portion constituted by the band-shaped member to the total area of the wall surface forming the film forming space. That is, the specific shape of the cylindrical film-forming space formed by the band-shaped member is such that the ratio of the length of the side wall (width dimension of the band-shaped member) to the inner diameter dimension of both opposing end surfaces is set as much as possible. It is desirable to increase the size. By doing so, it is possible to form a desired functional deposited film on the inner wall surface of the side wall with a high recovery rate.

In the method of the present invention, in order to prevent the deposited film formed on the substrate from peeling off from the substrate due to the influence of temperature difference from the time of film formation, humidity, etc. when the deposited film is taken out into the atmosphere, The strip member is curved into a substantially columnar shape and subjected to mechanical compressive stress in advance, and a deposited film is formed on the concave curved surface of the strip member curved into a columnar shape at a desired film forming temperature. The belt-shaped member and the deposited film are expanded so that the side on which the deposited film is formed is planar or convex, and slowly cooled to room temperature while converting the pre-applied mechanical compressive stress into mechanical tensile stress. Preferably, a method is used in which the thermal compressive stress caused by the difference in the expansion coefficient between the two is alleviated by the mechanical tensile stress.

By using a material for the band-shaped member whose coefficient of linear expansion is larger than that of the deposited film,
The method of stress relaxation as described above becomes possible.

Conventionally, in order to avoid peeling of the deposited film, measures have been taken from the perspective of strengthening the adhesion between the substrate and the deposited film.
This type of countermeasure is limited to cases where the strength of the base is above a certain level, and for bases made of relatively soft materials such as polyimide or PET (polyethylene terephthalate), the above-mentioned countermeasures alone will not work. This cannot be said to be a sufficient measure against wrinkles on the substrate. Therefore, in addition to strengthening adhesion, stress relaxation can also be an important measure.

In particular, in cases such as solar cell devices that are manufactured by laminating multiple deposited films, the method of the present invention described above is important because the compressive stress may be amplified by stacking the deposited films. be.

In the method of the present invention, in order to efficiently generate and maintain plasma, the impedance of the microwave must be adjusted according to the complex dielectric constant of the plasma, and the inner diameter of the equivalent outer conductor of the coaxial line including the plasma inside the deposition space. The outer diameter of the microwave transparent member is adjusted and selected in advance so that it is equal to the inner diameter of the outer conductor of the coaxial line outside the film forming space.

The expression "equivalent" used here is based on the results of actual discharge experiments, which show that the inner diameter of the outer conductor containing the plasma varies depending on conditions such as the type and flow rate of source gas, the pressure in the deposition chamber, and the microwave power. This is because it has been found that it is difficult to predict the value of the outer diameter theoretically because it affects not only the real part of the permittivity of the plasma but also the imaginary part, that is, the absorption rate, causing a phase inversion. . Therefore, it is certain that the inner diameter of the outer conductor formed by the plasma can be verified experimentally as described below.

Conventionally, in microwave devices with impedance mismatching, that is, with a strong reflective surface, the tuner is used to detect other reflected waves that have the same intensity as the reflected wave generated on the reflective surface and have an inverted phase with the reflected wave. Therefore, a method is used to match the impedance by canceling out these two anti-wave resistances by interference, but even when matching is achieved by canceling out the apparent wave resistance of the building in this way, the above-mentioned reflection surface and A large standing wave is generated between the tuner and the tuner, which often causes large Joule heat loss.

Therefore, in order to eliminate this Joule heat loss, the distance between the reflective surface and the tuner should be made as close as possible, preferably coincident. That is, in the microwave antenna means of the present invention, before discharge starts, both the inside of the film forming chamber and the outside of the film forming chamber have a dielectric constant of 1, and the inner diameter of the outer conductor of the coaxial line is larger than that of the inner diameter of the outer conductor of the coaxial line. Because of the large size, it is difficult to match the impedance at the interface of the deposition chamber, but after the start of discharge, the interior of the deposition chamber is filled with plasma whose dielectric constant is smaller than l, and an equivalent If the inner diameter becomes smaller and the outer diameter of the microwave transparent member is appropriately selected, a situation will be created in which the inner diameters of the outer conductor of the coaxial line inside and outside the film forming chamber can be matched and matched. In this way, it is possible to match the impedance in the state after release.

In the method of the present invention, the gas composition and its state outside the film-forming space are controlled so that the bottom film space is defined by the band-shaped member and the deposited film is formed only within the film-forming space. For example, the gas composition outside the film-forming space may be set to be a gas atmosphere that does not directly participate in the formation of the deposited film, or the gas composition outside the film-forming space may be set to be different from that inside the film-forming space. The atmosphere may include. Although plasma is of course confined within the film forming space, it is also necessary to prevent the plasma and microwaves from leaking outside the film forming space and to suppress abnormal discharge. However, it is also effective in improving plasma stability and reproducibility and preventing film deposition in unnecessary locations.

In addition, in the apparatus shown in FIG. 1, microwave power is input in the TEM mode, so as long as the width of the opening is narrow, microwave leakage is automatically suppressed due to this mode.
When the width of the opening is approximately 1/2 wavelength of the microwave, it is necessary to provide means for preventing microwave leakage. That is, a conductive punching board or the like having a hole diameter of about 1/2 of the wavelength of the microwave as shown in FIG. 6 may be disposed in the gap formed in the longitudinal direction of the strip member.

In the method of the present invention, the pressure outside the film forming space is set to 6 mTo.
As an alternative to maintaining the same effect as maintaining below rr, a gas with a small ionization cross section (such as He or H2)
The abnormal discharge may be suppressed by flowing outside the film-forming space.Of course, the pressure outside the film-forming space is set to 6 mTor.
The gas having a small ionization cross section may be flowed at the same time while maintaining the temperature at or below r.

That is, in the method of the present invention, by confining plasma within the film-forming space and suppressing abnormal discharge outside the film-forming space, the recovery rate of the raw material gas for forming the deposited film can be improved, and the film-forming speed can be dramatically increased. This can enable the production of solar cells on an industrial scale.

In the method of the present invention, in order to form a deposited film with uniform film thickness and film quality over a large area, the microwave antenna means is arranged so as to be parallel to the strip member forming the side wall of the film forming space. Microwave power is injected into the film forming space through a microwave antenna means that penetrates into the film space and radiates microwaves in all directions perpendicular to the direction of propagation of the microwaves, such as a coaxial line or a Gitano coil. This is done by generating plasma. Further, in order to sustain a discharge with a constant plasma density for a long time, it is sufficient to surround the microwave antenna means with the microwave transparent member and completely isolate it from the plasma.

In the method of the present invention, the microwave antenna means is arranged parallel to the strip member, and the distance between the strip member and the microwave antenna means is relatively short;
It is also desirable that the distances be kept equal in the longitudinal direction of the antenna.

By doing this, the antenna means to which the microwave power is applied almost uniformly in the width direction of the band-shaped member with the side wall tS is provided, so that the plasma density distribution is made uniform.

In particular, in the case of a coaxial line in which the center conductor is isolated from the plasma by the microwave-transparent member mentioned above, as the microwave power input into the deposition space via the coaxial line is increased, the inside of the deposition space Microwave absorption into the plasma depends on the type of gas introduced into the plasma and turned into plasma by the microwave power, and the gas flow rate. There is a dark value at which JjLt power becomes saturated. Therefore, the larger the microwave power input into the film forming space, the wider the region where the absorbed power is saturated, so that the same power as the dark value where the absorbed power is saturated is deposited from each part in the longitudinal direction of the antenna. The plasma is injected into the space, and the plasma density is made uniform, that is, the film thickness and quality are made uniform over a large area.

However, when such a large amount of microwave power is input into the film-forming space, the electrical properties of the deposited film to be formed may deteriorate, heat may be generated inside the microwave-transparent member, or the microwave-transparent member may deteriorate. The member may be damaged due to temperature rise caused by exposure to plasma, and the microwave power that can be input into the film forming space may be restricted.

In such a case, the microwave power input into the film forming space is restricted, so the saturation of the absorbed power does not occur and the plasma density does not become uniform, that is,
The microwave power input into the film forming space from the microwave antenna means disposed inside the film forming space gradually decreases along the direction of propagation of the microwaves, resulting in a spatially non-uniform distribution of plasma density. I end up having it.

In order to avoid this and form a deposited film with uniform thickness and quality over a large area, along the direction of microwave propagation,
The microwave i! is shaped like a truncated cone or a cone whose inner diameter gradually increases to compensate for the gradual decrease in the microwave power input into the film forming space along the direction of propagation of the microwave. 3
! The distance between the above-described band-shaped base and the microwave antenna means may be narrowed along the direction of propagation of the microwave by arranging the 4-wire member.

As explained above, the method of the present invention makes it possible to form a deposited film with uniform thickness and quality over a large area, regardless of the magnitude of the microwave power input.

In the method of the present invention, it is desirable that the inner wall surface of the film-forming space has conductivity necessary for a bias current of a desired current density to flow. For this purpose, first, the strip member is made of a conductive material. However, it is necessary that at least the surface facing the film forming space is subjected to conductive treatment.

In the method of the present invention, in order to control the plasma potential of the microwave plasma, it is preferable that the bias applying means be disposed so that at least a part thereof is in contact with the plasma generated in the film forming space. The means may also serve as a gas supply means for introducing a raw material gas for forming a deposited film into the film forming space, and may also be one or more bias rods provided separately from the gas supply means. Also good.

In the former case, the gas is It is desirable that the supply system and the gas supply to which the bias voltage is applied be insulated and separated in the middle. It is preferable that the insulation-isolated position be close to the film-forming space.

It is desirable that at least a portion of the bias application means that also serves as the gas supply means, which comes into contact with the microwave plasma, be subjected to conductive treatment so that the bias voltage can be applied, but it may be deformed or damaged by plasma heating or the like. , the material must be carefully selected to prevent melting, etc. Specifically, it is desirable to construct the structure by coating a high melting point metal on a high melting point metal or a high melting point ceramic.

Further, the bias applying means that also serves as the gas supply means is arranged in the film forming space so that it is in contact with the microwave plasma, since the microwave plasma acts as a substantially uniform conductor. Although there is no particular limitation as long as it is provided, in order to suppress the occurrence of abnormal discharge, etc., it is preferable to arrange it at a distance of at least 1Q mm, more preferably at least 20 mm, from the inner surface of the band-shaped member.

On the other hand, in the latter case, the material for applying the bias rod and the position thereof are considered in the same manner as in the case where the bias applying means also serves as the gas supply means. However, it is preferable that the gas supply means be made of a dielectric material in order to suppress the occurrence of abnormal discharge and to form a uniform plasma potential in the film forming space, but when the applied bias voltage is relatively low, etc. There are no particular restrictions on the material.

In the method of the present invention, when a single bias rod or bias applying means that also serves as the gas supply means is provided, direct current, pulsating current, and alternating current voltage may be applied singly or in a superimposed manner as the bias voltage. is desirable, and when a plurality of bias rods are provided, the same or different DC voltages may be applied to each of them, or each of DC, pulsating current, and AC voltage may be applied singly or in a superimposed manner. By applying multiple types of bias voltages, which may be applied at different times, it is possible to not only widen the control range of the plasma potential, but also to improve plasma stability, reproducibility, and film properties, and to suppress the occurrence of defects. It will be done.

Said intersection 2i! Preferable examples of the voltage include a sine wave, a square wave, a triangular wave, a pulse wave, and a waveform obtained by superimposing these waves. In addition, examples of the pulsating voltage include a waveform obtained by preferably half-wave rectification or full-wave rectification of the AC voltage, a ramp wave, and the like. Furthermore, the direct current voltage or maximum amplitude voltage of the bias voltage is appropriately set in consideration of the film characteristics of the deposited film to be formed, the rate of occurrence of defects, etc. Although the spark may be kept constant until the end of the process, it is preferable to change it continuously or at appropriate intervals in order to control the characteristics of the deposited film formed and to suppress the occurrence of defects.In particular, the spark If an abnormal discharge such as
Since a sudden change in bias voltage occurs, it is necessary to detect this electrically and reduce the bias voltage immediately, or -
It is preferable to interrupt the process and then return to the predetermined bias voltage again in order to suppress the occurrence of defects in the deposited film. Of course, these steps may be performed manually, but it is preferable to provide an automatic control circuit in the control circuit of the bias application means in order to improve the yield of the deposited film.

In the method of the present invention, the bias applying means may also serve as the strip member. In this case, a ground electrode is provided in the film forming space.

The ground electrode may also serve as the gas supply means.

In the method of the present invention, the strip member is made of a conductive material or an insulating material whose surface is subjected to conductive treatment, and the strip member is heated and maintained at least during the formation of the deposited film. It is necessary to be constructed of a material having a conductivity that ensures sufficient current density at the temperature. Specifically, so-called metals, semiconductors, etc. can be mentioned. Further, a region partially made of an insulating material may be provided on the band-shaped member for the purpose of facilitating the element isolation process. If the area is large, a deposited film with controlled plasma potential will not be formed in that area, but if the area is small, a film with almost the same characteristics as a film formed on a conductive member will be formed. is formed.

According to the method of the present invention, a microwave applicator means is provided for uniformly radiating or transmitting microwave energy in the width direction of such a band-shaped member constituting the side wall of the film forming space, thereby generating and generating microwave plasma. By adjusting and optimizing the maintenance conditions and bias application means, it is possible to continuously form a high quality functional deposited film over a large area with good uniformity and reproducibility.

Further, according to the method of the present invention, by appropriately controlling the plasma potential, a high-quality functional deposited film having desired characteristics and few defects can be continuously formed efficiently and at a high yield. .

In the method of the present invention, in order to uniformly and stably generate and maintain plasma in the columnar film forming space,
The shape and volume of the film forming space, the flow rate of the raw material gas introduced into the t2 film forming chamber, the pressure in the film forming space,
Although there are optimal conditions for the amount of microwave power input into the film forming space, microwave matching, etc., these parameters are organically linked to each other and cannot be generally defined. It is desirable to set favorable conditions as appropriate.

Hereinafter, the apparatus of the present invention will be explained in more detail.

In the apparatus of the present invention, when the strip member functions as a structural material, the outside of the film forming chamber may be in the atmosphere, but the functional deposited film is formed by the inflow of air into the film forming chamber. If the characteristics of the product are affected, an appropriate means for preventing atmospheric inflow may be provided, specifically, a mechanical sealing structure using O-rings, gaskets, helicotrex, magnetic fluid, etc., or , a diluent gas atmosphere that has little or no effect on the properties of the deposited film that is formed;
Alternatively, in the case of the mechanical sealing structure, in which it is preferable to arrange an isolation container around the device to create an appropriate vacuum atmosphere, the band member can maintain a sealed state while continuously moving. Special consideration must be given to the following: 0 When the apparatus of the present invention and a plurality of other deposited film forming apparatuses are connected to successively stack deposited films on the strip-shaped member,
It is desirable to connect each device using a gas gate means or the like. Also, when multiple devices of the present invention are connected, each device has an independent film forming atmosphere in the film forming chamber. The container may be a single container or may be provided in each device.

In the apparatus of the present invention, the pressure outside the film forming chamber may be in a reduced pressure state or a pressurized state, but if the band member is significantly deformed due to a pressure difference within the film forming chamber, an appropriate auxiliary structure may be used. All you have to do is arrange the materials.

The auxiliary structural material may be formed of a wire rod, thin plate, etc. made of metal, ceramics, reinforced resin, etc., and having approximately the same shape as the side wall of the film forming chamber, and having an appropriate strength. Desirably, the contact portion of the strip member that contacts and supports the surface of the auxiliary structural material that is not exposed to the microwave plasma is substantially in the shadow of the auxiliary structural material, so that the formation of a deposited film is prevented. Almost never done. Therefore, it is desirable that the projected area of the auxiliary structural material onto the strip member be designed to be as small as possible.

Further, by bringing the auxiliary structural material into close contact with the belt-like member and rotating or moving it in synchronization with the conveyance speed of the belt-like member, the mesh pattern etc. applied on the auxiliary structural member can be transferred onto the belt-like member. It can also be formed.

First, regarding the material of the band-shaped member used in the device of the present invention, a material that has flexibility that allows the band-shaped member to be continuously curved is used, and at the curved start end, curved end, and intermediate curved part, It is desirable to form a smooth shape. Further, it is preferable that the belt-shaped member has a strength that is difficult to bend or twist when it is continuously conveyed.

Specifically, thin plates and composites of metals such as stainless steel, aluminum and its alloys, iron and its alloys, copper and its alloys, and metal thin films of different materials on their surfaces are sputtered or vapor-deposited. , those whose surface has been coated by plating method, etc., and heat-resistant resin sheets such as polyimide, polyamide, polyethylene terephthalate, epoxy, etc., or composites of these with glass fibers, carbon fibers, boron fibers, metal fibers, etc. Metals or alloys and transparent conductive oxides (TC) on the surface.
Examples include those obtained by conducting conductive treatment using methods such as plating, vapor deposition, coating, and the like. In addition, SiOH, 5j3Na was applied on the conductive treated surface of the strip member having the above-mentioned structure.
,Aj! ! os, A14N.

Alternatively, a material partially formed with an insulating thin film such as the above-mentioned heat-resistant resin can also be used.

Further, the thickness of the band-shaped member is determined to be as thin as possible in consideration of cost, storage space, etc., as long as it is within a range that exhibits strength that maintains the curved shape formed during transportation by the transportation means. is desirable.

On the other hand, in order to increase the recovery rate of the deposited film mentioned above, one curved end support ring, indicated by 308 in FIG. In order to convey the member, the band-like member itself needs to have strength so that it does not sag between the pair of opposing end support rings of the curved portion, so it is better for the band-like member to be somewhat thick. Regarding stress relaxation of the deposited film mentioned above, the thicker the band member is, the better.Therefore, the thickness of the band member is adjusted appropriately in consideration of these points, but the type of material of the band member and the curvature of its bending For example, if the strip member is made of stainless steel, its thickness is 0.0
It is about 3 to 0.3 w. Similarly, in the case of aluminum or copper, it is about 0.05 to 0.5 wn, and in the case of synthetic resin, it is about 0.1 to 3 fi.

When the band-shaped member is used as a substrate for a solar cell, it may be used as an electrode for direct current extraction if it is made of electrically conductive material such as metal, or it may be made of electrically insulating material such as synthetic resin. In this case, A1. , Ag, Pt.

Au, Ni, Ti, Mo, W, Fe, V, Cr.

Cu, stainless steel, brass, nichrome, SnO,.

Inn0+, ZnO, SnO2-1ntO3 (ITO
), etc., and transparent conductive oxides (TCO) are preferably surface-treated in advance by plating, vapor deposition, svanta, etc. to form electrodes for current extraction. In order to facilitate the element isolation process, an insulating film may be partially formed.

Of course, even if the strip member is made of an electrically conductive material such as metal, it can improve the reflectance of long wavelength light on the substrate surface, or improve the mutual diffusion of constituent elements between the substrate material and the deposited film. A different metal layer or the like may be provided on the side on which the deposited film is formed on the substrate for the purpose of preventing this or forming an interference layer to prevent short circuits. In the case of a solar cell having a layered structure in which light enters from the side of the strip member, conductive F! of the transparent conductive oxide, metal thin film, etc. is used. It is desirable to deposit the film in advance.

Further, the surface properties of the band-shaped member may be a so-called smooth surface or a minutely uneven surface.

In the case of a minutely uneven surface, the shape of the unevenness is spherical, conical, pyramidal, etc., and the maximum height (Rmax)
is preferably 500 to 5,000 people, whereby light reflection on the surface becomes diffused reflection, resulting in an increase in the optical path length of the reflected light on the surface.

In the apparatus of the present invention, in order to control the thickness of the film deposited within the film forming chamber, it is preferable to insert a substrate cover that partially covers the side wall.

The center conductor used in the device of the present invention is preferably made of a metal member with a small ohmic resistance. Specifically, the conductor may be made of silver, copper, aluminum, etc., or may be plated on a center conductor made of other materials. In this device, a silver-plated stainless steel tube was used.

In addition, the center conductor that has been thrust into the film forming chamber is separated from the plasma by a microwave-transparent member around it, and a deposited film is formed on the center conductor, which acts as a microwave absorber and generates microwaves. This avoids a decrease in power input efficiency.

In the film forming chamber, the wall surface opposite to the surface into which the center conductor is inserted is made of a microwave reflecting member, while the surface into which the center conductor is inserted transmits microwaves and simultaneously reflects the inside of the film forming chamber. The side wall of the film forming chamber is covered with a conductive strip member, so if the width of the strip member is appropriately selected, resonance can be achieved. It becomes a vessel structure.

As is well known, electromagnetic waves are strongly reflected at interfaces and short-circuit surfaces where the impedance of the w@ path suddenly changes.

Here, the opposite end surfaces of the film forming chamber described above each correspond to short-circuit surfaces with the aforementioned boundary surfaces, so they strongly reflect microwaves, and when electromagnetic waves are injected into a cavity in which two strong reflecting surfaces are appropriately arranged, A resonator structure with a high Q value can be constructed.

In the apparatus of the present invention, a resonator structure may be constructed by making both opposing end surfaces of the film forming chamber movable, but a semi-coaxial resonator structure is formed by the central conductor insertion length adjustment mechanism, which is superior in terms of operability. Alternatively, the resonator length may be equivalently made variable, that is, the impedance may be adjusted by inserting a microwave-transparent high dielectric constant member into a desired location in the film forming chamber.

If the resonator structure is adjusted in advance before discharge as described above, discharge can be easily started due to the power storage effect of the resonator structure, and the impedance can be matched by the above-mentioned center conductor insertion length adjustment mechanism after discharge. For example, a constant discharge state can be maintained over a long period of time over a wide film-forming pressure range.

The microwave transparent member used in the apparatus of the present invention includes, for example, a dielectric tube designated by 103 in FIG.

The material of the dielectric tube may be any material as long as it has a small dielectric loss tan δ (tan delta) in the microwave band to be used. This is even better because it prevents the film from changing in quality and increasing the reflection and absorption of microwave power, and also prevents thermal damage to the dielectric tube. Suitable materials for such conditions include Berria, Algos ceramics, boron nitride, and quartz, with alumina ceramics being the most suitable.

In order to generate a microwave glow discharge and to discharge it stably and constantly, the dielectric tube is required to have the function of transmitting microwaves and maintaining airtightness. As for the shape of the dielectric tube that fulfills this function, either of the following two methods is optimal. That is, an open-end cylindrical tube in which one perforated flange is welded to each end of an open cylindrical tube, or a closed-end cylindrical tube in which a perforated flange is welded to the open end of a cylindrical tube with one end closed. Either.

Then, the flange part should be placed in close contact with one wall of the opposite end face of the film forming chamber via the ○ ring to maintain airtightness.From the point of view of maintenance and inspection, the latter closed-end cylindrical tube is even more convenient.

The microwave-transparent high dielectric constant member used in the device of the present invention is made of a material such as alumina ceramics, beryllia, or boron nitride, and is a semi-coaxial member configured by the center conductor insertion length adjustment mechanism described above. The inventors of the present invention have confirmed through studies that by disposing the resonator inside or at the end of the resonator structure, the effect of changing the resonator length within a uniform range can be obtained.

As a result of further investigation by the present inventors, it was found that the optimum dimensions of the microwave-transparent high dielectric constant member have a correlation with the insertion length of the center conductor.

Therefore, with the insertion length of the center conductor fixed, HP87
Using the 57A Scalar Nesotowork Analyzer (manufactured by Hiereosoto Pancard), the resonant frequency was determined to be 2.
The shape of the microwave-transparent high dielectric constant member may be determined so that the frequency is 45 GHz.

Regarding the means for supporting and transporting the belt-shaped member used in the apparatus of the present invention, since the belt-shaped member (substrate) forms the side wall of the film forming chamber, the belt-shaped member is twisted, bent, or bent during transport. If meandering or the like occurs, the discharge becomes unstable and it becomes difficult to produce a large quantity of films of the same quality with good reproducibility.

Furthermore, if dirt or grime adheres to the surface of the means for supporting and conveying the belt-like member, this often causes defects in the deposited film, which has been a problem. In other words, the means for supporting and transporting the strip-shaped member includes preventing deformation of the film-forming chamber and placing the strip-shaped member on the surface on which the deposited film of the strip-shaped member is formed (hereinafter referred to as the "film-forming surface"). It has been found that two important points are to avoid contact between supporting and transporting means as much as possible.

That is, in order to prevent deformation of the film forming chamber at the second point, a known crown mechanism is incorporated into the means for supporting and conveying the strip member to prevent twisting and meandering, and a known tension adjustment mechanism is used to prevent deflection. I can do it.

In addition, in order to prevent the means for supporting and transporting the strip member from coming into contact with the film forming surface at the second point as much as possible, support on the a-film side of the strip member is performed only at the peripheral edge of the strip member, and the strip member is The back side of the film-forming surface of the member may be supported and conveyed over the entire width of the band-shaped member.

In other words, in the case where the curved portion forming means of the band-shaped member is installed inside the film-forming chamber, only the peripheral edge of the band-shaped member is contacted or
The supporting ring for supporting the curved part end face, which is installed outside the film forming chamber, is a roller that contacts and supports the belt-shaped member over the entire width thereof. In order to support and transport the inner side of the band-shaped member with the curved part end support ring, it may be supported by a number of curved part support inner rings shown at 113 in FIG. 1, or by 308 in FIG. It may be supported by a pair of curved portion support inner rings having substantially the same size as the opposing end surfaces of the cylindrical film forming chamber shown.

Here, in order to form a columnar film forming chamber with a curved strip member as a side wall and a gap provided in the longitudinal direction of the strip member described above, the strip member that is continuously conveyed is connected to a pair of openings. The conveyance direction is gently changed by a bending start end forming roller consisting of a support inner roller and an opening support outer roller, and the belt-like member is curved to form a side wall of the film forming chamber by the curved part end support ring. This is done by gently changing the conveyance direction of the curved end forming roller, which is composed of a pair of opening support inner roller and opening support outer roller, which are different from those mentioned above.

Here, if the diameter of the aperture support outer roller is too large, the distance from the center conductor to the strip member varies depending on the direction, resulting in many areas with uneven plasma density, which is undesirable. If the diameter of the roller is too small, the bending stress will leave distortions in the strip member or cause the film to peel off. Therefore, for a metal strip member with a thickness of 0.15 m, a roller with a diameter of 60 mφ to 100 mφ,
For a thickness of 0.05 mm, it is desirable to use a roller with a diameter of about 25 wφ.Furthermore, in order to quickly finish vacuuming after maintenance, the distance between the curved start end forming roller and the curved end forming roller is adjusted. The device may have a variable configuration.

Note that the band-shaped member is supported by the curved part end face support ring.
The conveying method may be simple sliding friction alone, or the strip member may be processed into a sprocket 6 or the like, and at the same time, the curved portion end support ring may be a sprocket.

Furthermore, in the apparatus of the present invention, the surface temperature of the strip member is an important parameter that influences the film quality of the deposited film, and lamp radiation as shown in FIG. By heating, the belt-shaped member can be heated from the back side of the film-forming surface. However, if the conveyance speed of the belt-shaped member is slow, that is, the time the belt-shaped member stays in the film forming chamber is long, or if the input power of the microwave is large, the temperature of the belt-shaped member increases significantly, and lamp radiation heats the belt-shaped member. You may not be able to adjust the temperature if you do so only. In such a case, in addition to the curved part supporting inner ring shown at 308 in FIG. By bringing the curved portion supporting outer roller into pressure contact and incorporating a heat exchange medium inside the curved portion supporting outer roller, both heating and cooling become possible and temperature adjustment becomes possible.

The present inventors have investigated incorporating a function to prevent the occurrence of problems (i) to (iii) below into the means for introducing the film-forming raw material gas and the means for evacuating the film-forming chamber. .

(1) Defects occur on the film formation surface due to IRI separation of the film; (ii
) most of the film is deposited on the means of introducing the source gas;
and (iii) the spatial distribution of the source gas is non-uniform.

As a result, it became clear that there was a decline.

That is, regarding the problem (i) above, a load lock mechanism as shown in Figure 5 is installed, and if the deposited film begins to peel off significantly during the deposition process, the deposition process is stopped and the film forming chamber is closed. Peeling of the film can be suppressed by replacing the internal fixing members, such as the raw material gas introduction pipe and the dielectric pipe.

Regarding (it), if the means for introducing the raw material gas becomes high temperature, the raw material gas will be thermally decomposed and will stick to the means for introducing the raw material gas, so to prevent this, it should be made of metal, especially nickel or stainless steel. suitable.

On the other hand, regarding (iii), the plurality of small holes provided on the surface of the bias application front 106 which also serves as the raw material gas introduction pipe are oriented in the opposite direction to the slit-shaped opening 110 as shown in FIG. As is well known, the distance between the small holes may be made longer on the upstream side and shorter on the downstream side.

In the apparatus of the present invention, the bias applying means provided for controlling the plasma potential is arranged so that at least a portion thereof is in contact with the plasma generated in the film forming chamber. Typical examples of the arrangement and the like will be specifically explained below with reference to the drawings, but the bias applying means in the via of the present invention is not limited to these.

19(A) to 19(D) show HH' in the cross-sectional schematic diagram shown in FIG. 4 of the apparatus of the present invention shown in FIG.
A schematic side cross-sectional view in the direction is shown.

In these drawings, only the main constituent members are shown.

The example shown in FIG. 19(A) is a typical example where the bias application means also serves as a gas supply means, and the belt-like member 1901
is grounded and is being conveyed while maintaining its curved shape by support/conveyance rollers 1902. 1903 is a bias application tube that also serves as a gas introduction tube, and the gas supply tube 19
10 and an insulating joint 19 (19). A bias voltage generated by a bias application power supply 1907 is applied to a bias application front 1903 which also serves as a gas introduction pipe. In addition to commercially available DC stabilized power supplies, AC power supplies, high-frequency power supplies, etc., the 1907 can also be used to precisely convert the waveform output generated by a function generator in order to apply bias voltages with various waveforms and frequencies. You can make your own power supply system that amplifies it with a power amplifier.

It is preferable to constantly monitor the bias applied voltage and bias current value using a recorder, etc., to ensure plasma stability and
It is desirable to incorporate this data into a control circuit for improving reproducibility and suppressing the occurrence of abnormal discharge.

The position where the pre-bias application 1903 is disposed in the film forming chamber is such that the pre-bias application 1903 is placed in the microwave plasma.
Although there is no particular limitation as long as the strip members 19 are arranged in contact with each other, in order to suppress the occurrence of abnormal discharge etc.
It is desirable that the distance from the inner surface of 01 is preferably 104 or more, more preferably 20f1 or more.

Since the bias application tube 1903 also serves as a gas introduction tube, it is desirable that holes or thrusts are formed in the circumferential direction, particularly in the longitudinal direction, so that the raw material gas can be discharged uniformly.

Further, the diameter and length of the tube are designed to ensure a desired current density, but the surface area is preferably made as small as possible as long as the current density is ensured. Thereby, it is possible to suppress a decrease in the utilization efficiency of the raw material gas due to the formation of a deposited film on the surface, and an increase in the defect occurrence rate of the deposited film formed on the strip member due to peeling of the deposited film and scattering. . Moreover, by adopting this configuration, it is possible to further improve the decomposition efficiency of the raw material gas.

The example shown in FIG. 19 (B) and FIG. 19 CD> is a typical example in which the gas supply means and the bias application means are provided independently.
Although one bias rod 1904 and a second bias rod 1906 are provided in FIG. 19(D),
If desired, another bias rod may be additionally provided.

1907 and 1908 are power supplies for bias application, respectively;
The specifications may be exactly the same, or they may be of different specifications so that independent bias voltages can be applied to each.The raw material gas is introduced into the film forming chamber through the gas introduction pipe 1905. Ru. The bias rod 1904 and the second bias rod are each made of a heat-resistant metal such as stainless steel, nickel, titanium, vanadium, niobium, tantalum,
It is preferable to use a rod-like or tubular material made of molybdenum, tungsten, or the like. By having a tubular structure, it is possible to flow a cooling medium therein to suppress abnormal heat generation of the bias rod.

Moreover, the positions where these are arranged are the same as those of the bias application tube 1.
This is almost the same as the case of 103.

The gas introduction pipe 1905 is preferably made of a dielectric material in order to suppress the occurrence of abnormal discharge and form a uniform plasma potential, but it can also be used without any problem even if it is conductive and grounded.

The example shown in FIG. 19(C) is a typical example in which a bias voltage is applied to a band-shaped member, and a bias-applying power source 1907 is connected to the band-shaped member 901. and,
The gas introduction pipe 1905 is made of a conductive member and is grounded. Note that the gas introduction pipe 1905 may be made of a dielectric material, and a ground electrode may be provided separately from this. The position where the gas introduction pipe 1905 is disposed is not particularly limited as long as it is in contact with the plasma.

According to the device of the present invention, by applying appropriate bias voltages to the bias applying means alone or in combination,
A desired plasma potential can be controlled. and,
As a result, a high-quality functional deposited film with few defects can be continuously and efficiently formed with high yield and good reproducibility.

The functional deposited films that are continuously formed in the method and apparatus of the present invention include 3i, Qe,
So-called group III raw conductor thin films such as C, 5iGe, SiC, 5i
So-called ■ group alloy semiconductors such as Sn'iR'iIf! , Ga
As, GaP, GaSb.

So-called m-v group compound semiconductor thin films such as InP and InAs, and Zn5e, ZnS, ZnTe+Cd5CdSe,
Examples include so-called II-VI group compound semiconductor thin films such as CdTe.

The raw material gas for forming the functional deposited film used in the method and apparatus of the present invention is preferably a hydride, a halide, an organometallic compound, etc. of the +** element of the various semiconductor thin films described above. Those that can be introduced in a gaseous state are selected and used.

Of course, these raw material compounds can be used not only alone, but also in combination of two or more. Further, these raw material compounds are TTe, Ns, Ar, and Kr.

Noble gases such as Xe and Rn, and H! , HF, HCl, or the like.

Further, the continuously formed semiconductor thin film can perform valence electron control and forbidden band width control. Specifically, a raw material compound containing an element serving as a valence electron control agent or a forbidden band width control agent may be introduced into the film forming chamber alone or mixed with the deposited film forming raw material gas or the diluent gas. .

[Equipment example]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific examples of devices of the present invention will be described with reference to the drawings, but the present invention is not limited to these device examples.

FIG. 1 is a perspective view schematically showing a typical example of a film-forming chamber and its peripheral mechanism, which is constructed by using a moving band-shaped member as a side wall, which is a feature of the present invention.

In FIG. 1, 101 is a band-shaped member, 102 is a center conductor of a coaxial line for inputting microwaves, 103 is a dielectric tube that is a microwave-transparent member, 104 is a film forming chamber, 1
05 is a small hole, 106 is a bias application tube that also serves as a raw material gas introduction tube, 107 is a vacuum exhaust port, 108 is a strip member supporting outer roller 1 (19 is a strip member supporting inner roller, 11
0 is a slint-like opening of the film forming chamber, 111 is an outer roller supporting the opening, 112 is an inner roller supporting the opening 113 is an inner ring supporting the curved part, 114 is an insulating joint, 115 is a gas supply pipe, and 116 is a bias application 117 is a conductive wire.

Note that the two arrows in FIG. 1 each indicate the flow of the raw material gas.

In FIG. 1, a film forming chamber 1 composed of a strip member 101 is shown.
Reference numeral 04 has a cylindrical shape, and a central conductor 102 of a coaxial line is disposed on the rotation axis of the film forming chamber, and a dielectric conductor which is a microwave transparent member is coaxially connected to the central conductor 102 inside the film forming chamber 104. A body tube 103 is arranged. This film forming chamber 104 includes an opening support outer roller 111 and an opening support inner roller 11.
2, the belt-shaped member 101 is sandwiched between the belt-shaped member 101 and the belt-shaped member 101, and the direction of conveyance is changed. The member 101 is supported and conveyed to form a columnar side wall, and the belt-shaped member 101 is again sandwiched between the opening support outer roller 111 and the opening support inner roller 112 while changing its conveyance direction, thereby forming a columnar shape. I can do it. In addition, as described above, in order to prevent twisting, sagging, etc. of the belt-shaped member 101 during transportation,
The belt-like member supporting outer roller 108 and the belt-like member supporting inner roller 1 (1
The belt-shaped member 101 is supported and conveyed while being sandwiched between the belt-shaped member 9 and the belt-shaped member 9.

In FIG. 1, a slit-shaped opening 110 formed of a strip member 101 maintains the shape of the opening by supporting the strip member 101 with an opening support outer roller 111 and an opening support inner roller 112. The opening support inner roller 112 contacts only the peripheral edge of the strip member 101, and drives the strip member 101 from outside the film forming chamber by a separately provided drive mechanism (not shown). By providing the drive mechanism with a tension adjustment mechanism, it is possible to carry out the conveyance without slack.

In FIG. 1, a bias application tube 106 that also serves as a raw material gas introduction tube is introduced into the film forming chamber 104, and its arrangement is as shown in FIG. Arranged on the opposite side of the slit-shaped opening +10,
A large number of small holes 105 are provided on a bias application tube 106 that also serves as a source gas introduction tube, and are arranged in a direction toward the strip member 101 .

A bias voltage generated by a bias application power supply +16 is applied to the bias application tube 106, which also serves as a raw material gas introduction pipe, via a conductive wire 117.

Further, the bias application tube 106 which also serves as a gas introduction tube is insulated and separated from the gas supply tube 115 via an insulating joint 114.

The strip member 101 is grounded, but is preferably grounded uniformly over almost the entire side wall portion of the columnar film forming chamber, and includes an opening support outer roller 111, an opening support inner roller 112, and a curved portion support inner ring. 113, and an electric brush (not shown) that contacts the side wall of the strip member 101.

A mechanism for introducing microwave power into the film forming chamber 104 shown in FIG. 1 will be explained using FIG. 3.

In FIG. 3, a coaxial line will be described as an example of the microwave antenna means, but antenna means such as a Risitano coil may also be used.

In FIG. 3, 301 is a rectangular waveguide, 302 is a coaxial plunger (movable P end), 303 and 304 are 1i magnetic shield members, 305 is a coaxial plunger fixing member, and 306
307 is a microwave transparent high dielectric constant member, 308 is a curved part support inner ring, 3 (
19 is a roller or bearing, 310 is a center conductor cooling gas inlet, 311 is a small hole, 312 is a stopper 31
3 is a waveguide coaxial converter.

As shown in FIG. 3, the center conductor 102 has a hollow structure, one end of which is inserted into the film forming chamber 104, exits to the outside of the coaxial line via a waveguide coaxial converter 313, and the other end of the center conductor 102 is hollow. serves as a center conductor cooling gas inlet 310. The center conductor 102 includes an electromagnetic shielding member 303 made of spring material,
304 and a central conductor fixing member (not shown), electrical contact is well maintained. For example, the center conductor fixing member may have the same structure as the coaxial plunger fixing member 305, but the mounting position may be rotated by 90 degrees around the axis of the center conductor. In FIG. 3, this fixing member is A simple bolt is used instead. By moving a portion of the center conductor 102 in the vicinity of which the electromagnetic shielding member 304 is in contact, the insertion length of the center conductor 102 into the film forming chamber 104 can be adjusted from outside the coaxial line.

In FIG. 3, the coaxial plunger 302 has a structure that can be operated from outside the coaxial line, as is clear from the figure. This coaxial plunger 302 includes an electromagnetic shielding member 30 that uses a spring material to make good electrical contact.
3 is fixed by fastening or spot H8 contact. A hole through which the center conductor 102 can pass is provided in the center of the coaxial plunger 302, and another electromagnetic shielding member made of a spring material is provided so that the coaxial plunger 302 can slide smoothly along the center conductor 102. 303 is provided at the contact portion.

Further, the center conductor 102 is provided with a stepped portion in the middle, for example, a stopper 312 or the like is provided, so that the microwave-transparent dielectric tube 103 and the end of the center conductor 102 come into contact and break the dielectric tube 103. It is more convenient in practice to take measures to prevent this from happening.

A similar stop bar is provided at the other end of the coaxial plunger 302 to prevent the end surface of the coaxial plunger 302 from protruding to the waveguide coaxial conversion section 313. If this part protrudes, abnormal discharge is likely to occur in the electromagnetic shielding member 303 that maintains good contact between the coaxial plunger 302 and the outer conductor, and in some cases, it may burn out, causing a practical problem.

In FIG. 3, a waveguide coaxial converter 313 is formed by penetrating a coaxial line having a center conductor 102 into a rectangular waveguide 301.

In FIG. 3, the rectangular waveguide 301 is connected to a 2.45 GHz microwave oscillator manufactured by Kouwick Shokai Co., Ltd. (not shown).

In FIG. 3, a microwave transparent high dielectric constant member 30
The shape of 7 is approximately a truncated cone, and a plurality of holes for discharging cooling gas are provided on the conical surface.

Therefore, the center conductor cooling gas flows through the center of the hollow center conductor 102 from the center conductor cooling gas inlet 310, passes through the end opening of the center conductor 102, and flows along the inner surface of the microwave transparent dielectric tube 103. , a plurality of small holes 31 provided in the side wall of the rectangular waveguide 301 pass through an outlet provided on the conical surface of the microwave-transparent high dielectric constant member 307.
It is discharged from 1.

In FIG. 3, only the peripheral edge of the band member 101 is supported and conveyed by a pair of curved part supporting inner rings 308,
It forms a cylindrical space. Curved part support inner ring 30
8 is rotatably supported by rollers (or bearings) 3 (19) arranged around it, both of which are grounded. Alternatively, small rings may be disposed on the peripheral edge of the strip-shaped base 101 so as to face each other.

In FIG. 3, the center conductor 102 is isolated from the plasma generated in the Jf chamber 104 by a dielectric tube 103. The dielectric tube 103 has a hemispherical shape at one end and is a closed tube, and the other end. has a vacuum flange, and the space between them is cylindrical, and the structure is such that vacuum sealing is possible with the vacuum flange.

In FIG. 3, a circular choke flange 306 is tightly fastened to the vacuum flange of the dielectric tube 103, and the circular choke flange 306 and the dielectric tube 10
The structure is such that there is no leakage of microwaves even if the electrical contact with the metal surface for vacuum sealing in step 3 is poor.

The apparatus of the present invention is a microwave plasma CV as described above.
In addition to the main mechanism as the D device, a load lock mechanism is provided as an auxiliary mechanism.

That is, by providing the load lock mechanism shown in FIG. 5, not only the number of defects was reduced, but also maintenance performance was dramatically improved. The details of the load lock mechanism will be explained below.

In FIG. 5, 501 is a replacement load lock chamber;
2 is a gate valve, 503 is a replacement door, 504 is a vacuum exhaust port, ■ is a predetermined position of a dielectric tube and a raw material gas introduction tube during deposition film formation, and ■ is a predetermined position for replacing these. Represents the position when pulled out.

In FIG. 5, the center conductor 102, dielectric window 103, and bias application tube 106, which also serves as a raw material gas introduction tube, can be replaced as a unit.
Fixing members (not shown) are prepared in advance at each position so that they can be fixed at any position. Further, an arm (not shown) for moving the unit from position (2) to position (2) is also provided in the replacement load lock chamber 501. A vacuum pump (not shown) is connected to the vacuum exhaust port 504, so that the inside of the replacement loadronk chamber 501 can be evacuated. Further, the center conductor 102 and the bias application tube 106 which also serves as a raw material gas introduction tube are both structured so that they can be attached and detached near the gate valve 502.

The load lock mechanism shown in FIG. 5 is arranged adjacent to the film forming chamber 104 shown in FIG. 1 via a gate valve 502.

In operating the microwave plasma CVD apparatus of the present invention as described above, first, it is necessary to make the initial discharge easy to occur, and to adjust the 1'li and film thickness according to the discharge conditions to form the desired deposited film. Adjusting and selecting the outer diameter of the dielectric tube 103 in advance so that impedance matching can be achieved between the coaxial line in the portion that has not entered the chamber 104 and the coaxial line in the portion that has entered the interior of the film forming chamber 104;
Of course, there may be situations where there is no problem with the operation of this device even if you do not perform these settings, but in order to make the most of the functions of this device, , the above settings are important.

First, in order to make it easier for the initial discharge to occur, which is the first setting, it is necessary to increase the pressure inside the deposition chamber, increase the input microwave power, or cause a spark discharge using a Tesler coil, etc. In the apparatus of the present invention, the film forming chamber 104 constitutes the above-mentioned semi-coaxial resonator, thereby making it easier to generate the initial discharge as described above. It has been found that a constant discharge can be sustained over a long period of time over a wide range of film-forming pressures. Here, to configure a semi-coaxial resonator, use an HP8757A Scalar Nesotowork Analyzer (manufactured by Hewlett-Paracard) to form a semi-coaxial resonator with the dielectric tube 103 attached at a predetermined position. The insertion length of the center conductor 102 into the film forming chamber 104 may be adjusted in advance while confirming the resonance state using the .

Next, the adjustment and selection of the outer diameter of the dielectric tube 103, which is the second setting, is carried out between the coaxial line of the part that has not entered the film forming chamber 104 and the coaxial line of the part that has entered the inside of the film forming chamber 104. This can be done so that impedance matching can be achieved between the coaxial line and the line; that is, a coaxial line with uniform scratches is formed in accordance with the plasma density inside the film forming chamber 104 where the discharge has occurred. The plasma density, that is, the complex dielectric constant of the plasma, changes mainly depending on the gas mixture ratio, gas pressure, or the dimensions of the microwave power dielectric tube introduced. Since these four variables are interrelated, it is difficult to theoretically predict the optimal diameter of the dielectric tube 103 that will bring the coaxial line that has entered the film forming chamber into a matching state with the coaxial line that has not entered the film forming chamber. It is.

Therefore, it is sufficient to experimentally confirm the matching state by selecting the outer diameter of the dielectric tube 103 and adjusting the insertion length of the central conductor 102 into the film forming chamber 104 after discharge.

As a specific example, in the case of the conditions shown in Table 8 of Film Formation Example 8, which will be described later, the conditions are as follows. That is, in a film forming chamber with an inner diameter of 40 mm, the center conductor is 6 mm in diameter and the outer conductor is 20 mm in diameter.
It is a coaxial line of nφ, and the outer diameter of the dielectric tube is approximately 1.8nφ.
It is preferable that the insertion length of the center conductor is 452 mm.In addition, in a film forming chamber with an inner diameter of 105 mm, the center conductor is a coaxial line of 15 mm and the outer conductor is a coaxial line of 30 mm.
Preferably, the outer diameter of the dielectric tube is approximately 23 tmφ, and the insertion length of the center conductor is 455 nm.

When the microwave plasma CVD apparatus of the present invention described above is operated, the following occurs.

The film forming chamber 104 in FIG. 1 is evacuated via a slit opening 110 and a vacuum exhaust port 107 by a vacuum pump (not shown). The pressure inside the deposition chamber is 1 x 10-”T
orr, the film-forming raw material gas whose flow rate is controlled by a mass flow controller (not shown) is ejected from the small hole 105 through the bias application tube 106 which also serves as a raw material gas introduction pipe to enter the film-forming chamber 104. to be introduced. In this state, after the pressure inside the film forming chamber reaches a predetermined pressure, 2.
Microwave power generated by a 45GH2 microwave oscillator (for example, manufactured by Kouwick Shokai Co., Ltd.) is transmitted through a rectangular waveguide 301, a waveguide coaxial converter 313, a center conductor 102, and a waveguide coaxial converter 313 as shown in FIG. It is introduced into the film forming chamber through a dielectric tube 103 that is transparent to microwaves. As is well known, in order to effectively utilize microwave power, it is preferable to match the impedance of the microwaves. In the apparatus of the present invention, a mechanism for adjusting the insertion length of the center conductor 102 and a coaxial plunger 302 shown in FIG. 3 are incorporated as a microwave impedance matching m structure. Among these microwave impedance matching mechanisms, the center conductor insertion length of the former is 1!
! Since the ff mechanism has a wider matching range, first adjust the insertion length adjustment mechanism using a reflected power meter that monitors the reflected power inside the coaxial or waveguide so that the reflected power is as small as possible.
Preferably, the impedances are then matched by fine adjustment using the coaxial plunger 302. As a result, plasma is generated inside the film forming chamber 104, so that a bias voltage is immediately applied from the bias application power source 116 via the conductive wire 117 to the bias application tube 106 which also serves as a raw material gas introduction tube. In this way, a desired high-quality functional deposited film is formed on the strip member 101 by the action of plasma with a controlled plasma potential.

Next, the load lock 41 shown in FIG. 5, which is an auxiliary mechanism!
! Explain the horizontal operating procedure. First, remove the center conductor 102 and the bias application tube 106 that also serves as a source gas introduction tube near the gate valve 502, and remove the microwave transparent dielectric tube 103 and the bias application tube 106 that also serves as a source gas introduction tube to be replaced as shown in the figure. Then, the loadronic chamber 501 is returned to atmospheric pressure using an inert gas such as N8 or Ar, the converter 503 is opened, and the dielectric tube 103 and The Rias application tube 106, which also serves as a raw material gas introduction tube, is replaced. Thereafter, the converter 503 is closed again, and exhaust is performed from the exhaust port 504 via an exhaust pump (not shown). When the pressures in the load candle chamber 501 and the film forming chamber become equal, the gate valve 502 is opened and the dielectric The body tube 103 and the bias application tube 106 which also serves as a source gas introduction tube are returned to the position (3), and the center conductor 102 and the bias application tube 106 which also serves as a source gas introduction tube are connected again near the gate valve 502. Formation of the deposited film can then be resumed.

As mentioned above, the load lock mechanism plays an important role in increasing the operating rate of the device, but if a conductance adjustment mechanism is installed at the exhaust port 107 in Fig. 1, the device will be further improved. Utilization rates will increase and equipment will be depreciated faster.

As shown in FIG. 6, the conductance adjustment mechanism uses a structure in which a rotatable conductance adjustment plate 601 or a microwave reflection plate 602 with a mesochet structure is provided, and at the time of initial evacuation, it is rotated to fully open and set to a predetermined value. After reaching the pressure, the rotational position is determined so that the desired conductance is achieved, and the raw material gas is allowed to flow.

Further, as another conductance adjustment mechanism, the conductance may be controlled by shifting the positions of the opposing rollers 111 and 112 shown in FIG. 6 to the left and right, thereby changing the area of the slit-shaped opening 110. .

Note that although this example device is equipped with a bias applying means having the configuration shown in FIG.
) to FIG. 19(D) may be provided.

Responsible team 1 In this example, three film forming chambers shown in FIG. 1 are connected, and an n-type semiconductor layer, a type semiconductor layer,
Microwave plasma CV suitable for manufacturing a pin-type photovoltaic device by successively stacking p-type semiconductor layers one after another
D device, and a schematic cross-sectional view is shown in FIG.

In FIG. 2, 201 is a strip-shaped member, 202 is a strip-shaped member loading chamber, 203 to 205 are isolation containers, 206 is a gas isolation passage, 207 is a strip-shaped member delivery chamber, 208 is a strip-shaped member delivery roller, 2 (19 is a strip-shaped member 210 is a scavenging gas inlet, 211 to 213 are film forming chambers, 214 to 216 are microwave coaxial line introduction parts, 2
17 to 225 are exhaust ports, 226 is a temperature control mechanism for the strip member, and 227 to 229 are bias application tubes that also serve as raw material gas introduction tubes.

In FIG. 4, the load lock mechanism described in device example 1 may be installed adjacent to isolation containers 203 to 205 via gate valves (not shown).

In addition, a belt-shaped member carrying-in chamber 202 and a belt-shaped member carrying-out chamber 207
A similar load-lock mechanism may also be installed.

In FIG. 2, a heating chamber is installed adjacent to the strip material carrying-in chamber 202, a cooling chamber is installed in front of the strip-shaped material carrying chamber 207, and a cooling chamber is installed in front of the strip material carrying-in chamber 207, depending on the inflow and outflow of heat from the plasma inside the film forming chamber. A cooling chamber or a heating chamber may be incorporated into the apparatus of the present invention as appropriate.

In FIG. 2, the inner diameters of the film forming chambers 211 to 213 are adjusted so that the transport speed of the strip member 201 remains constant even if the desired thickness of the deposited film varies.

In FIG. 2, a gas isolation passage 206 is installed between all adjacent isolation vessels, into which scavenging gas is introduced via a scavenging gas inlet 210.

The gas isolation passage 217 is required to have a function of preventing the deposited film forming raw material gas used between adjacent isolation containers from diffusing. The basic concept is U.S. Patent No. 4.438,
Although the means disclosed in No. 723 can be adopted,
In the present invention, the ability must be further improved, and the reason for this is that it is desirable that the deposited film be formed under a pressure of about 104 to 10-3 Torr in at least one of the film forming chambers of the present invention. , said U.S. Pat. No. 4.
This is because the film forming pressure in the present invention is lower than that disclosed in No. 438,723, and the source gas can easily diffuse. Specifically, it is necessary to be able to withstand a pressure difference of up to 106 times, and as an exhaust pump, an oil diffusion pump, a turbo molecular pump, a mechanical booster pump, etc. with a large exhaust capacity, or a combination thereof is preferably used. .

In order to reduce the conductance and improve the isolation function, the gas separation passage 217 has a cross-sectional shape that is approximately the same size as the cross section of the strip member, and the isolation capacity can be changed by changing the total length of the gas separation passage 217. be able to. Furthermore, in order to increase the isolation ability, it is preferable to use scavenging gas together, and such gases include Ar, Ne,
Gases that can be easily exhausted using turbo molecules, such as rare gases such as Kr and Xe, and gases that can be easily exhausted using an oil diffusion pump, such as H2 gas, are suitable. The optimum flow rate of the scavenging gas introduced into the gas isolation passage is approximately determined by the shape of the gas isolation passage and the mutual diffusion coefficient between the scavenging gas and the raw material gas for forming the deposited film, but in reality, It is desirable to determine the optimal conditions by measuring the amount of mutually diffusing gas using a mass spectrometer or the like.

Prior to the operation of this gH, the pretreated strip member 101 is placed on the feeding roller 208, and the feeding roller 208 and winding roller 2 (19) are placed on the strip material 101.
01, pass through the predetermined path of each film forming chamber 202 to 206, then close the lid of each film chamber to make it airtight, and then evacuate to about 1 x 10-'Torr to complete preparations. Become. The vacuum pump used at this time is a combination of a rotary pump, a mechanical booster pump, and an oil diffusion pump.

When this device is activated, the following occurs. Band member 1
01 is conveyed at a constant conveyance speed from the belt-shaped member carrying-in chamber 201 to the preheating chamber 202, where it is heated to a predetermined temperature, and then 1
1. The film is formed into a three-layer stack, cooled to a predetermined temperature in a cooling chamber 206, and finally rolled up by a winding roller 2 (19). After that, three layers of deposited film are formed in a stack from a strip-shaped member carrying-out chamber 207. A roll of strip material is adapted to be removed.

In this device example, the isolation containers 203 to 205 are equipped with bias applying means shown in FIG.
Any of the bias applying means having the configurations shown in A) to FIG. 19(D) may be provided.

Winding up and detachment of the strip member will be described in detail below.

First, we will explain the winding mechanism of the belt-shaped member. Regarding the winding mechanism of the device of the present invention, the functions include iv) protecting the film deposited during winding, and ■) creating a roller shape that does not cause peeling of the film. It is desirable that the

That is, when the strip-shaped member is wound up by the winding roller 2 (19), it is desirable that polyimide grar wool (so-called interleaf paper) be sandwiched together with the strip-shaped member.

The material of the interleaving paper preferably has heat resistance of about 150°C and flexibility, and in order to prevent the film from peeling off, the outer diameter of the roller is preferably 100 mm or more, or more. Preferably, it is 3001-φ.

Next, a mechanism for attaching and detaching (taking out and attaching) the strip member will be explained.

FIG. 7 and FIG. 8 (1) to (v) are schematic diagrams for explaining the outline of the band-shaped member processing chamber and the operation during film formation of the band-shaped member and the like.

In FIGS. 7 and 8, 701 is a strip processing chamber provided on the delivery side of the strip member, and 801 is a strip processing chamber provided on the winding side of the strip member. Roller 707.807, cutting blade 70
8,808, welding jig 7 (19,8 (19) is stored.

That is, FIG. 7(1) shows a state during normal film formation, in which the strip member 702 is moving in the direction of the arrow in the figure, and the roller 7
07, the cutting blade 708, and the welding jig 7 (19 are not in contact with the strip member 702.

710 is a connecting pipe with a strip member storage container (not shown); 71
1 is a connecting pipe with a film forming chamber (not shown).

FIG. 7 (Part 1) (ii) shows the first step for replacing the belt-shaped member with a new one after the film-forming process for one roll of the belt-shaped member is completed. First, the strip member 702 is stopped, and the roller 707 is moved in the direction of the arrow from the position indicated by the dotted line in the figure to bring it into close contact with the strip member 702 and the wall of the strip member processing chamber 701. In this state, the strip member storage container and the film forming chamber are hermetically separated. Next, the cutting blade 70B is moved in the direction of the arrow in the figure to cut the strip member 702. This cutting blade 7
08 is made of any one of those capable of cutting the strip member 702 mechanically, electrically, or thermally.

FIG. 7 (Part 1) (iii) shows how the cut and separated strip member 703 is wound up toward the strip member storage container.

The above-described cutting and winding steps may be performed in either a vacuum state or an atmospheric pressure leak state inside the band-shaped member storage container.

In FIG. 7 (Part 2) (iv), a new strip member 7
04 is fed in and connected to the strip member 702. The end portions of the band members 704 and 702 are brought into contact and welded together using a welding jig 7 (19).

In FIG. 7 (part 2) (v), the inside of the strip member storage container (not shown) is evacuated, and after the pressure difference with the film forming chamber is sufficiently reduced, the roller 707 is moved to the strip member 702 and the strip member processing chamber. The state in which the band-shaped members 702 and 704 are rolled up away from the wall of the chamber 701 is shown.

Next, the operation on the winding side of the strip member will be explained.

FIG. 8 (Part 1) (i) shows the state during normal acid film, and the jigs are arranged almost symmetrically to that described in FIG. 7 (Part 1) (i).

Figure 8 (Part 1) (ii) shows that after the film forming process on the band member II is completed, it is taken out and replaced with an empty bobbin for winding up the band member that has been subjected to the next film forming process. It shows the process for

First, the strip member 802 is stopped, and the roller 807 is moved in the direction of the arrow from the position indicated by the dotted line in the figure to bring it into close contact with the strip member 802 and the wall of the strip member processing chamber 801. In this state, the strip member storage container and the film forming chamber are hermetically separated. Next, the cutting blade 808 is moved in the direction of the arrow in the figure to cut the strip member 802. The cutting blade 808 is made of one that can cut the strip member 802 mechanically, electrically, or thermally.

FIG. 8 (Part 1) (iii) shows how the cut and separated strip member 805 after the film forming process is wound up toward the strip member storage container.

The above-described cutting and winding steps may be performed in either a vacuum state or an atmospheric pressure leak state inside the band-shaped member storage container.

FIG. 8 (Part 2) (iv) shows a preliminary winding strip member 80 attached to a new winding bobbin.
6 is fed in and connected to the strip member 802. Preliminary winding strip member 806 and strip member 8
02 is brought into contact with its end, and is welded and connected with the welding jig 8 (19).

In FIG. 8 (Part 2) (v), after the inside of the strip member storage container (not shown) is evacuated and the pressure difference with the film forming chamber is sufficiently reduced, the roller 807 is moved between the strip member 802 and the strip processing chamber. The state in which the strip members 802 and 806 are rolled up away from the wall of 801 is shown.

As shown in Figures 7 and 8, the strip member can be easily replaced while maintaining the vacuum state inside the deposition chamber, which improves work efficiency and also allows the deposition chamber to be exposed to atmospheric pressure. Therefore, the generation of adsorbed water on the inner wall of the film forming chamber can be eliminated, and high quality semiconductor devices can be stably formed.

In the present invention, the inside of the film forming chamber can be cleaned by dry etching as needed while maintaining the vacuum state.

A solar cell is an example of a semiconductor device suitably manufactured by the method and apparatus of the present invention. Figures 13 to 16 schematically show typical examples of the layer structure.

In the example shown in FIG. 13, a lower electrode 13 is placed on a support 1301.
02, n-type semiconductor layer 1303, l-type semiconductor layer 1304,
A photovoltaic element 1300 in which a p-type semiconductor 11305, a transparent electrode 1306, and a current collecting electrode 1307 are deposited in this order.
It is. Note that this photovoltaic element is based on the premise that light is incident from the transparent electrode 1306 side.

In the example shown in FIG. 14, a transparent electrode 1406, a p-type semiconductor layer 1405, an l-type semiconductor layer 1 are placed on a transparent support 140I.
404, a photovoltaic element 1400 in which an n-type semiconductor layer 1403 and a lower electrode 1402 are deposited in this order. This photovoltaic element is based on the premise that light is incident from the transparent support 1401 side.

The example shown in FIG. 15 is a so-called tandem type, which is constructed by laminating two pin junction type photovoltaic elements 1511 and 1512 using two types of semiconductor layers with different band gaps and/or layer thicknesses as the i-layer. This is a photovoltaic element 1513. 1501 is a support body, which includes a lower electrode 1502, an n-type semiconductor layer 1503, a 1-type semiconductor layer 1504, and a p-type semiconductor J.
i1505, n-type semiconductor layer 1508, i-type semiconductor layer 15
(19. A p-type semiconductor layer 1510. A transparent electrode 1506 and a current collecting electrode 1507 are laminated in this order, and it is assumed that light is incident from the transparent electrode 1506 side in this photovoltaic element.

The example shown in the 1st R1ff is a so-called triple stacked pin junction photovoltaic device 1620, 1621°1623 using three types of semiconductor layers with different band gaps and/or layer thicknesses as iN. It is a type photovoltaic element 1624. 1601 is a support body, which includes a lower electrode 1602, an n-type semiconductor JiF 1603, and an i-type semiconductor layer 1.
6o4, p-type semiconductor layer 1605, n-type semiconductor Nl 61
4, i-type semiconductor layer 1615, p-type semiconductor layer 1616, n
type semiconductor layer 1617, i-type semiconductor layer 1618, p-type semiconductor layer 1619, transparent mold 11606, and current collecting electrode 1607
are laminated in this order, and this photovoltaic element is based on the premise that light is incident from the transparent electrode 1606 side.

Note that in any photovoltaic element, the n-type semiconductor layer and the p-type semiconductor layer can be used by changing the stacking order of each layer depending on the purpose.

The configurations of these photovoltaic elements will be explained below.

Supports 13o1 to 1601 used in the present invention
A material that is flexible and capable of forming a curved shape is suitably used, and is electrically conductive. Further, although they may be transparent or non-transparent, the supports 1301 to 16o1
When light is incident from the side, it is of course necessary to be transparent.

Specifically, the above-mentioned band-shaped member used in the present invention can be mentioned, and by using the substrate, it is possible to reduce the weight, improve the strength, and reduce the transportation space of the manufactured solar cell.

In the photovoltaic device of the present invention, an appropriate tpi is selected and used depending on the configuration of the device. Examples of these electrodes include a lower electrode, an upper electrode (transparent electrode), and a current collecting electrode. (However, the upper electrode here refers to the one provided on the light incident side, and the lower electrode refers to the one provided opposite the upper electrode with the semiconductor layer in between.) The electrodes will be explained in detail below.

Lower electrodes 1302 to 160 used in the present invention
2, because the surface to which light for photovoltaic generation is irradiated differs depending on whether the material of the supports 1301 to 1601 described above is translucent or not (for example, if the support 1301 is made of metal or other non-transparent material) (If the transparent material is made of a transparent material, the light for generating photovoltaic force is irradiated from the transparent electrode 1306 side as shown in FIG. 13), but the location where it is installed differs.

Specifically, in the case of a layer structure as shown in FIG.
02 is provided. However, when the support 1301 is conductive, the support can also serve as the lower electrode. However, even if the support 1301 is conductive, if the sheet resistance value is high, the electrode may be used as a low-resistance electrode for current extraction or for the purpose of increasing the reflectance on the support surface and making effective use of incident light. 1302 may be installed.

The same applies to the cases shown in FIGS. 15 and 16.

In the case of FIG. 14, a transparent support 14o1 is used, and light enters from the support 1401 side, so
For the purpose of extracting current and reflecting light at the electrode, a lower @pi 1402 is provided facing the support 1401 with the semiconductor layer in between.

In addition, when an electrically insulating material is used as the support 1401, the support 1401 can be used as an electrode for taking out current.
A lower electrode 1402 is provided between the n-type semiconductor layer 14o3 and the n-type semiconductor layer 14o3.

The electrode materials include Ag, Au, Pt, and Ni.

Examples include metals such as Cr, Cu, ACTi, Zn, Mo, and W, or alloys thereof, and thin films of these metals are formed by vacuum evaporation, electron beam evaporation, sputtering, or the like. In addition, care must be taken so that the formed metal thin film does not become a resistance component with respect to the output of the photovoltaic element, and the sheet resistance value is preferably 50Ω or less, more preferably 1OΩ.
The following is desirable.

Lower electrodes 1302 to 1602 and n-type semiconductor layer 1303
Although not shown in the figure, a diffusion prevention layer such as conductive zinc oxide may be provided between the electrodes 1302 to 1603. In addition to preventing diffusion into the n-type semiconductor layer, by providing a slight resistance value, the lower electrodes 1302 to 1602 provided across the semiconductor layer and the transparent electrode $li! 306 to 1606 due to defects such as pinholes, and the thin film generates multiple interference to confine incident light within the photovoltaic element. can.

(11) Above. (゛) Transparent electrodes 1306 to 160 used in the present invention
As for 6, it is desirable that the light transmittance is 85% or more in order to efficiently absorb light from the sun, white fluorescent lamp, etc. into the semiconductor layer, and furthermore, electrically, it is desirable that The sheet resistance value is set to 1 so that it does not become a resistance component.
00Ω or less, materials with such characteristics include 3nOH, In103, ZnO, and Cd.
O.

CdzSnOa, I To (In*03 +
5110g), and metal oxides such as Au, AI, Cu
Examples include metal thin films made of extremely thin, translucent metals such as metals. The i3 bright electrode is shown in Figures 13, 15, and 1.
In Figure 6, the p-type semiconductor F11305, 1505°1
605 layers, and in FIG.
Since it is to be laminated on top of 01, it is necessary to select materials that have good adhesion to each other.

As a method for producing these, a resistance heating evaporation method, an electron beam heating evaporation method, a sputtering method, a spray method, etc. can be used, and the method is appropriately selected depending on the desire.

] "U" v44 loss Current collecting electrodes 1307 to 160 used in the present invention
7 is provided on the transparent electrodes 1306 to 1606 for the purpose of reducing the surface resistance value of the transparent electrodes 1306 to 1606. The electrode materials include Ag, Cr, Ni, A1. A
g, Au, Ti.

Examples include thin films of metals such as PL, Cu, Mo, and W, or alloys thereof. These thin films can be used in a stacked manner. Further, the shape and area of the semiconductor layer are appropriately designed so that a sufficient amount of light incident on the semiconductor layer is ensured.

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

In addition, the sheet resistance value is preferably 50Ω or less,
More preferably, it is 10Ω or less.

As the semiconductor material constituting the i-type semiconductor layer suitably used in the photovoltaic device, a-Si:I(, a
-3i:F, a-3i:H:F.

a-3iC:H, a-3iC:F, a-3iC:H
:F, a-3iGe:H, a-3iGe:F.

a-5+Ge:H:F, poly-5r:H.

In addition to the so-called ■group and ■group alloy semiconductor materials such as poly-3i:F, poly-3t:H:F, ■■group and m-
Examples include so-called compound semiconductor materials of the V group.

An example of a semiconductor material for controlling the p-type or n-type semiconductor layer suitably used in the photovoltaic element is doping the semiconductor material constituting the above-mentioned i-type semiconductor layer with a valence electron control agent. obtained by.

[Film formation example]

Hereinafter, specific examples of film formation using the microwave plasma CVD apparatus of the present invention will be shown, but the present invention is not limited to these film formation examples in any way.

Using the continuous microwave plasma CVD apparatus (FIG. 2) shown in Goyo Kinugasa Apparatus Example 2, amorphous silicon films were continuously deposited.

First, a belt-shaped member loading chamber 2 having a belt-shaped member delivery mechanism
02, a 5US430BA strip member (width 46mm x length 100m x thickness 0.2m+) was thoroughly degreased and washed.
+) Wrapped belt-shaped member feeding roller 20
8, and the strip member 201 is connected to the gas isolation passage 206.
And the opening support outer roller 1.1L in each of the isolation containers 203 to 205. The strip was passed through to the unloading chamber 207, and the tension was adjusted to such an extent that there was no slack.Table 6 shows the conditions such as the curved shape of the strip member.

Therefore, the belt-shaped member carrying-in chamber 201 and the belt-shaped member carrying-out chamber 207
, and the isolation containers 203 to 205 are roughly pumped with a rotary pump (not shown), and then a mechanical booster pump (not shown) is started to evacuate to around lo-3 Torr, and then a temperature control device installed inside the isolation container 204 is applied. While operating only the mechanism 226 and maintaining the substrate surface temperature at 250°C, an oil diffusion pump (not shown) (Varian HS-3) was operated.
2), the vacuum was evacuated to 5 X I O-'' Torr or less.

When sufficient degassing has been performed, 5iHn 140 sccm,
5jFn 2sccm and Hl 80sccs were introduced, and the pressure inside the film forming chamber 212 was adjusted to 24mTo by adjusting the opening degree of the throttle valve attached to the oil diffusion pump.
It was held at rr. At this time, the pressure inside isolation container 204 was 13 mTorr. When the pressure stabilized, a microwave with an effective power of 1.4
Microwaves of kW were radiated from the central conductor 102.

Immediately, the introduced raw material gas turns into plasma and enters the film forming chamber 2.
A plasma region was formed within 12.

Therefore, when a DC voltage of +70V was applied from the bias application type 1iut6 to the bias application tube 106, which also serves as a gas introduction pipe, through the conductor 117, a bias current of 6.7A flowed, and the brightness of the plasma was slightly reduced by visual observation. Increased.

Therefore, the opening support outer roller 111, the opening support inner roller 112, and the curved part support inner ring 113 (
In both cases, a drive mechanism (not shown) was started, and the conveyance speed of the strip member was controlled to be 43 cm/s+in.

Even after starting tS feeding, the plasma remained stable, and there was no change in either the bias voltage or current.

Note that H! gas is supplied to the gas isolation passage 206 from the scavenging gas inlet 210 as scavenging gas. Gas was flowed at 50 sccm. *The deposited film was formed continuously for 30 minutes after the start of feeding. Note that since a long strip-shaped member is used, after the completion of this film-forming example, another deposited film is formed, and after all the depositions are completed, the strip-shaped member is cooled and taken out, and then the main film-forming process is carried out. When the thickness distribution of the deposited film on the strip-shaped member formed in the example was measured in the width direction and the sand direction, it was within 5%, and the average deposition rate was 115 people/sec. In addition, a part of it was cut out and FT-IR (Parkin
When the infrared absorption spectrum was measured by the reflection method using Elmer's 1720X), 2000 Rho 1 and 63
Absorption was observed at the 0 cm arch, which was an absorption pattern specific to the a-3i:H:F film. Furthermore, RHEED (JEM-
1003X.

When the crystallinity of the film was evaluated by JEOL Ltd., it was found to be amorphous with a halo. Further, the amount of hydrogen in the film was quantified using a hydrogen in metal analyzer (EMGA-1100, manufactured by Horiba, Ltd.) and found to be 21±2 atomic%.

Furthermore, the amorphous silicon film deposited on the strip member was mechanically moved to 8M over an area of approximately 5 mm to measure its volume, and then an ESR device (JES-RE2
When the spin density was measured with X, JEOL type), it was 3
．． 5 X IO"5 pins/c1, and it was found that the film had few defects.

Moreover, l as X l from other parts of the band-shaped member
A sample piece of CS was arbitrarily cut out at 5 locations, set in a reactive sputtering device (in-house product), and a layer of ITO (rn
tos +5nOt) film was deposited.

Then, this sample piece was subjected to CPM (Constant P
When the inclination of the urban hem (Urbach Ta1l) was measured by setting it in a photo-current method (in-house manufactured device) and injecting light from the ITO film side, it was 50 ± 1 + meV, indicating that it was a film with few defects. It turns out.

Continuing from the deposited film formation step carried out in Kinomata twist main film formation example 1,
After stopping the introduction of the used raw material gas and evacuating the internal pressure of the isolation container 204 to 5×10-' Torr or less, SiH4
22sccs, G e H, 18sccs+sS i
Introduced Fal, 5sccm, Hz 50scc,
Continuous deposition of amorphous silicon germanium films was performed under the same deposition film conditions except that the internal pressure of the film forming chamber 212 was maintained at 21 mTorr and the microwave power was 0.75 kW.

In addition, when a DC voltage of +40V was applied from the bias application power supply 116 to the bias application tube 106 which also serves as a gas introduction tube through the conductor &11117, a bias current of 6.2A flowed, and the brightness of the plasma was slightly decreased by visual observation. Increased.

After this film formation example and other acid film examples were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this film formation example was measured in the width direction and longitudinal direction, and it was within 5%. The deposition rate was 34 persons/sec on average. In addition, when we cut out a part of it and measured its infrared absorption spectrum by reflection method using FT-IR (Perkin Elmer 1720X), we found that it was 2000 cm- ', 188
Absorption was observed at 0 cm-' and 630 cm-' a-3
The absorption pattern was unique to the iGe:H:F film. Furthermore, when the crystallinity of the film was evaluated by RHEED (JEM-100SX, JEOL Ltd.), it was found that it was halo and amorphous. In addition, the hydrogen in metal analyzer (EMGA)
-1100, manufactured by Horiba, Ltd.), and the amount of hydrogen in the film was determined to be 15±2 atomic%.

Furthermore, the amorphous silicon germanium film deposited on the strip member was mechanically peeled off over an area of about 5 cd to measure its volume, and then the ESR device (
When the spin density was measured using a JES-RE2X (JEOL model), it was found to be 4.8 x 10''5 pins 7 cm3, indicating that the film had few defects.

Also, 1 (JIXICll
Five sample pieces were arbitrarily cut out, placed in a reactive sputtering device (in-house product), and 1,500 IT professionals
An O(rnx03 +5nOt) film was deposited. and,
This sample piece was processed using CPM (Constant Photo Shoot).
rrrent Method) device (in-house manufactured device), and incident light from the ITO film side to create an urban hem (
When the slope of Urbach Ta1l) was measured, it was 55
It was found that the film had a value of ±1 meV with few defects.

Continuing from the deposited film forming step carried out in Sandwich Team Main Acid Film Example 1,
After stopping the introduction of the used raw material gas and evacuating the internal pressure of the isolation container 204 to 5×10-” Torr or less, 5iH4
58sccm, CHa 9 sccm, 5iFa 2
sccmSHg 180sccm was introduced into the film forming chamber 2.
Continuous deposition of amorphous silicon carbide films was performed under the same deposition film forming conditions except that the internal pressure of No. 12 was maintained at 25 m Torr.

Note that when a DC voltage of +60V was applied from the bias application power supply 116 to the bias application tube 106 which also serves as a gas introduction tube through the conductor 117, a bias current to 6.3 flows, and as visually observed, the brightness of the plasma increased. It increased slightly.

After this film formation example and other acid film examples were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this film formation example was measured in the width direction and longitudinal direction, and it was within 5%. The average deposition speed was 7 seconds for 54 people.

In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-IR (1720X manufactured by Perkin Elmer), the results were 2080 cm-', 12
50cm-', 960cm-', 777113-'
Absorption was observed at 660c*-' and a-3iC:)(
:The absorption pattern was unique to F film. Furthermore, 1? H.E.
When the crystallinity of the film was evaluated by ED (JEM-100SX, JEOL Ltd.), it was found to be halo and amorphous. We also have a metal hydrogen analyzer (EMGA-110
The amount of hydrogen in the film was quantified using a method (manufactured by Horiba, Ltd.) and found to be 14±2 atomic%.

Furthermore, the amorphous silicon carbide film deposited on the strip member was mechanically peeled off over an area of about 5 mm to measure its volume, and then an ESR device (JE
When the spin density was measured with S-RE2X (JEOL), it was 8.5X101Sspins 7cm3,
It was found that the film had few defects.

In addition, five sample pieces of lc*X1cs+ were arbitrarily cut out from other parts of the band-shaped member, placed in a reactive sputtering device (in-house product), and placed on the surface on which the amorphous silicon carbide film was deposited. ITO(
In2O2+Snow) III was deposited. Then, this sample piece was processed using CPM (Constant Photocurrence)
Rent Method) equipment (in-house manufactured equipment), and light is incident from the ITO film side to create an urban hem (U).
When the slope of rbach Ta11) was measured, it was 57±
At 1 meV, it was found that the film had few defects.

Continuing from the deposited film formation step carried out in Example 1 of the Floating Mottled Film Formation Example,
After stopping the introduction of the raw material gas used and evacuating the internal pressure of the isolation container 204 to 5 X 10-' Torr or less, 5iHa 6
0sccm, B F3 (30001)lull H!
Dilution) 14sccms S i F, 3sccm
s Hz 180sec+ was introduced into the film forming chamber 212.
The internal pressure of the was maintained at 33 mTorr, and the microwave power was set to 1
．． P-type microcrystalline silicon films were continuously deposited under the same deposition film formation conditions except that the power was 7 kW.

When a DC voltage of +70V was applied from the bias application type 'a116 to the bias application tube 106, which also serves as a gas introduction tube, through the conductor 117, a bias current of 6.6 flows, and the brightness of the plasma was visually observed. has increased slightly.

After the completion of this film formation example and other film formation examples, the substrate was cooled and taken out, and the III thickness distribution of the deposited film formed in this film formation example was measured in the width direction and longitudinal direction, and it was found that it was 5%
The average deposition rate was 46 persons/sec.

In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-IR (1720X manufactured by Perkin Elmer), the infrared absorption spectrum was found to be 2100 cm-' and 63 cm-'.
Absorption was observed at the 0 value -1, which was an absorption pattern unique to the μC-3i:H:F film. Furthermore, RHEED (JEM
-1003X.

When the crystallinity of the film was evaluated by JEOL Ltd., it was found to be ring-shaped and non-oriented polycrystalline. Also,
When the amount of hydrogen in the film was determined using a metal hydrogen analyzer (EMGA-1100, manufactured by Horiba, Ltd.), it was 4 ± 1 ato.
+*ic%.

Furthermore, for the film deposited on the strip member, 5 f
A sample piece of lX 5 tm was arbitrarily cut out at five locations, and its surface condition was observed using an ultra-high resolution, low acceleration FB-3EM (Hitachi S-900 model). The film surface was smooth and there were no abnormal protrusions. Almost no occurrence was observed.

Continuing from the deposited film formation step carried out in Film Formation Example 1,
After stopping the introduction of the used raw material gas and evacuating the internal pressure of the isolation container 204 to 5×10-” Torr or less, 5iH4
88sccm, P Hz (1% H2 dilution) 11S
CC11% 5iF45secs, Hz 25sec
An n-type amorphous silicon film was continuously deposited under the same deposition film forming conditions except that the internal pressure of the film forming chamber 212 was maintained at 38 mTorr, and the microwave power was set at 1.05 kW.

Note that when a DC voltage of +65V was applied from the bias application power supply 116 to the bias application tube 106 that also serves as a gas introduction tube through the conductor 117, a bias current of 6.4A flowed, and as visually observed, the brightness of the plasma slightly increased. Increased.

After this film formation example and other film formation examples were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this film formation example was measured in the width direction and longitudinal direction, and it was within 5%. The average deposition rate was 70 persons/sec.

In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-IR (1720X manufactured by Perkin Elmer), the infrared absorption spectrum was found to be 2000 cm-' and 63 cm-'.
Absorption was observed at 0(J-', which was an absorption pattern specific to a-3i:H:F film. Furthermore, RHEED (JE
When the crystallinity of the film was evaluated using M-1003X (manufactured by JEOL Ltd.), it was found to be halo and amorphous. In addition, the amount of hydrogen in the film was determined using a metal hydrogen analyzer (EMGA-1100, manufactured by Horiba, Ltd.) and was found to be 22±2a.
tomic%.

Furthermore, for the film deposited on the strip member, 5 i
@
-900 model), the film surface was smooth and almost no abnormal protrusions were observed.

Film Formation Example 6 In Film Formation Example 1, instead of the 5US430BA band-shaped substrate, an Al film of 2 μm thick was deposited on the side on which the deposited film was formed (part of it had an Al film of 70 μm in diameter and a length of 1 (In PET (polyethylene terephthalate) band-shaped substrate (width 46C1l x length lQQm x thickness 0.8
An amorphous silicon film was continuously deposited using exactly the same procedure except that the substrate surface temperature was 210°C.

Note that when a DC voltage of +70V was applied from the bias application power supply 116 to the bias application tube 106 which also serves as a gas introduction tube through the conductor 117, a bias current of 6.6 flows, and as visually observed, the brightness of the plasma increased. It increased slightly.

After the substrate was cooled, it was taken out, and the film thickness distribution was measured in both the width direction and the length direction, and it was found to be within 5%, and the average deposition rate was 112 A/see. Also,
A part of it was cut out and its infrared absorption spectrum was measured using FT-IR (Perkin Elmer 1720X) using the reference Mimic 3-pass method.
Absorption was observed at -' and 630 cm-', a-3i:
The absorption pattern was unique to the H:F film. Also, 200
When the amount of hydrogen in the film was determined from the absorption attributed to 5i-H near 0 cm-', it was found to be 22±2 atomic%.

Furthermore, when the crystallinity of the film was evaluated by RHEED (JEM-100sX, manufactured by JEOL Ltd.), it was found that it was amorphous with a halo.

In addition, 20 of the pre-formed gasob electrodes
Randomly cut out f1 locations and calculate %AM- for each
The photocurrent value under 1 light (100 mW/cj) irradiation and the dark current value in the dark were measured using I (P4140B), and the Meishun electrical conductivity σP (S/ell) and the dark conductivity σd
(S/cs) was found to be (4,0
±0.5) x 10-'S/cm and (2,0±0.
5)×10°IIS/(2).

In addition, this sample piece was subjected to CPM (Constant Ph
The inclination of Urbach Ta11 was measured by setting it in an in-house Oto-Current Method device (in-house manufactured device) and injecting light from the ITO film side, and it was 51 ± 1 meV, indicating that it was a film with few defects. It turns out.

Each deposited film was formed under the same operations and plasma generation conditions as in Examples 1 to 5 of film formation on agricultural products, except that the applied bias voltage was changed to the conditions shown in Table 9. went.

The results of evaluation of the formed deposited film using the same method as in Film Examples 1 to 5 are summarized in Table 9. In all cases, no abnormal discharge occurred and no plasma was detected. was stable and a film with good properties was obtained.

Johan 115 Hini 16 Films were formed using the same operations and plasma generation conditions as in Film Examples 1 to 5, except that the bias voltage applied to the second bias rod was changed to the conditions shown in Table 10. , each deposited film was formed. The bias application method is the 19th
In each case, +30 V was applied to the first bias rod using the method shown in Figure (D).

The results of evaluating the formed deposited film using the same method as in Film Forming Examples 1 to 5 are summarized in Table 1. In all cases, no abnormal discharge occurred and no plasma was detected. was stable and a film with good properties was obtained.

1. In this film-forming example, a strip of 50cm
A Schottky diode having the N configuration shown in FIG. 12 was fabricated while being transported at a transport speed of m/PAin. 12th
In the figure, I201 is a stainless steel strip member, 120
2 is a Cr vapor deposited layer (0.1 μm thick), 1203 is an n-type a-
3i:H film (0,2,c+m thickness, hereinafter abbreviated as n''-3i layer), 1204 is a non-doped a-3i:H film (0,4
μm thick, hereinafter abbreviated as 1-3i layer), 1205 is gold vapor deposition 1
(100 people thick), 1206 and 1207 are electrical connection terminals.

The manufacturing procedure will be explained below.

First, the band-shaped member 12 was subjected to the same cleaning treatment as in Film Formation Example 1.
A Cr layer 1202 with a thickness of 1,000 thick was formed on the strip member 1201 using a continuous vacuum thin deposition apparatus.Then, the Cr layer 1202 was deposited on the strip member 1201 using a microwave plasma CVD apparatus of the present invention as shown in FIG. n'-3iN1203 was formed in the same manner as in Film Forming Example 1 under the film forming conditions shown in Table 10.

After continuous film formation for 20 minutes, the formation of the n''-3i layer 12o3 was completed, and the microwave power, S + H4, H was diluted with PH, +
10-'T in the isolation container 203.
Vacuumed to orr.

Next, while the strip member 201 wound around the strip member collection roller 208 is conveyed in reverse from the right side to the left side in the figure,
1- according to the procedure described above under the film-forming conditions shown in Table 10.
Continuous formation of the 3i layer 1204 was performed for 20 minutes.

Note that the conveyance speed at this time was 50 cm/sin.

After the formation of the 1-3i layer 1204 was completed, the strip-shaped substrate 201 was taken out from the strip-shaped member carrying-out chamber 202 according to the procedure described above.

At this time, the average total thickness of the n''-3i layer and the 1-3i layer was about 0.6 μm, and the in-plane uniformity was as good as ±4%.

Furthermore, sample pieces are arbitrarily cut out from 20 locations in the strip member 201, and each sample piece is set in a vacuum evaporation apparatus.
On the 3i layer 1204, a gold evaporated film 1205 of 100 layers with a diameter of 5 mm and a thickness of +11i was formed.

Electrical connection terminals 1206 are connected to the gold vapor deposited film and the Cr vapor deposited film.
．． 1207 was pressed into contact with each other and the characteristics of the Schottky diode were investigated, and the diode factor n=1. I2
It was found that good diode characteristics of ±0.05 were exhibited. Further, the uniformity of in-plane properties was also good.

Continuous microwave plasma CV of the present invention shown in Fig. 2
A pin type a-S with the layer structure shown in FIG.
+ Thick! The ponds were produced continuously.

In Fig. 13, 1301 is stainless steel (SUS43
0BA) Band-like member, 1302 is made of aluminum and C"
The lower electrode is made up of two layers, 1303 is an n-type a-3i layer (
n-3i), 1304 is type 1 a-3i layer (i-3i)
, 1305 is a p-type microcrystal St layer (hereinafter abbreviated as p-type μx-3ill), 1306 is a transparent electrode, 130
7 is an aluminum collection IIi electrode.

First, after thoroughly cleaning and degreasing a stainless steel (SUS430BA) band-like member, AI and Cr are continuously deposited using a continuous vacuum deposition device (not shown), and the lower electrode 130 is
2 was formed. The strip member 201, which has been formed up to the lower electrode 1302, is set in the apparatus shown in FIG. 2 so that the surface on which the lower electrode 1302 is formed faces downward in the figure.
nSt,
, 1-3iSp type px-3t were successively stacked in this order.

Furthermore, an indium tin oxide film 1306 (ITO) as a transparent electrode is deposited on the p-type μx-3L film, an All electrode 1307 as a current collecting electrode is deposited, and a resin is applied as a surface protective layer. A solar cell of Nfjl composition was manufactured. The completed solar cell is AMl, 5 (100mW/-)
As a result of measurement using a solar simulator, the photoelectric conversion efficiency was 8.4% or more on average, indicating good characteristics.

Furthermore, when the defect occurrence rate due to sheets etc. was compared with that of a solar cell module formed without applying a bias voltage, it was found to be improved by more than 20%.

Using the continuous microwave CVD apparatus of the present invention shown in Fig. 2, pin type a-3i/a-3i with the layer structure shown in Fig.
C. 11iSii ponds were produced continuously.

However, in Fig. 13, l304 is 1-3+C layer, 1
305 was changed to p-type μx-3+ (: membrane).

Other than that, the process was completely the same as that of film formation example 18, and n-3+% 1-
Deposited films were formed in the order of 3iCSp-μx-3iC.

In addition, the raw material gas utilization efficiency when using a 1-3iC layered structure is 50%.
As a result of measurement and evaluation using a solar simulator similar to that used in Film Formation Example 18, the average photoelectric conversion efficiency was 6.
It was 3% or more.

Further, when the rate of change in photoelectric conversion efficiency with respect to the initial value was measured after 500 hours of continuous irradiation with AMl,5 (100 mW/aj) light, it was within 9%.

Continuous microwave CVD device membrane chamber 20 shown in Figure 2
5 and the belt-shaped member carrying-out chamber 207, using a device (not shown) newly connected with three film-forming chambers.
A tandem solar cell with a layer of t# as shown in FIG. 5 was manufactured continuously.

In FIG. 15, 1501 is a stainless steel strip member;
1502 is a lower electrode composed of 2N of an AA' extraction electrode and an Ag reflective layer, 1503 is a first n-type a-3i layer, 1
504 is the first i-type amorphous silicon germanium (i-a-31Ge) JfW, 1505 is the first p-type px-3i layer, 1508 is the second n-type a-3+ layer, 15
(19 is the second 1-aSiji, 1510 is the second p-type px-3i layer, 1506 is a transparent conductive film, and 1507 is a patterned Al current collecting electrode.

This apparatus continuously manufactured solar cells under the film-forming conditions shown in Table 13 and the same procedure as described in Apparatus Example 8. As a result of measurement using a solar simulator similar to that used in Film Formation Example 18, the photoelectric conversion efficiency was 6 on average.
．． It was more than 6%.

In addition, 500 mW/cd of AM 1.5 (100 mW/cd) light
When the rate of change in photoelectric conversion efficiency with respect to the initial value after continuous irradiation was measured, it was within 9%.

Furthermore, when compared with the case of a solar cell module formed without applying a bias voltage, the defect occurrence rate due to short circuits and the like was improved by more than 20%. By connecting these modules, we were able to create a 3kW power iJL supply system.

(The following are blank spaces) Table 3 Table 3 Table 10 Table 1 [Summary of the effects of the invention] According to the method of the present invention, the strip-shaped member constituting the side wall of the film-forming space is continuously formed. At the same time, microwave antenna means is thrust into the film-forming space so as to be parallel to the width direction of the band-shaped member that constitutes the side wall of the film-forming space, and a microwave antenna is directed from the microwave antenna means in the direction of propagation of the microwave. By emitting microwave power in all vertical directions to generate plasma, a large area of functional deposited films can be continuously deposited.
It can be formed with good uniformity.

Furthermore, according to the method of the present invention, by appropriately controlling the plasma potential, a high-quality functional deposited film having desired characteristics and few defects can be continuously formed efficiently and at a high yield. .

By confining the plasma within the film forming space and controlling the plasma potential, the method and apparatus of the present invention improve the stability and reproducibility of the plasma, and dramatically improve the utilization efficiency of the raw material gas for forming the deposited film. can be increased. Furthermore, by continuously conveying the belt-shaped member,
By varying the length of the curve and the conveyance speed, a deposited film of any thickness can be continuously deposited over a large area with good uniformity.

According to the method and apparatus of the present invention, it is possible to form a functional deposited film continuously and with good uniformity on the surface of a relatively wide and long strip member. Therefore, it can be particularly suitably used as a mass production machine for large-area solar cells.

Further, since a deposited film can be continuously formed without stopping the discharge, good interface characteristics can be obtained when manufacturing a stacked device or the like.

In addition, it is possible to form a deposited film under low pressure, suppressing the generation of polysilane powder, and reducing the amount of polymerization of active species.
This reduces defects and improves film properties.
The stability of film properties can be improved.

Therefore, you can improve the operating rate and yield, and create inexpensive and highly efficient solar cells! It becomes possible to commercialize it.

Furthermore, the solar cell produced by the method and apparatus of the present invention has high photoelectric conversion efficiency and exhibits little property deterioration over a long period of time.

[BRIEF DESCRIPTION OF THE DRAWINGS] Fig. 1 is a transparent explanatory view of the film forming chamber and its peripheral mechanism in the apparatus of the present invention; Fig. 2 is a schematic diagram showing the arrangement of the apparatus for forming each pin layer of a solar cell; 3 is a detailed explanatory diagram of the microwave coaxial line, FIG. 4 is a sectional view taken along line A-A' in FIG. The figure is an explanatory diagram of the operation of the exhaust port of the film-forming chamber. Figures 7 and 8 are a schematic diagram of the strip-shaped substrate attachment and detachment mechanism. Figure 9 is a schematic diagram of a conventional RF plasma CVD apparatus. Figures 10 and 11 are , data of membrane result evaluation examples, Figures 12 to 16 are laminated film configuration diagrams, Figures 17 and 18 are explanatory diagrams of conventional microwave antenna systems, and Figure 19 is a typical bias application means. FIG. FIG. 20 is a current-voltage characteristic diagram when a bias voltage is applied, obtained in an experimental example of the present invention. FIG. 21 is a diagram showing the rate of change in plasma potential during application of a bias voltage obtained in an experimental example of the present invention. Regarding each of FIG. 1 to FIG. 19, 101.1901... Band-shaped member, 102... Center conductor, 103... Dielectric tube, 104... Film forming chamber, 10
61903... Bias application tube that also serves as source gas introduction tube, 110... Slit-shaped opening, 113... Curved part support inner ring, 114.19 (19... Insulating joint, 115.1910...・Gas supply pipe, 116, 19
07゜1908...Bias application power supply, 117...
・i-line, 201... band-shaped member, 203-205...
Isolation container, 206... Gas isolation passage, 210... Scavenging gas inlet, 211-213... Film forming chamber, 214-
216...Microwave coaxial vA path introduction part, 217-2
25...Exhaust port, 301...Rectangular waveguide, 302...
... Coaxial plunger, 307 ... Microwave transparent high dielectric constant member, 313 ... Waveguide coaxial converter, 501
... Replacement load lock chamber, 502... Gate valve, 601... Conductance adjustment plate, 602...
Microwave reflecting plate with mesh structure, 701... Strip-shaped substrate processing chamber provided on the delivery side of the strip-shaped substrate, 80
1... Strip-shaped substrate processing chamber provided on the winding side of the strip-shaped substrate, 708.808... Cutting blade, 7 (19, 8 (1)
9... Welding jig, 902... Cathode electrode, 903
...Base body, 904...Base body holder, 905...
Support stand with built-in heater, 1301, 1401.15
01゜1601...Support, 1302, 1402.1
502゜1602...lower electrode, 1303, 1403
゜1503.1508.1603,1614.1617
---n-type semiconductor layer, 1304, 1404, 15041
5 (19.1604, 1615.1618...i-type semiconductor layer, 1305, 1405, 1505° 1510.1
605,1616.1619...p-type semiconductor layer, 13
06,1406,1506°1606...transparent electrode,
1307.1507゜1607...Collecting electrode, 171
... Reaction vessel, 172 ... Rondo antenna, 17
9... Microwave transmission member, 181... Reaction container,
184... Coaxial line, 185... Gap provided in outer conductor, 186... Cylindrical body, 1904. I90
6./<I7S rod, 1905...Gas introduction pipe.

Claims (36)

[Claims] (1) While continuously moving a strip member in the longitudinal direction, a columnar film forming space that can be maintained in a substantially vacuum state is formed with the moving strip member as a side wall midway through the movement, and within the film forming space. A source gas for film formation is introduced into the film formation space through a gas supply means, and at the same time, microwaves are radiated in all directions perpendicular to the direction of propagation of the microwaves through a microwave antenna to supply microwave power into the film formation space. of the band-shaped member that constitutes the side wall exposed to the microwave plasma and moves continuously while controlling the plasma potential of the microwave plasma. A method for continuously forming a large-area functional deposited film using a microwave plasma CVD method, which is characterized by forming a deposited film on a surface. (2) In the middle of the moving band-like member, a curved start end forming means and a curved end forming means are used to create a space between the curved start end forming means and the curved end forming means, so that the longitudinal direction of the band-like member is 2. The method for continuously forming a large area functional deposited film according to claim 1, wherein the side wall of the film forming space is formed by curving the strip member leaving a gap in the direction. (3) As the material for the band-shaped member, a material whose linear expansion coefficient is larger than that of the deposited film is used, and the band-shaped member is continuously curved while maintaining the desired film-forming temperature above room temperature. A deposited film is formed on the concave curved surface formed by the deposited film, and the belt-shaped member on which the deposited film is formed is cooled to room temperature outside the film-forming space, and the belt-shaped member is expanded into a flat shape and cooled. 3. The method for continuously forming a large-area functional deposited film according to claim 2, wherein the functional deposited film is formed in a convex shape and cooled. (4) The microwave antenna means is inserted into the film forming space from either one of the opposing end surfaces of the columnar film forming space formed with the band member as a side wall so as to be parallel to the band member. 2. The method for continuously forming a large-area functional deposited film according to claim 1, further comprising the step of injecting microwave power into the film forming space. (5) Microwave power is introduced into the film forming space from the microwave antenna means through a microwave transparent member provided between the microwave antenna means and the film forming space. A method for continuously forming a large-area functional deposited film as described in . (6) Continuously forming a large area functional deposited film according to claim 5, wherein the microwave antenna means is separated from the plasma generated in the film forming space via the microwave transparent member. Method. (7) The method for continuously forming a large-area functional deposited film according to claim 1, wherein the plasma potential is controlled via bias applying means separated from the strip member. (8) The large area functional deposited film according to claim 7, wherein the bias applying means is disposed so that at least a portion thereof is in contact with the microwave plasma, and a bias voltage is applied to the bias applying means. How to form. (9) The method for continuously forming a large-area functional deposited film according to claim 8, wherein at least a portion of the bias applying means that is in contact with the microwave plasma is subjected to a conductive treatment. (10) The method for continuously forming a large-area functional deposited film according to claim 8, wherein the bias voltage is a direct current, a pulsating current, and/or an alternating current. (11) The method for continuously forming a large-area functional deposited film according to claim 8, wherein the bias applying means also serves as the gas supplying means. (12) The method for continuously forming a large-area functional deposited film according to claim 8, wherein the bias application means is arranged separately from the gas supply means. (13) The method for continuously forming a large-area functional deposited film according to claim 12, wherein the bias applying means comprises one or more bias rods. (14) The method for continuously forming a large area functional deposited film according to claim 1, wherein the plasma potential is controlled by a bias voltage applied to the strip member. (15) The method for continuously forming a large-area functional deposited film according to claim 14, wherein the gas supply means is set to a ground potential and is disposed so that at least a portion thereof is in contact with the microwave plasma. . (16) The method for continuously forming a large-area functional deposited film according to claim 14, wherein at least a portion of the gas supply means that is in contact with the microwave plasma is subjected to a conductive treatment. (17) The method for continuously forming a large area functional deposited film according to claim 1, wherein the outer diameter of the microwave transparent member is adjusted and selected in advance according to the complex dielectric constant of the plasma. (18) The method of continuously forming a large-area functional deposited film according to claim 1, wherein at least a conductive treatment is performed on the side of the band-shaped member exposed to the microwave plasma. (19) An apparatus for continuously forming a functional deposited film by a microwave plasma CVD method on a continuously moving strip-shaped member, wherein the strip-shaped member is continuously moved in its longitudinal direction, and A columnar film forming chamber is formed using the band-shaped member as a side wall and can maintain a substantially vacuum inside the film forming chamber through a curved part forming means for curving the film at A microwave coaxial line configured to supply microwave power for generating plasma; and a microwave coaxial line configured to transmit the microwave power supplied from the microwave coaxial line, and to transmit the microwave power from the microwave plasma to the center of the microwave coaxial line. a center conductor separating means for separating the conductors; a means for evacuating the film forming chamber; a gas supply means for introducing a film forming raw material gas into the film forming chamber; and a plasma potential of the microwave plasma. a bias applying means for controlling the temperature control means for heating and/or cooling the strip-shaped member, and a temperature control means for heating and/or cooling the strip-shaped member, the strip-shaped member forming the side wall of the film-forming chamber while continuously moving. 1. An apparatus for continuously forming a large-area functional deposited film, characterized in that the deposited film is continuously formed on a surface exposed to microwave plasma. (20) The curved portion forming means includes a curved start end forming roller, a curved end end forming roller, and an opposing curved portion end surface support ring, and the curved end forming roller and the curved end forming roller are connected to each other in the strip shape. 20. The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein the members are disposed in parallel with a gap left in the longitudinal direction of the members. (21) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein the bias applying means is arranged separately from the strip member. (22) The bias applying means is arranged such that at least a portion thereof is in contact with the microwave plasma, and a bias voltage is applied to the bias applying means.
An apparatus for continuously forming a large-area functional deposited film according to item 1. (23) The apparatus for continuously forming a large-area functional deposited film according to claim 22, wherein at least a portion of the bias applying means that is in contact with the microwave plasma is subjected to conductive treatment. (24) The apparatus for continuously forming a large-area functional deposited film according to claim 22, wherein the bias voltage is a direct current, a pulsating current, and/or an alternating current. (25) The apparatus for continuously forming a large-area functional deposited film according to claim 22, wherein the bias application means also serves as the gas supply means. (26) The apparatus for continuously forming a large-area functional deposited film according to claim 22, wherein the bias application means is arranged separately from the gas supply means. (27) The apparatus for continuously forming a large-area functional deposited film according to claim 26, wherein the bias applying means comprises one or more bias rods. (28) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein the bias applying means also serves as the strip member. (29) The apparatus for continuously forming a large-area functional deposited film according to claim 28, wherein the gas supply means is grounded and arranged so that at least a portion thereof is in contact with the microwave plasma. (30) The apparatus for continuously forming a large-area functional deposited film according to claim 29, wherein at least a portion of the gas supply means in contact with the microwave plasma is subjected to conductive treatment. (31) The center conductor of the microwave coaxial line is inserted into the film forming chamber from either one of the opposing end surfaces of the columnar film forming chamber, and is located near the central axis of the columnar film forming chamber. Claim 1: The strip member is arranged substantially parallel to the width direction of the strip member.
9. An apparatus for continuously forming a large-area functional deposited film according to 9. (32) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein the center conductor separating means is rotationally symmetrical. (33) The apparatus for continuously forming a large-area functional deposited film according to claim 32, wherein the center conductor separating means has a cylindrical shape, a truncated conical shape, or a conical shape. (34) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein at least two tuning means are arranged on the microwave coaxial line. (35) Continuously forming a large-area functional deposited film according to claim 34, wherein one of the two tuning means is an insertion length adjusting mechanism for the center conductor inserted into the film forming chamber. Device. (36) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein at least a conductive treatment is performed on the side of the band-shaped member exposed to the microwave plasma.