JPH0215869B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on light (here, light in a broad sense, ultraviolet light).
rays, visible rays, infrared rays, X-rays, gamma rays, etc.)
Electrophotographic photoconductive parts sensitive to electromagnetic waves such as
Regarding materials. Solid-state imaging devices or electronics in the image forming field
Photoconductivity in photographic image forming members and document reading devices
As a photoconductive material forming a layer, it is highly sensitive and SN
The ratio [photocurrent (Ip)/dark current (Id)] is high and the irradiation
Absorption that matches the spectral characteristics of electromagnetic waves
It has spectral characteristics and fast photoresponsiveness.
It must have a desired dark resistance value, and it must have a desired dark resistance value.
It must be non-polluting to the human body and solid-state photography.
In imaging devices, afterimages can be easily removed within a predetermined time.
Characteristics such as being able to manage
In particular, electronic photocopying machines used in offices as business machines
In the case of an electrophotographic imaging member incorporated into a real device.
In some cases, non-polluting during the above use is important.
It is a point. Based on these points, light guide has recently been attracting attention.
Amorphous silicon (hereinafter referred to as a-Si) is used as an electrical material.
For example, German Publication No. 2746967,
Publication No. 2855718 describes an image forming member for electrophotography.
The application of photoelectric technology in German publication no.
An application to a conversion reader is described. However, the conventional light guide made of a-Si
A photoconductive member having a conductive layer has a dark resistance value, photosensitivity,
electrical, optical, photoconductive properties such as photoresponsiveness, and
In terms of usage environment characteristics such as moisture resistance and
Need to improve overall characteristics in terms of quality
There is a point that can be further improved.
This is the reality. For example, when applied to an electrophotographic imaging member
Attempts were made to achieve high light sensitivity and high dark resistance at the same time.
Conventionally, when using the product, there is no residual
Cases where a potential remains are often observed, indicating that this type of photoconductivity
If parts are used repeatedly for a long time, they will
Accumulation of fatigue due to
If the
If you use it repeatedly, the responsiveness will gradually decrease.
There were many cases where inconveniences occurred. Furthermore, compared to the short wavelength side of the visible light region, a-Si
Therefore, the absorption in the wavelength region longer than the wavelength region on the long wavelength side is
It has a relatively small absorption coefficient and is currently in practical use.
In matching with conductor lasers,
The halogen lamp or fluorescent lamp used is the light source.
In this case, the long wavelength light cannot be used effectively.
There is still room for improvement in each aspect.
ing. In addition, if the irradiated light is in the photoconductive layer,
The amount of light that reaches the support without being fully absorbed.
When the amount increases, the support itself passes through the photoconductive layer.
If the reflectance of the incoming light is high, the photoconductive layer
Interference due to multiple reflections occurs within the image, resulting in
This is one of the causes of "blur". This effect is due to the fact that the illumination spot is
The smaller the size, the larger the size, especially for semiconductor lasers.
This is a big problem when using the light source as a light source. Furthermore, when configuring the photoconductive layer with a-Si material,
in order to improve its electrical and photoconductive properties.
In addition, hydrogen atoms or halo atoms such as fluorine atoms and chlorine atoms
Gen atoms, and boron atoms for control of electrical conductivity type
or phosphorus atoms, or for other property improvements.
Other atoms are included in the photoconductive layer as constituent atoms, respectively.
However, how are these constituent atoms contained?
Depending on the electrical or photoconductive
There may be problems with the characteristics. That is, for example, when a formed photoconductive layer is exposed to light,
Lifespan of photocarriers generated in this layer
If the support is not strong enough or in the dark,
This may be due to insufficient prevention of charge injection from the side.
This occurs in many cases. Therefore, efforts have been made to improve the properties of the a-Si material itself.
On the other hand, when designing photoconductive materials, the above-mentioned
It is necessary to devise ways to solve all of these problems.
be. The present invention has been made in view of the above points, and includes a
- Regarding Si, image forming members for electrophotography and solid-state imaging devices
As a photoconductive member used in equipment, reading devices, etc.
Comprehensive and thorough from the perspective of applicability and applicability
As a result of continued research and consideration, we found that silicon atoms are the base material.
and either a hydrogen atom H or a halogen atom X
Amorphous materials containing at least
Hydrogenated amorphous silicon, halogenated amorphous silicon
Fuas silicon or halogen-containing hydrogenated ammonium
Rufus silicon [hereinafter referred to as a generic term]
is composed of "a-Si (H, X")],
Layer of a photoconductive member having a photoreceptive layer exhibiting photoconductivity
The configuration is designed with specificity as explained below.
The photoconductive material created using this method has outstanding practical properties.
It not only shows the characteristics but also compares with conventional photoconductive materials.
It is superior in all respects.
It is particularly excellent as a photoconductive member for electrophotography.
It has the characteristic that
We found that it has excellent absorption spectrum characteristics.
Based on points. The present invention always has electrical, optical, and photoconductive properties.
Stable and almost unrestricted by usage environment
Compatible with all environments and has excellent photosensitivity characteristics on the long wavelength side
In addition, it has excellent resistance to light fatigue, and can withstand repeated use.
No deterioration phenomenon occurs even when the product is used, and there is no or almost no residual potential.
To provide a photoconductive member for electrophotography that is not observed
The main purpose is to Another object of the present invention is to provide light sensitivity in the entire visible light range.
It has a high degree of accuracy and is especially good for matching with semiconductor lasers.
We propose a photoconductive member for electrophotography that has a fast photoresponse.
It is to provide. Another object of the invention is to provide an imaging member for electrophotography.
When applied as a
for electrostatic imaging to the extent that it can be effectively applied.
Photoconductive material with sufficient charge retention ability during charging treatment
The goal is to provide the following. Still another object of the present invention is to
Images with clear tones and high resolution
An electronic device that allows you to easily obtain high-quality images without any blemishes.
An object of the present invention is to provide a photoconductive member for photographic use. Yet another object of the present invention is high photosensitivity,
Providing a photoconductive member for electrophotography with high signal-to-noise ratio characteristics.
It is to provide. The photoconductive member for electrophotography of the present invention is for use in electrophotography.
Support for photoconductive member and content 1 to 10×
Ten^FiveAmorphous containing atomic ppm germanium atoms
A first layer region with a layer thickness of 30 Å to 50 μ made of high quality material
(G) and containing silicon atoms (germanium
Layer thickness composed of amorphous material (does not contain atoms)
A second layer region (S) of 0.5 to 90 μm is formed from the support side.
Layer thickness 1 showing the photoconductivity of the layer structure provided in the order of
~100μ first layer and silicon atoms and 1×10^-3
Constructed of an amorphous material containing ~90 atomic% carbon atoms.
and a second layer with a layer thickness of 0.03 to 30μ.
A photoconductive member for electrophotography consisting of a receptor layer and
The first layer may include silicon atoms and germanium.
0.001 to the sum of nium atoms and nitrogen atoms
Layer region containing 50 atomic% nitrogen atoms (N)
and the substance that controls conductivity (C) by 0.01 to 5
Ten^Fourhaving a layer region (PN) containing atomic ppm;
The maximum distribution concentration of the substance (C) that controls conductivity
a large value is in the second layer region (S) and in the support
It is characterized by being located on the side of the body. It was designed to have the layer structure described above.
The electrophotographic photoconductive member of the present invention has the above-mentioned problems.
Extremely superior electrical and optical technology that can solve all problems
physical properties, photoconductive properties, electrical voltage resistance, and usage environment characteristics.
Show your gender. In particular, it has been applied as an electrophotographic imaging member.
In some cases, even when using coherent light, there is sufficient interference
It can be prevented and there is no residue left on image formation.
There is no influence of storage potential, and its electrical characteristics are stable.
It is highly sensitive and has a high signal-to-noise ratio.
It has excellent light fatigue resistance, repeated use characteristics, and high concentration.
The halftones are clear, and the resolution is high.
You can reliably obtain high-quality images over and over again.
Wear. Furthermore, the photoconductive member for electrophotography of the present invention has all possible
High photosensitivity in the visual range, especially semiconductor lasers
Excellent matching with other devices and quick response. Hereinafter, according to the drawings, the electrophotographic light guide of the present invention will be described.
The electrical components will be explained in detail. FIG. 1 shows the layers of the electrophotographic photoconductive member of the present invention.
Schematic configuration shown schematically to explain the configuration
It is a diagram. The photoconductive member 100 shown in FIG.
On top of the support 101 for use, a first layer ()
102 and a second layer ( ) 105
layer 107, the light-receiving layer 107 has a free surface 1
06 on one end face. The first layer ( ) 102 is formed from the support 101 side.
Germanium atoms and optionally silicon atoms
(Si), hydrogen atoms (H), and halogen atoms (X).
Amorphous material containing at least one [hereinafter referred to as “a-Ge
(Si, H, X)]
Consisting of layer region (G) 103 and a-Si (H,X)
a second layer region (S) 104 having photoconductivity;
It has a layered structure in which these are laminated in order. If the first layer ( ) 102 contains nitrogen atoms
Both contain a substance (C) that controls conduction properties,
The substance (C) is present in the first layer () 102.
The maximum value of the distribution concentration in the layer thickness direction is the second layer.
in the region (S) and in the second layer region (S)
In this case, it is distributed more toward the support 101 side.
Contains. Germanium source in the first layer region (G)
In the in-plane direction parallel to the surface of the support
is contained in a uniform state, but in the layer thickness direction,
It may be uniform or non-uniform. Also, germanium in the first layer region (G)
When the distribution state of atoms is non-uniform in the layer thickness direction,
The distribution concentration C in the layer thickness direction is determined from the support side or
or gradually toward the second layer region (S) side, or
or stepwise or linearly.
is desirable. In particular, germanium in the first layer region (G)
The distribution state of umium atoms is germanium in the entire layer region.
Atoms are continuously distributed, and the layer thickness of germanium atoms is
Distribution concentration C in the direction is from the support side to the second layer region
If a decreasing change toward (S) is given,
In this case, the first layer region (G) and the second layer region
(S) and has excellent affinity with
As shown in the figure, germanium atoms are formed at the end of the support.
By extremely increasing the distribution concentration C, semiconductor
Second layer region when using a body laser etc.
(S) absorbs almost no light on the long wavelength side.
In the first layer region (G), the absorption is substantially completely
It is possible to prevent drying due to reflection from the support surface.
It is possible to prevent the layer area (G) from
It is possible to sufficiently suppress reflection at the interface between the layer region (S) and the
I can do that. FIG. 2 to FIG. 10 show the light guide in the present invention.
Gel contained in the first layer region (G) of the electrical member
A typical example of the distribution state of manium atoms in the layer thickness direction is
shown. In Figures 2 to 10, the horizontal axis is germanium.
The vertical axis represents the distribution concentration C of umium atoms in the first layer region.
Indicates the layer thickness of (G), t_Bis the first layer region on the support side
The position of the end face of area (G) is t_Tis opposite to the support side
The position of the end face of the first layer region (G) on the side is shown. Immediately
First, the first layer region containing germanium atoms
(G) is t_BT from the side_TLayering takes place towards the sides. In FIG. 2, the content contained in the first layer region (G) is shown.
The first distribution state of germanium atoms in the layer thickness direction
A typical example is shown. In the example shown in Figure 2, the germanium atom
Support on which the first layer region (G) containing is formed
The surface of the body and the surface of the first layer region (G) are in contact with each other.
interface position t_BMoret₁Up to the position, germanium
The distribution concentration C of atoms is C₁while taking a certain value
The first layer region where germanium atoms are formed
Contained in (G), position t₁Rather than concentration C₂More interface
position t_Tis gradually and continuously reduced until
Ru. Interface position t_TIn this case, the fraction of germanium atoms is
Cloth density C is C₃It is said that In the example shown in Figure 3, the contained
The distribution concentration C of rumanium atoms is at position t_BMore position_T
Concentration C up to_Fourgradually and continuously decreasing from
position t_Tconcentration C at_FiveForm a distribution state such that
are doing. In the case of Figure 4, position t_BMore position₂until then
The distribution concentration C of rumanium atoms is the concentration C₆and a constant value
and position t₂and position t_Tgradually between
Continuously decreased position t_T, the distribution concentration C
is substantially zero (here, substantially zero and
is below the detection limit). In the case of Figure 5, the distribution concentration of germanium atoms is
Degree C is position t_BMore position_Tup to the concentration C₈Than
Continuously gradually decreased position t_Tsubstantially in
It is said to be zero. In the example shown in Figure 6, germanium atoms
The distribution concentration C of is given by the position t_Band position t₃In between,
Concentration C₉is a constant value, and the position t_TIn the case of concentration
C_TenIt is said that position t₃and position t_TThe distribution density is
The degree C is a linear function of the position t₃More position_Tup to
has been reduced. In the example shown in FIG. 7, the distribution concentration C is
position t_BMore position_Fouruntil the concentration C₁₁Take a constant value of
position t_FourMore position_Tuntil the concentration C₁₂More concentration C₁₃to
It is assumed that the distribution state decreases linearly. In the example shown in FIG. 8, the position t_BMore position_T
Until , the distribution concentration C of germanium atoms is
degree C₁₄It decreases linearly to more effectively reach zero.
There are a few. In Figure 9, position t_BMore position_Fiveuntil
Then, the distribution concentration C of germanium atoms is the concentration C₁₅
More concentration C₁₆is linearly decreased until the position t_Five
and position t_TBetween, the concentration C₁₆with a constant value of
An example is shown. In the example shown in FIG.
The distribution concentration C of mu atoms is at position t_Bconcentration C at₁₇in
Yes, position t₆This concentration C until it reaches₁₇the beginning
is gradually decreased, and t₆around the position of
is sharply decreased at position t₆Then the concentration C₁₈considered to be
Ru. position t₆and position t₇At first, the relationship between
decreased, and then slowly decreased gradually
position t₇At concentration C₁₉and position t₇and position t₈between
is very slowly and gradually reduced to position t.₈to
, the concentration C₂₀leading to. position t₈and position t_TBetween
Then, the concentration C₂₀In the figure, so that it becomes more substantially zero.
It is reduced according to a curve of the shape shown. As described above, from FIGS. 2 to 10, the first layer region
Layer thickness of germanium atoms contained in region (G)
As we have explained some typical examples of direction distribution states,
In addition, in the present invention, gel is formed on the support side.
It has a part with a high distribution concentration C of manium atoms, and
face t_TOn the side, the distribution concentration C is on the support side.
germanium, which has a considerably lowered area compared to
The distribution state of atoms is provided in the first layer region (G).
It is. First layer constituting the photoconductive member in the present invention
The first layer region (G) constituting () is preferably
As mentioned above, there are germanium atoms on the support side.
It has a localized region A in which it is contained at a relatively high concentration.
It is desirable to do so. In the present invention, the localized region (A) is shown in FIG.
To explain using the symbols shown in Figure 10, the interface
position t_BIt is preferable to set the distance within 5μ.
It is. In the present invention, the localized region (A) is a field
surface position t_BFull layer area up to 5μ thick (L_T) is said to be
In some cases, the layer region (L_T) is considered part of
In some cases. The localized region (A) is transformed into a layered region (L_T) as part of
Whether it is all or all depends on the layer being formed
It is determined as appropriate according to the characteristics. The localized region (A) is the germanium contained therein.
Germanium atoms are distributed in the layer thickness direction.
Maximum value C of the distribution concentration of mu atoms_naxis a silicon atom
preferably less than 1000 atomic ppm
above, more preferably 5000 atomic ppm or more, optimally
is 1×10^FourDistribution pattern that is considered to be more than atomic ppm
It is desirable that the layer be formed in such a way that it can be formed into a layer. That is, in the present invention, germanium atoms
The first layer region (G) contained is from the support side
Within 5μ at layer thickness (t_BThe distribution concentration is in the layer region of 5μ thick from
Maximum value of degrees C_naxIt is preferable that the structure be formed so that there is
Delicious. In the present invention, contained in the first layer region (G)
The content of germanium atoms is determined according to the aim of the present invention.
Make appropriate decisions according to your wishes so that the objectives are effectively achieved.
preferably from 1 to 10×10^Fiveatomic
ppm, more preferably 100-9.5×10^Fiveatomic
ppm, optimally 500 to 8×10^Fiveconsidered to be atomic ppm
It is desirable to In the present invention, the first layer region (G) and the second layer
The layer thickness of the region (S) effectively achieves the purpose of the present invention.
Formation is one of the important factors to achieve
The desired properties are sufficiently imparted to the photoconductive member to be used.
As such, due care must be taken when designing photoconductive materials.
need to be taught. In the present invention, the layer thickness of the first layer region (G)
T_Bis preferably 30Å to 50μ, more preferably 40
Desired to be Å~40μ, optimally 50Å~30μ.
Yes. Further, the layer thickness T of the second layer region (S) is preferably
is 0.5 to 90μ, more preferably 1 to 80μ, optimally
It is desirable that the thickness be 2 to 50μ. Layer thickness T of the first layer region (G)_Band second layer area
The sum of the layer thicknesses T of (S) (T_B+T) is required for both layer regions.
Required characteristics and characteristics required for the entire photoreceptive layer
Based on the organic relationship between the photoconductive members
It is determined as desired when designing the layers. In the photoconductive member of the present invention, the above (T_B
The numerical range of +T) is preferably 1 to 100μ, etc.
The preferred value is 1 to 80μ, optimally 2 to 50μ.
is desirable. In a more preferred embodiment of the present invention,
Above layer thickness T_BAnd the layer thickness T is preferably
T_BWhen satisfying the relationship /T≦1, for each
It is desirable that appropriate values be selected accordingly. Layer thickness T in the above case_Band the value of layer thickness T
In selecting T, more preferably T_B/T≦0.9,
Optimally T_B/T≦0.8 so that the relationship is satisfied
Layer thickness T_BIt is desirable that the values of the layer thickness T and the layer thickness T be determined.
stomach. In the present invention, contained in the first layer region (G)
The content of germanium atoms is 1×
Ten^FiveIn the case of atomic ppm or more, the first layer region
(G) layer thickness T_BIt is desirable to make it as thin as possible.
preferably 30μ or less, more preferably 25μ or less
The optimum thickness is preferably 20μ or less. In the present invention, the first layer constituting the first layer () is
1 layer region (G) or/and second layer region (S)
Halogen atom (X) contained as necessary in
Specifically, fluorine, chlorine, bromine, and iodine
Among them, fluorine and chlorine are particularly preferred.
It can be mentioned as follows. In the present invention, composed of a-Ge (Si, H, X)
To form the first layer region (G), for example
Glow discharge method, sputtering method, or ionic
Vacuum that utilizes discharge phenomena such as amplating method
It is done by a deposition method. For example, glow discharge method
According to
In order to form layer region 1 (G), basically
Raw material for supplying Ge that can supply rumanium atoms Ge
Supply gas and silicon atoms (Si) if necessary
Introducing hydrogen atoms (H) as a raw material gas for supplying Si
Introducing raw material gas or/and halogen atom (X) for
The raw material gas for
Glue is introduced into the deposition chamber at the desired gas pressure.
– to generate an electrical discharge and to
The layer may be formed on the surface of a predetermined support. gel
In order to distribute the manium atoms non-uniformly, it is necessary to
The distribution concentration C of germanium atoms is set to the desired rate of change.
a-Ge(Si,H,X) while controlling according to the curve
What is necessary is to form a layer consisting of. In addition, when forming by sputtering method, e.g.
For example, inert gas such as Ar, He, etc.
composed of Si in a mixed gas atmosphere based on
target, or a combination of the target and Ge.
Using two of the prepared targets, or Si
Using a mixed target of
Ge diluted with diluent gas such as He, Ar etc.
The raw material gas for supply or the raw material gas for Si supply is
Hydrogen atom (H) or/and halogen as required
Sputtering with gas for introducing atoms (X)
The plasma atmosphere of the desired gas is introduced into the deposition chamber for
At the same time as forming gas, the raw material gas for supplying Ge
Or/and desired gas flow rate of raw material gas for Si supply
while controlling according to the rate of change curve of
All you have to do is sputter the Tsuto. In the case of ion plating, for example,
Crystalline silicon or single crystal silicon and polycrystalline germanium
aluminum or single crystal germanium as evaporation sources, respectively.
The evaporation source is housed in the evaporation board as a
Thermal method or electron beam method (EB method)
etc. to heat and evaporate the flying evaporated matter to the desired gas.
Except for passing through a spasm atmosphere,
This can be done in the same way as the talling method.
come. Raw material gas for supplying Si used in the present invention
SiH is a substance that can become_Four,Si₂H₆,Si₃H₈，
Si_FourH_Tensilicon hydride in a gaseous state or capable of being gasified, such as
Elements (silanes) are listed as being effectively used.
In particular, ease of handling during layer creation work and Si supply
SiH in terms of good feeding efficiency, etc._Four,Si₂H₆is preferable
It is mentioned as Substances that can be used as raw material gas for Ge supply include:
GeH_Four,Ge₂H₆,Ge₃H₈,Ge_FourH_Ten,Ge_FiveH₁₂，
Ge₆H₁₄,Ge₇H₁₆,Ge₈H₁₈,Ge₉H₂₀gaseous such as
germanium hydride is effective
It is used for layer creation, especially for layer creation.
Ease of handling during work, good Ge supply efficiency, etc.
So, GeH_Four,Ge₂H₆,Ge₃H₈is preferred.
can be mentioned. For introducing halogen atoms used in the present invention
Many halogenated gases are effective as raw material gases for
For example, halogen gas, halogen
compounds, interhalogens, halogen-substituted
Gaseous or gasifiable materials such as silane derivatives
Preferred examples include rogene compounds. Furthermore, silicon atoms and halogen atoms
Constituent halves in a gaseous state or capable of being gasified
Silicon hydride compounds containing rogen atoms are also effective.
In the present invention, the following can be mentioned. Halogen compounds that can be suitably used in the present invention
Specifically, the substances include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF₃，
BrF_Five,BrF₃,IF₃,IF₇, ICl, IBr, etc.
Intermediate compounds can be mentioned. Silicon compounds containing halogen atoms, so-called halogens
Examples of silane derivatives substituted with carbon atoms include
For example, SiF_Four,Si₂F₆,SiCl_Four, SiBr_Fouretc.
Silicon rogenide is preferred.
I can do it. Adopts silicon compounds containing such halogen atoms
The characteristic light guide of the present invention is produced by the glow discharge method.
When forming electrical parts, raw material gas for Ge supply is required.
Hydrogenation as a raw material gas that can supply Si along with gas
can be deposited on the desired support without the use of silicon gas.
A first layer region made of a-SiGe containing rogen atoms
It is possible to form a region (G). According to the glow discharge method,
When creating the layer area (G) of 1, basically,
For example, silicon halide, which is the raw material gas for supplying Si.
and germanium hydride, which is the raw material gas for supplying Ge.
Mu and Ar, H₂, He and other gases at a predetermined mixing ratio.
Form the first layer region (G) so that the flow rate becomes
This is introduced into a deposition chamber to generate a glow discharge.
By forming a plasma atmosphere of gases such as
to form a first layer region (G) on a desired support.
However, it is possible to control the introduction ratio of hydrogen atoms.
to these gases to make it even easier to measure
Hydrogen gas or silicon compound gas containing hydrogen atoms
They may also be mixed in desired amounts to form a layer. In addition, each gas can be used not only as a single species but also in a predetermined mixing ratio.
It is safe to use a mixture of multiple types.
Ru. Sputtering method, ion plating method
In either case, halogen atoms are added to the layer formed.
To introduce the above-mentioned halogen compounds or the above-mentioned
A silicon compound gas containing halogen atoms is introduced into the deposition chamber.
to form a plasma atmosphere of the gas.
That's fine. In addition, when introducing hydrogen atoms, hydrogen atom guide
Necessary raw material gas, e.g. H₂, or the above
Gases such as silanes and/or germanium hydride
The gas is introduced into a deposition chamber for sputtering.
All that is required is to form a plasma atmosphere of gases. In the present invention, raw materials for introducing halogen atoms
The halogen compounds or halogens listed above as gases
Silicon compounds containing gen are used as effective ones.
In addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH₂F₂，
SiH₂I₂,SiH₂Cl₂,SiHCl₃,SiH₂Br₂,SiHBr₃etc
halogen-substituted silicon hydride, and GeHF₃，
GeH₂F₂, GeH₃F₁, GeHCl₃, GeH₂Cl₂，
GeH₃Cl, GeHBr₃, GeH₂Br₂, GeH₃Br,
GeHI₃, GeH₂I₂, GeH₃Hydrogenation and halogenation of I, etc.
germanium, etc., with hydrogen atoms as one of its constituent elements
halides, GeF_Four, GeCl_Four, GeBr_Four，
GeI_Four, GeF₂, GeCl₂, GeBr₂, GeI₂etc. halogen
Germanium oxide, etc. in gaseous state or gasified
Materials that can be used are also effective for forming the first layer region (G).
It can be mentioned as a starting material. Halogenated substances containing hydrogen atoms in these substances
When forming the first layer region (G), halogens are added to the layer.
Electrical or photoelectric properties upon introduction of gen atoms
Hydrogen atoms, which are extremely effective in controlling
Therefore, in the present invention, a suitable source for introducing halogen is
used as a fee. Hydrogen atoms are structurally introduced into the first layer region (G).
In addition to the above, press H₂Or SiH_Four,Si₂H₆，
Si₃H₈,Si_FourH_TenTo supply Ge with silicon hydride such as
germanium or germanium compound, or
is GeH_Four,Ge₂H₆,Ge₃H₈,Ge_FourH_Ten,Ge_FiveH₁₂，
Ge₆H₁₄,Ge₇H₁₆,Ge₈H₁₈,Ge₂H₂₀Hydrogenation of etc.
Silicon or Si to supply germanium and Si
A discharge is generated by coexisting a recon compound and a recon compound in the deposition chamber.
It can also be done by causing it to occur. In a preferred embodiment of the invention, the light guide formed
Hydrogen contained in the first layer region (G) of the electrical member
The amount of atoms (H) or the amount of halogen atoms (X) or
The sum of the amounts of hydrogen atoms and halogen atoms (H+X) is favorable.
Preferably 0.01~40atomic%, more preferably 0.05~
30 atomic%, optimally 0.1 to 25 atomic%
is desirable. Hydrogen atoms contained in the first layer region (G)
Control the amount of (H) or/and halogen atom (X)
For example, support temperature or/and hydrogen atom
(H) or to contain a halogen atom (X)
Introducing into the deposition system the starting materials used for
It is sufficient to control the amount, discharge power, etc. In the photoconductive member of the present invention, germanium
Second layer region (S) containing no atoms, germanium
In the first layer region (G) containing nium atoms
contains a substance (C) that controls conduction properties.
By this, said second layer region (S) and said first layer region (S)
The conduction properties of the layer region (G) can be controlled arbitrarily as desired.
can be controlled. At this time, the above contained in the second layer region (S)
The substance (C) covers the entire first layer region (G) or
It may be contained in some layer areas, but in any case
It is also contained in a state where it is distributed more towards the support side.
need to be That is, the material provided in the second layer region (S)
The layer region (SPN) containing (C) is the second layer
Provided as a full layer area of the area (S), or
Support side end layer as part of the second layer region (S)
It is established as an area (SE). The former region
If it is provided as a distribution concentration C_(S)but
linearly or stepwise in the direction of the support side.
It is provided so as to increase in a shape or a curve. Distribution concentration C_(S)Supported if increases in a curvilinear manner
The conductivity is controlled so that it monotonically increases toward the body side.
A controlling substance (C) is provided in the second layer region (S).
It is desirable to layer region (SPN) into the second layer region (S),
If provided as part of the layer area (SPN)
The distribution state of substance (C) inside is the surface of the support.
It is assumed that the layer is uniform in the in-plane direction parallel to the
It does not matter if it is uniform or non-uniform in the thickness direction.
stomach. In this case, in the layer region (SPN), the material
(C) is provided so that it is distributed non-uniformly in the layer thickness direction.
In this case, it is set in the entire layer area of the first layer area (S).
It should be set so that the distribution concentration line is the same as when
is desirable. Material that controls conductivity in the first layer region (G)
A layer containing the substance (C) by containing (C)
Also when providing a region (GPN), the second layer region (S)
This can be done in the same way as when creating a layer region (SPN) in
I can do that. In the present invention, the first layer region (G) and the first layer region (G)
The conduction properties can be controlled in either of the two layer regions (S).
When containing substance (C), it is contained in both layer regions.
The substances (C) to be treated may be of the same type but different from each other.
Also good. However, controlling the same kind of conductivity in both layer regions
When containing a substance (C) that
The maximum distribution concentration in the layer thickness direction of (C) is the second
in the layer region (S), i.e. the second layer region (S)
or at the interface with the first layer region (G)
It is preferable to provide the same. In fact, the maximum distribution
The concentration is at the contact interface with the first layer region (G) or at the contact interface with the first layer region (G).
It is desirable to provide it near the interface. In the present invention, as described above, the first layer ()
Containing a substance (C) that controls conduction characteristics inside
The layer region (PN) containing the substance (C) is
occupies at least a part of the layer area (S) of
Preferably, the support side of the second layer region (S)
Provided as an end layer region (S)E. The layer region (PN) is the first layer region (G) and the second layer region (G).
When provided so as to straddle both layer regions (S) of
includes a layer region of material (C) that controls the conduction properties.
Maximum distribution concentration C at (GPN)_(G)naxand the layer area
Maximum distribution concentration C at (SPN)_(S)naxBetween
C_(G)nax<C_(S)naxSo that the relational expression is established,
(C) is contained in the first layer (). Control the conductivity contained in the layer region (PN)
The substance (C) is what is called in the semiconductor field.
In the present invention, impurities can be mentioned.
gives p-type conductivity to Si or Ge
p-type impurity and n-type impurity that provides n-type conduction characteristics
I can name things. Specifically, as a p-type impurity,
Atoms belonging to the group (Group atoms), for example, B (B)
element), Al (aluminum), Ga (gallium), In
Especially suitable are Tl (thallium), etc.
B and Ga are used for this purpose. As an n-type impurity, it belongs to group of the periodic table.
atoms (group atoms), e.g. P (phosphorus), As (arsenic)
element), Sb (antimony), Bi (bismuth), etc.
In particular, P and As are preferably used. In the present invention, provided in the first layer ()
to control the conductive properties contained in the layer region (PN).
The content of the substance (C) required in the layer region (PN) is
The required conduction properties or the layer area (PN) are
a support or other layer area provided in contact with the
organic relationships, such as the relationship with the properties at the contact interface.
It can be selected as appropriate depending on the gender. Also, before
of other layer areas provided in direct contact with the recording area.
properties and properties at the contact interface with other layer regions
The relationship between substances that control conduction properties is also taken into consideration.
The content of (C) is appropriately selected. In the present invention, contained in the layer region (PN)
The content of the substance (C) that controls the conduction properties of
Preferably 0.01~5×10^Fouratomic ppm, more preferred
is 0.5~1×10^Fouratomic ppm, optimally 1-5×
Ten³It is preferable to set it as atomic ppm. Substance (C) that controls conduction properties in the present invention
The layer region (PN) containing
In contact with the contact interface between (G) and the second layer region (S),
Or part of the layer region (PN) is the first layer region
(G), and the layer
The content of the substance (C) in the region (PN) is
Preferably 30 atomic ppm or more, more preferably
50 atomic ppm or more, optimally 100 atomic ppm or more
By the above, for example, the substance to be included
is the above-mentioned p-type impurity, free of the photoreceptive layer.
When the surface is polarized and charged, the support side
Movement of electrons injected into the second layer region (S) from
It can effectively prevent the above-mentioned
If the substance to be exposed is the above-mentioned n-type impurity, the photoreceptor
When the free surface of the layer is subjected to polar charging treatment,
Injected from the support side into the second layer region (G)
The movement of holes can be effectively prevented. In the above case, the above-mentioned basic structure of the present invention
The layer area excluding the layer area (PN) below the formation
In the region (Z), there is a conduction contained in the layer region (PN).
conduction characteristics with a polarity different from the polarity of the material that governs its properties.
It may contain a substance that controls sex, or
is the material that governs the conduction properties of the same polarity in the layer region
much less than the actual amount contained in (PN).
It may be contained in a small amount. In such a case, the material contained in the layer region (Z)
The content of the substance that governs the conduction properties varies depending on the layer region.
The polarity and content of the above substances contained in the range (PN)
It shall be determined as appropriate according to the desire.
but preferably 0.001 to 1000 atomic ppm, more preferably
Suitably 0.05~500atomic ppm, optimally 0.1~
It is desirable to set it to 200 atomic ppm. In the present invention, a layer region (PN) and a layer region
(Z) contains a substance that controls the same kind of conductivity.
In the case where the content in the layer region (Z) is
Preferably, it should be 30 atomic ppm or less.
stomach. In addition to the above-mentioned cases, in the present invention, the first
in the layer () supporting conductivity with one polarity.
The polarity of the layer region containing the substance to be disposed and the polarity of the other
A layer region containing a substance that controls conductivity
are placed in direct contact with each other, and a so-called
A depletion layer can also be provided. That is, for example,
Contains the above p-type impurity in the first layer ()
layer region and the layer region containing the n-type impurity,
They are placed in direct contact to form a so-called p-n junction.
Thus, a depletion layer can be provided. In Figures 11 to 24, in the first layer ()
layer of substance (C) that controls conduction properties contained in
A typical example of the distribution state in the thickness direction is shown. In these figures, the horizontal axis is the layer thickness of material (C)
Directional distribution concentration C_(PN), the vertical axis is the support of the first layer
The layer thickness t from the side is shown. In the figure, t_Bis the support
The position of the end face of the first layer region (G) on the side, t_Tis against
The position of the end face of the second layer region (S) on the side, t₀is a layer
Indicates the position of the contact interface between region (G) and layer region (S).
vinegar. FIG. 11 shows the amount contained in the first layer ().
Distribution of substance (C) that controls conduction properties in the layer thickness direction
A first typical example of the condition is shown. In the example shown in FIG. 11, the substance (C)
It is not contained in the first layer region (G) and is not contained in the second layer region (G).
Concentration C only in layer region (S)₁Contained with a constant distribution concentration of
is possessed. In other words, the second layer region (S) is t₀
and t₁The substance (C) has a concentration C in the end layer region between₁constant
It is contained in a distributed concentration of In the example of FIG. 12, in the first layer region (G),
Substance (C) is contained evenly, but the second
The layer region (S) does not contain the substance (C).
stomach. And the substance (C) is t₀and t₂In the layer area between
has a distribution concentration of C₂is contained at a constant concentration, t₂and t_T
The layer area between C₂The concentration C is much lower than₃of
Contained at a certain concentration. Such a distribution concentration C_(PN)The first layer of substance (C) is
() in the second layer region (S) constituting the
By doing so, the second layer region (G) is separated from the first layer region (G).
It is effective to move the charge injected into (S) toward the surface.
It can be effectively prevented, and at the same time, the photosensitivity and
It is possible to measure the improvement in light and dark resistance. In the example of FIG. 13, the material is added to the second layer region (S).
Although (C) is uniformly contained, t₀in
concentration C_Fourt decreases monotonically toward the upper surface._Tto
The distribution concentration C is such that the concentration becomes 0 at_(PN)has changed
Substance (C) is contained in the state where it is present. first
The layer region (G) does not contain the substance (C). In the case of the examples in Figures 14 and 15, the substance
(C) is in the lower end layer region of the second layer region (S).
This is an example where it is unevenly contained. That is, the 14th
In the case of the example shown in the figure and FIG. 15, the second layer region
(S) is a layer region containing substance (C);
This layer area does not contain substance (C).
It has a layered structure in which the layers are stacked in order from the support side. The difference is in the cases of the examples in Figures 14 and 15.
In the case of Fig. 14, the points are distributed concentration C_(PN)ist₀and t₃while
In t₀Concentration C at position_FiveMoret₃Darkness at position
While the degree decreases monotonically to 0, the first
In the case of figure 5, t₀and t_FourIn between, t₀at the position of
Concentration C₆Moret_FourContinuous linearly until concentration 0 at position
This means that the number of people living in Japan is decreasing. Figure 14 and 1
In the case of the example shown in Fig. 5, the first layer region (G) also contains a substance.
(C) is not contained. In the examples of FIGS. 16 to 24, the second
The layer region (S) is a layer containing the substance (C)
area and the layer area that does not contain substance (C) are supported.
It has a two-layer structure laminated in this order from the holding side.
What they have in common is that Among them, Figure 17 to
In the example of FIG. 21, both are in the first layer region.
The distribution state of substance (C) in (G) is the second
Interface position t with layer region (S)₀towards the support
The distribution concentration C is decreasing due to_(PN)has a change state of
It is that you are. In the case of the examples in Figures 23 and 24, the first layer
Substance (C) in the layer thickness direction over the entire layer area of ()
are contained evenly. In addition, in the case of FIG. 23, the first layer region (G)
In t_BConcentration C at_{twenty three}Moret₀darkness in
degree C_{twenty two}until t_BMoret₀increases linearly towards the second
In the layer region (S) of t₀Concentration C at_{twenty two}
Moret_Tt up to 0 concentration at₀Moret_Tmonotonous towards
has been decreasing continuously. In the case of Figure 24, t_Band t₁₃In the layer area between
So, the concentration C_{twenty four}Contains substance (C) at a constant distribution concentration of
possessed, t₁₃and t_TIn the layer region between
C_{twenty five}more linearly decreasing, t_Treaches 0 at
ing. In the above figures 11 to 24, the first layer
() of the substance (C) that controls conductivity in
Distribution concentration C_(PN)Explained typical cases of changes in
Similarly, in each example, the maximum of substance (C)
The substance has a distributed concentration in the second layer region (S).
(C) is contained in the first layer (). In the present invention, it is composed of a-Si(H,X).
To form the second layer region (S), the above-mentioned step
In the starting material () for forming the layer region (G) of
excluding the starting material which becomes the raw material gas for Ge supply.
[Starting material for forming the second layer region (S)]
Shape the first layer region (G) using
be carried out in the same manner and under the same conditions as those used in
I can do it. That is, in the present invention, a structure composed of a-Si(H,X)
For example, to form the second layer region (S)
Glow discharge method, sputtering method, or ionic
Vacuum that utilizes discharge phenomena such as amplating method
It is made by a deposition method. For example, glow discharge method
, the second composed of a-Si(H,X)
To form the layer region (S), basically the above-mentioned steps are performed.
Si supply source that can supply silicon atoms (Si)
Hydrogen atoms (H) are introduced as necessary along with the feed gas
or/and raw material for introducing halogen atoms (X)
A gas is introduced into a deposition chamber whose interior can be reduced in pressure.
A glow discharge is generated in the deposition chamber, and a predetermined
a- on a given support surface in place;
A layer made of Si(H,X) may be formed. or,
For example, when forming by sputtering method,
Inert gas such as Ar, He, etc. or a base gas such as
A silicon-based material is
When sputtering a target, hydrogen atoms
(H) or/and halogen atom (X) introduction gas
If the gas is introduced into the deposition chamber for sputtering,
good. In the present invention, the first layer () to be formed is
Hydrogen contained in the constituent second layer region (S)
The amount of atoms (H) or the amount of halogen atoms (X) or
The sum of the amounts of hydrogen atoms and halogen atoms (H+X) is
Preferably 1 to 40 atomic%, more preferably 5 to 40 atomic%
30 atomic%, optimally 5-25 atomic%
is desirable. There is a conductive characteristic in the layer region constituting the first layer ().
Substances that control the properties (C), such as group atoms or
Alternatively, group atoms may be structurally introduced to form the substance.
To form a layer region (PN) containing (C)
is the starting material for the introduction of group atoms during layer formation.
Alternatively, the starting material for introducing group atoms may be in a gaseous state.
Starting to form the first layer () in the deposition chamber
It is best to introduce it together with the substance. a tribe like this
Possible starting materials for atom introduction include:
gaseous or at least layer-forming conditions at room temperature and pressure;
It is desirable that materials that can be easily gasified under
Delicious. Starting materials for the introduction of such group atoms and
Specifically, for the introduction of boron atoms, B₂H₆，
B_FourH_Ten,B_FiveH₉,B_FiveH₁₁,B₆H_Ten,B₆H₁₂,B₆H₁₄
Silicon hydride, BF etc.₃, BCl₃,BBr₃etc. halogen
Examples include silicon oxide. In addition, AlCl₃，
GaCl₃, Ga(CH₃)₃,InCl₃, TlCl₃I also list
I can do that. As a starting material for the introduction of group atoms,
It is effectively used for introducing phosphorus atoms.
So, PH₃,P₂H_FourHydrogenated phosphorus, PH etc._FourI, P.F.₃，
P.F._Five, PCl₃, PCl_Five, PBr₃, PBr_Five, P.I.₃etc. halogen
Examples include phosphorus chloride. In addition, AsH₃,AsF₃，
AsCl₃, AsBr₃,AsF_Five,SbH₃,SbF₃,SbF_Five，
SbCl₃,SbCl_Five, BiH₃, BiCl₃, BiBr₃etc. family
Listed as effective starting materials for atom introduction
I can do it. In the photoconductive member of the present invention, high photosensitivity and
High dark resistance, furthermore, support and first layer ()
For the purpose of improving the adhesion between
Nitrogen atoms are contained in (). first layer
The nitrogen atoms contained in () are the first layer ()
It may be evenly contained in the entire layer area, or
contains only some layer regions of the first layer ()
It may also be unevenly distributed. In addition, the distribution state of nitrogen atoms is such that the distribution concentration C(N) is
The first layer () is uniform in the thickness direction.
However, the distribution concentration C(N) is non-uniform in the layer thickness direction.
It's okay to be. In the present invention, provided in the first layer ()
The layer region (N) containing nitrogen atoms is photosensitive.
If the main purpose is to improve the power and dark resistance,
It is set so that it occupies the entire layer area of the first layer ().
, the support and the first layer ( ) or the first layer region
(G) and the second layer region (S)
If the main purpose is to measure the
The support side end layer region of the layer () or the first and second layer regions
It is provided so as to occupy the area near the interface between the two layer regions.
Ru. In the former case, nitrogen contained in the layer region (N)
The atomic content is relatively low to maintain high photosensitivity.
In the latter case, the strength of the adhesion between the layers
It is desirable that the amount be relatively large in order to reliably measure the
stomach. Also, the purpose of achieving both the former and the latter at the same time.
In order to
and relatively low concentration on the free surface side of the first layer.
or on the free surface side of the first layer.
Nitrogen atoms are actively included in the surface layer of the
The distribution state of nitrogen atoms in the layer region (N)
Just form it. Furthermore, the support or the first layer region (G)
to prevent charge injection into the second layer region (S).
When the purpose is to increase the apparent dark resistance
is a high concentration at the support side end of the first layer region (G).
Nitrogen atoms are distributed between the first layer region and the second layer region.
Nitrogen atoms are distributed in high concentration near the interface of the layer region.
Ru. Figures 25 to 40 show the entire first layer ().
A typical example of the distribution state of nitrogen atoms as a body is shown.
It will be done. Please note that we do not wish to explain any of these figures.
Symbols used without exception are shown in Figures 11 to 24.
It has the same meaning as used in . In the example shown in FIG. 25, the position t_BMore position₁
Up to nitrogen atom distribution concentration C₁is assumed to be a constant value, and the position
Placement₁from position t_TNitrogen atom distribution concentration up to C₂and constant
has been done. In the example shown in FIG. 26, the position t_BMore position₂
Up to nitrogen atom distribution concentration C₃is assumed to be a constant value, and the position
Placement₂More position₃Up to nitrogen atom distribution concentration C_FourTosa
, position t₃from position t_TUp to nitrogen atom distribution concentration C_Five
The nitrogen atom distribution concentration is reduced in three stages.
There is. In the example in Figure 27, position t_BMore position_Fourup to nitrogen
Atomic distribution concentration C₆and position t_Fourfrom position t_Tup to nitrogen
Atomic distribution concentration C₇It is said that In the example in Figure 28, position t_BMore position_Fiveup to nitrogen
Atomic distribution concentration C₈and position t_Fivefrom position t₆up to nitrogen
Atomic distribution concentration C₉and position t₆from position t_Tup to nitrogen
Atomic distribution concentration C_TenIt is said that 3 steps like this
The nitrogen atom distribution concentration is increasing. In the example of Figure 29, position t_BMore position₇up to nitrogen
Atomic distribution concentration C₁₁and position t₇from position t₈up to nitrogen
Atomic distribution concentration C₁₂and position t₈from position t_Tup to nitrogen
Atomic distribution concentration C₁₃It is said that Support side and self
The nitrogen atom distribution concentration should be high on the outer surface side.
There is. In the example shown in FIG. 30, position t_BMore position₉
Up to nitrogen atom distribution concentration C₁₄and position t₉from
position t_TenNitrogen atom distribution concentration up to C₁₅and position t_Tenmosquito
ra position t_TNitrogen atom distribution concentration up to C₁₄It is said that In the example shown in FIG. 31, the position t_Bfrom position t₁₁
Nitrogen atom distribution concentration up to C₁₆as position t₁₁from position
t₁₂Nitrogen atomic distribution concentration up to C₁₇and increased stepwise.
Set, position t₁₂from position t_TNitrogen atom distribution concentration up to C₁₈
and is decreasing. In the example in Figure 32, position t_Bfrom position t₁₃up to nitrogen
Atomic distribution concentration C₁₉and position t₁₃from position t₁₄until nitrogen
The elementary atom distribution concentration is C₂₀and stepwise increase in position
t₁₄from position t_Tnitrogen atom distribution concentration up to the initial concentration
concentration less than C_{twenty one}It is said that In the example shown in FIG. 33, the position t_Bfrom position t₁₅
The nitrogen atom distribution concentration is up to C_{twenty two}and position t₁₅Kara position
Placement₁₆Nitrogen atomic distribution concentration up to C_{twenty three}decrease to
Placement₁₆from position t₁₇Nitrogen atom distribution concentration up to C_{twenty four}and stairs
increase position t₁₈from position t_TUp to nitrogen atoms
Cloth density C_{twenty three}has been reduced to. In the example shown in Figure 34, the distribution concentration of nitrogen atoms is
The degree C(N) is the position t_BMore position_TThe distribution density becomes
degree 0 to C_{twenty five}It continues to monotonically increase up to . In the example shown in Figure 35, the distribution concentration of nitrogen atoms is
The degree C(N) is the position t_B, the distribution concentration C₂₆in,
The distribution concentration C₂₆From position t₁₈It's monotonous until
continuously decreases to position t₁₈distribution concentration C₂₇Tonatsu
ing. position t₁₈More position_TIn between, nitrogen
The distribution concentration of atoms C(N) is given by the position t₁₈more consecutively
increases monotonically, position t_TThe distribution concentration C at₂₈and
It's summery. In the example in Figure 36, compare with the example in Figure 35.
Similar but different in position t₁₉and position
t₂₀Because it does not contain nitrogen atoms,
be. position t_Band position t₁₉Between position t_Bdistribution in
Concentration C₂₉More position₁₉Continuous until distribution concentration 0 in
decreases monotonically, and the position t₂₀and position t_Tbetween the positions
t₂₀The distribution density at position t from 0_Bdistribution density in
degree C₃₀It continues to monotonically increase up to . In the photoconductive member of the present invention, FIGS.
As a typical example is shown in Fig. 36, the first layer
( ) on the lower surface and/or upper surface side.
The inside of the first layer () contains nitrogen atoms.
In order to
, the distribution concentration C(N) of nitrogen atoms in the layer thickness direction is
By continuously changing, for example, the first layer
Efforts are being made to increase the light sensitivity and dark resistance of (). In addition, in Figures 34 to 36, nitrogen
Continuously changing the distribution concentration C(N) of elementary atoms
In the layer thickness direction due to the inclusion of nitrogen atoms,
Coherence of laser light, etc. is achieved by slowing the change in refractive index.
It effectively prevents interference caused by light. In the example shown in FIG. 37, the position t_BMore position_{twenty one}
Up to the nitrogen atomic concentration C₃₁and position t_{twenty one}from position
t_{twenty two}increases to position t_{twenty two}The nitrogen atom concentration is the peak value
C₃₂become. position t_{twenty two}from position t_{twenty three}Nitrogen atomic concentration up to
decreases and position t_Tand the nitrogen atomic concentration C₃₁becomes. In the example shown in FIG. 38, the position t_Bfrom position t_{twenty four}
Up to the nitrogen atomic concentration C₃₃and position t_{twenty four}from position t_{twenty five}
increases rapidly until position t_{twenty five}The nitrogen atom concentration is p
value C₃₄Take position t_{twenty five}from position t_TNitrogen concentration up to
The degree decreases until it is almost zero. In the example shown in FIG. 39, position t_Bfrom position t₂₆
Nitrogen atomic concentration up to C₃₅from C₃₆slowly increasing to
addition, position t₂₆The nitrogen atom concentration is the peak value C₃₆Tona
Ru. position t₂₆from position t_TThe nitrogen atomic concentration rapidly increases until
decrease position t_Tand the nitrogen atomic concentration C₃₅becomes. In the example shown in FIG. 40, the position t_Bnitrogen atom in
Concentration C₃₇at position t₂₇The nitrogen atomic concentration decreases until nitrogen
Atomic concentration C₃₈becomes. position t₂₇from position t₂₈up to nitrogen
The atomic concentration is C₃₈is constant. position t₂₈from position t₂₉
The nitrogen atom concentration increases until the position t₂₉nitrogen atom in
Concentration is peak value C₃₉Take. position t₂₉from position t_TMa
The nitrogen atom concentration decreases at position t_TNitrogen atomic concentration at
C₃₈becomes. In the present invention, the layer region (N) is the first layer.
() or the first layer ()
Even if it does not occupy the entire area of the layer area (N), the layer thickness T₀
The proportion of the first layer () in the layer thickness T is sufficiently large.
If the nitrogen atoms contained in the layer region (N)
The upper limit of the content of
It is desirable to In the case of the present invention, the layer thickness T of the layer region (N)₀but
The ratio of the first layer () to the layer thickness T is 5
In the case where it is more than 2/2, in the layer area (N)
The upper limit for the amount of nitrogen atoms contained in
The sum of the three elements: germanium atom, germanium atom, and nitrogen atom [hereinafter referred to as
later written as “T (SiGeN)”], preferably
is less than 30 atomic%, more preferably 20 atomic%
Below, the optimum value is preferably 10 atomic% or less.
Delicious. In the present invention, nitrogen constituting the first layer ()
The layer region (N) containing elementary atoms is as described above.
Nitrogen atoms are near the support side and the free surface side.
Localized region (B) containing relatively high concentration
It is desirable that the former be provided as having
In the case of , the adhesion between the support and the first layer is
We plan to further improve the acceptance potential.
Rukoto can. The above localized region (B) is shown in FIGS. 25 to 40.
To explain using the symbols shown in , the interface position t_BAlso
is the free surface t_TIt is desirable to set the distance within 5μ.
stomach. In the present invention, the localized region (B) is a field
surface position t_Bor free surface t_TFull layer area up to 5μ thick
Area (L_T), or the layer area
(L_T). The localized region (B) is transformed into a layered region (L_T) as part of
Whether it is all or all depends on the layer being formed
It is determined as appropriate according to the characteristics. The localized region (B) is the nitrogen source contained therein.
The distribution concentration of nitrogen atoms is expressed as the distribution state of the atoms in the layer thickness direction.
The maximum value Cmax of the degree is preferably 500 atomic ppm
or more, more preferably 800 atomic ppm or more, optimal
The distribution state is such that it is said to be more than 1000 atomic ppm.
It is desirable that the layers be formed in such a way that the following can be achieved. That is, in the present invention, nitrogen atom-containing
The layer area (N) that
Within 5μ for layer thickness (t_Bor t_T(from 5μ thick layer area)
is formed such that there is a maximum value Cmax of the distribution concentration at
It is desirable that In the present invention, the layer region (N) is the first layer.
() or the first layer ()
Even if it does not occupy the entire area of the layer area (N), the layer thickness T₀
The proportion of the first layer () in the layer thickness T is sufficiently large.
If the nitrogen atoms contained in the layer region (N)
The upper limit of the content of
It is desirable to In the case of the present invention, the layer thickness T of the layer region (N)₀but
The ratio of the first layer () to the layer thickness T is 5
In the case where it is more than 2/2, in the layer area (N)
The upper limit of the amount of nitrogen atoms contained in T
(SiGeN) preferably 30 atomic% or less,
More preferably less than 20 atomic%, optimally
It is desirable that it be 10 atomic% or less. In the present invention, the purpose of the present invention can be achieved more effectively.
of nitrogen atoms in the layer region (N) to achieve
The distribution concentration line in the layer thickness direction is
The layer area is smooth and continuous.
It is desirable that (N) contains a nitrogen atom.
Also, the distribution concentration line has its maximum distribution concentration Cmax
is designed to exist inside the first layer ()
By doing so, the effects described later will be clearly demonstrated.
Ru. In the present invention, the maximum distribution concentration Cmax
is preferably opposite to the support of the first layer ().
Provided near the paired surface (free surface side in Figure 1)
It is desirable to be able to do so. In this case, the maximum distribution concentration
By appropriately selecting Cmax, the free surface side of the photoreceptive layer can be
When subjected to charging treatment, the inside of the photoreceptive layer is
to effectively prevent charge from being injected into the
I can do it. In addition, near the free surface, nitrogen atoms
Maximum distribution concentration Cmax when the distribution concentration is towards the free surface
Nitrogen atoms are added to the first layer so that they decrease more steeply.
() in a humid atmosphere.
The durability of can be further improved. The distribution concentration curve of nitrogen atoms is the maximum distribution concentration Cmax
in the first layer (), further
The distribution is divided so that the maximum value of the distribution concentration is on the side of the support.
Design the fabric concentration curve to include nitrogen atoms.
and the adhesion between the support and the first layer ()
This can improve charge injection prevention. In the present invention, nitrogen atoms are present in the first layer ().
In the central layer region, efforts are made to increase the dark resistance.
However, it is contained in an amount that does not reduce photosensitivity.
It is desirable to In the present invention, the maximum distribution concentration of nitrogen atoms
Cmax is preferably for T(SiGeN)
67 atomic% or less, more preferably 50 atomic% or less
Below, the optimal value is preferably 40 atomic% or less.
Yes. In the present invention, provided in the first layer ()
The content of nitrogen atoms contained in the layer region (N) is
Characteristics required for the layer region (N) itself or the layer
If the region (N) is provided in direct contact with the support
In this case, the characteristics of the contact interface with the support
Make appropriate selections in terms of organic relationships such as relationships.
I can do that. In addition, other layer regions may be directly contacted with the layer region (N).
If a layer area is provided, the characteristics of the other layer area and
Relationship with characteristics at the contact interface with other layer regions
The content of nitrogen atoms is selected appropriately, taking into account
Ru. The amount of nitrogen atoms contained in the layer region (N) is
Depending on the characteristics required for the photoconductive member to be formed.
Although it can be determined appropriately according to the desire, T (SiGeN)
preferably 0.001 to 50 atomic%, more preferably
Ideally 0.002~40atomic%, optimally 0.003~
It is desirable to set it to 30 atomic%. In the present invention, nitrogen atoms are added to the first layer ().
To provide a contained layer region (N), the first layer
The starting material for nitrogen atom introduction during the formation of ()
Used with starting materials for the formation of the first layer ()
and contain the amount in the formed layer while controlling the amount.
Just do it. Glow discharge method is used to form layer region (N)
If present, starting materials for the formation of the first layer ()
Nitrogen atoms selected from among
Starting material for introduction is added. Such a nitrogen source
At least a nitrogen source is used as a starting material for the introduction of nitrogen.
A gaseous substance whose constituent atoms are atoms that can be gasified
Most of the gasified substances used are
can be done. For example, a material whose constituent atoms are silicon atoms (Si).
Raw material gas and raw material containing nitrogen atoms (N) as constituent atoms
gas and, if necessary, hydrogen atoms (H) or/and
A raw material gas containing halogen atoms (X) as constituent atoms
Use by mixing at the desired mixing ratio, or use the
A raw material gas whose constituent atoms are silicon atoms (Si),
Nitrogen atom (N) and hydrogen atom (H) as constituent atoms
The raw material gas is also mixed at the desired mixing ratio.
Or, the constituent atoms of silicon atoms (Si)
raw material gas, silicon atoms (Si), and nitrogen sources.
The three constituent atoms are the child (N) and the hydrogen atom (H).
It can be used by mixing with raw material gas.
Ru. Also, separately, silicon atoms (Si) and hydrogen atoms
Nitrogen atoms in the raw material gas whose constituent atoms are (H)
Used by mixing raw material gases whose constituent atoms are (N)
You may do so. Nitrogen source used when forming layer region (N)
As a source gas for introducing nitrogen (N)
Starting materials usefully used include, in particular, e.g.
Nitrogen (N₂), ammonia (NH₃), hydrazine
(H₂NNH₂), hydrogen azide (HN₃), ammo azide
Nium (NH_FourN₃), etc., which are gaseous or capable of being gasified.
Nitrogen compounds such as nitrogen, nitrides and azides are listed.
You can get it. In addition, nitrogen atoms (N)
In addition to the introduction, halogen atoms (X) can also be introduced.
Nitrogen trifluoride (F₃N), Nitrogen tetrafluoride
element (F_FourN₂) and other halogenated nitrogen compounds.
I can do it. In the present invention, nitrogen is present in the layer region (N).
In order to further enhance the effect obtained with atoms, nitrogen
In addition to atoms, it is also possible to contain oxygen atoms.
come. Acid for introducing oxygen atoms into the layer region (N)
For example, oxygen is used as a raw material gas for introducing elementary atoms.
(O₂), ozone (O₃), nitric oxide (NO), dioxide
Nitrogen (NO₂), nitrogen monoxide (N₂O), sesquioxide
Nitrogen (N₂O₃), trinitrogen tetraoxide (N₂O_Four), pentoxide
Nitrogen (N₂O_Five), nitrogen trioxide (NO₃), silicon raw material
(Si), oxygen atom (O), and hydrogen atom (H)
Constituent atoms, e.g. disiloxane
(H₃SiOSiH₃), trisiloxane
(H₃SiOSiH₂OSiH₃) and other lower siloxanes.
You can get it. Nitrogen-containing
To form the layer region (N), single crystal or polycrystalline
Si wafer or Si₃N_FourWafer or Si
Si₃N_FourA wafer containing a mixture of
These are used as targets in various gas atmospheres.
This can be done by sputtering. For example, using a Si wafer as a target
If so, the nitrogen atom and optionally the hydrogen atom or/
and raw material gas for introducing halogen atoms.
Dilute with diluting gas as necessary to make it suitable for sputtering.
A gas plasma of these gases is introduced into the deposition chamber.
The Si wafer is sputtered by forming
That's fine. Also, separately, Si and Si₃N_Fourtarget different from
as or Si and Si₃N_FourA single target mixed with
By using the
in an atmosphere of diluent gas as a gas or at least
Hydrogen atom (H) or/and halogen atom (X)
Sputtering in a gas atmosphere containing constituent atoms
It is done by ringing. Introduction of nitrogen atom
As raw material gas for
The raw material gas for introducing nitrogen atoms into the raw material gas shown in
gas is also effective in sputtering.
can be used. In the present invention, when forming the first layer ()
A layer region (N) containing nitrogen atoms is provided in
In this case, the amount of nitrogen atoms contained in the layer region (N)
Create a desired layer by changing the cloth concentration C(N) in the layer thickness direction.
Layer with depth profile
To form the region (N), in the case of glow discharge
is the nitrogen atom whose distribution concentration C(N) should be changed.
Select the starting material gas for introduction and its desired gas flow rate.
Deposition while changing the rate of change appropriately according to the rate of change curve of
This can be done by introducing it indoors. For example, the hand
Usually used as motor or external drive motor etc.
installed in the middle of the gas flow path system by some method.
Gradually change the opening of a given needle valve
All you have to do is do the operation to make it happen. At this time, the change in flow rate
The rate does not have to be linear; for example, when using a microcomputer, etc.
to follow a pre-designed rate of change curve using
You can also control the flow rate to obtain the desired content curve.
can. Form layer region (N) by sputtering method
In this case, the distribution concentration of nitrogen atoms in the layer thickness direction C(N)
is changed in the layer thickness direction to determine the location of nitrogen atoms in the layer thickness direction.
To form the desired depth profile,
Firstly, as with the glow discharge method,
The starting material for introducing elementary atoms is used in a gaseous state, and the
Adjust the gas flow rate when introducing gas into the deposition chamber as desired.
Therefore, it can be achieved by changing it appropriately. Second, targets for sputtering, e.g.
For example, Si and Si₃N_Fourusing a mixed target with
If so, Si and Si₃N_FourThe mixing ratio with
Change the layer thickness direction of the layer in advance.
It is accomplished by In the photoconductive member 100 shown in FIG.
A second layer formed on the first layer ( ) 102
()105 has a free surface and is mainly moisture resistant,
Continuous repeated use characteristics, electrical voltage resistance, usage environment characteristics
In order to achieve the purpose of the present invention in terms of performance and durability,
provided. Further, in the present invention, the first layer ( ) 102
and the second layer ( ) 105
each have a common constituent element, silicon atoms.
chemical stability at the laminated interface.
have been sufficiently ensured. The second layer () in the present invention is a silicon raw material.
(Si), carbon atom (C), and hydrogen as necessary
Contains an atom (H) or/and a halogen atom (X)
[hereinafter referred to as “a-(Si_xC_1-x)_y(H,X)
_1-y” However, it is written as 0<x, y<1].
Ru. a-(Si_xC_1-x)_y(H,X)_1-yThe second consists of
The layer () is formed by glow discharge method, sputtering
method, ion plantation method, ion play
made by the Teing method, electron beam method, etc.
be done. These manufacturing methods depend on the manufacturing conditions and equipment capital.
Drop load level, manufacturing scale, photoconductive part to be manufactured
Selection is made as appropriate depending on factors such as the desired properties of the material.
photoconductive materials with the desired properties.
It is relatively easy to control the manufacturing conditions for manufacturing parts.
Along with silicon atoms, carbon atoms and halogen
Introducing atoms into the second layer to be prepared ()
Glow discharge method or
The sputtering method is preferably employed. Furthermore, in the present invention, glow discharge method and spa
The second method can be used in conjunction with the Tuttering method within the same system.
A layer () may be formed. Forming the second layer () by glow discharge method
is a-(Si_xC_1-x)_y(H,X)_1-yraw material for formation
Mix a predetermined amount of feed gas with diluent gas as needed
For vacuum deposition with mixed ratio and support installed
The gas is introduced into the deposition chamber of the
By generating electricity, the gas becomes plasma and the above-mentioned
on the first layer () already formed on the support
to a-(Si_xC_1-x)_y(H,X)_1-yAll you have to do is deposit it. In the present invention, a-(Si_xC_1-x)_y(H,X)_1-y
As raw material gas for formation, silicon atoms (Si),
Carbon atom (C), hydrogen atom (H), halogen atom
A group whose constituent atoms are at least one of (X)
Gasified substances or substances that can be gasified
Most of them can be used. Si as one of the constituent atoms among Si, C, H, and X
When using a raw material gas that is
A raw material gas consisting of constituent atoms and a source gas containing C as constituent atoms.
raw material gas and, if necessary, raw material containing H as a constituent atom
gas or/and source gas containing X as a constituent atom
Use by mixing at the desired mixing ratio, or use Si as a structure.
A raw material gas with constituent atoms and C and H as constituent atoms.
raw material gas or/and raw material containing X as a constituent atom
and gas, also at the desired mixing ratio.
Or, a raw material gas containing Si as a constituent atom and Si,
A raw material gas containing three constituent atoms of C and H, or
A raw material gas containing three constituent atoms: Si, C, and X.
Can be used in combination. In addition, there is also a raw material gas whose constituent atoms are Si and H.
mixed with raw material gas containing C as a constituent atom.
It is also possible to use a raw material gas containing Si and X as constituent atoms.
mixed with raw material gas containing C as a constituent atom.
You may do so. In the present invention, contained in the second layer ()
Suitable halogen atoms (X) are F, Cl,
Br, I, with F, Cl being particularly desirable.
Ru. In the present invention, forming the second layer ()
It can be used as a raw material gas that can be effectively used for
The gas must be in a gas state at room temperature and pressure, or it can be easily
There are substances that can be gasified. In the present invention, the raw material for forming the second layer ()
The gases that can be effectively used are Si and H.
SiH as a constituent atom_Four,Si₂H₆,Si₃H₈,Si_FourH_Tenetc.
Silicon hydride gas such as silane, C and H
and, for example, saturated carbon atoms with 1 to 4 carbon atoms.
Hydrocarbon, ethylene hydrocarbon having 2 to 4 carbon atoms,
Acetylenic hydrocarbons with 2 to 3 carbon atoms, halogens
Single substance, hydrogen halide, interhalogen compound, halo
silicon hydride, halogen-substituted silicon hydride, silicon hydride
I can list the basics. Specifically, methane is a saturated hydrocarbon.
(CH_Four), ethane (C₂H₆), propane (C₃H₈), n
-butane (n-C_FourH_Ten), pentane (C_FiveH₁₂),workman
Ethylene (C₂H_Four),
Propylene (C₃H₆), butene-1 (C_FourH₈), Butte
N-2 (C_FourH₈), isobutylene (C_FourH₈), pente
(C_FiveH_Ten), as acetylenic hydrocarbons,
Acetylene (C₂H₂), methylacetylene
(C₃H_Four), butin (C_FourH₆), as a single halogen
is a halogen gas of fluorine, chlorine, bromine, and iodine.
Hydrogen halides include FH, HI, HCl,
HBr, interhalogen compounds include BrF, ClF,
ClF₃,ClF_Five,BrF_Five,BrF₃,IF₇,IF_Five, ICl, IBr,
SiF as silicon halide_Four,Si₂F₆,SiCl_Four，
SiCl₃Br, SiCl₂Br₂,SiClBr₃,SiCl₃I, SiBr_Four，
As halogen-substituted silicon hydride, SiH₂F₂，
SiH₂Cl₂,SiHCl₃,SiH₃Cl, SiH₃Br, SiH₂Br₂，
SiHBr₃, as silicon hydride, SiH_Four,Si₂H₈，
Si_FourH_TenSilanes such as
I can do that. In addition to these, CF_Four,CCl_Four, CBr_Four,CHF₃，
CH₂F₂,CH₃F, CH₃Cl, CH₃Br, CH₃I,
C₂H_FiveHalogen-substituted paraffinic hydrocarbons such as Cl,
science fiction_Four,SCIENCE FICTION₆Fluorinated sulfur compounds such as Si(CH₃)_Four，
Si(C₂H_Five)_FourAlkyl silicides such as SiCl(CH₃)₃，
SiCl₂(CH₃)₂,SiCl₃CH₃Halogen-containing silicification such as
Silane derivatives such as alkyl are also listed as effective.
You can get it. These second layer () forming substances are
silicon with a predetermined composition ratio in the second layer ()
atoms, carbon atoms and halogen atoms as appropriate
of the second layer () so that hydrogen atoms are contained.
They are selected and used as desired during formation. For example, silicon atoms, carbon atoms, and hydrogen atoms
can be easily incorporated and a layer with desired properties can be formed.
Si(CH₃)_Fourand contains halogen atoms.
SiHCl as a material₃,SiH₂Cl₂,SiCl_FourOr
is SiH₃Cl, etc. are mixed in a predetermined mixing ratio in a gas state.
It is introduced into the device for forming the second layer () and released with glow.
By generating electricity, a-(Si_xC_1-x)_y(Cl
+H)_1-yforming a second layer () consisting of
I can do it. The second layer () by sputtering method
To form a single or polycrystalline Si wafer
Or C wafer or a mixture of Si and C.
Targeting wafers that are
halogen atom or/and hydrogen atom as necessary
spa treatment in various gas atmospheres containing
This can be done by tuttering. For example, using a Si wafer as a target
Then, the raw materials for introducing C and H or/and X
Add the gas to the spa, diluting it with diluent gas if necessary.
These gases are introduced into the deposition chamber for
The Si wafer is sputtered by forming a sputtering plasma.
All you have to do is tarling. Additionally, Si and C are separate targets.
or using a single target with a mixture of Si and C.
By using hydrogen atoms or
is/and in a gas atmosphere containing halogen atoms.
It is done by sputtering.
As a material that becomes the raw material gas for introducing C, H and
This is the second layer shown in the glow discharge example above.
() When the forming material is sputtering method
It can also be used as an effective substance. In the present invention, the second layer () is glow discharged
Used when forming by sputtering method or sputtering method.
The diluent gas used is so-called noble gas, for example.
He, Ne, Ar, etc. are preferred.
I can do it. The second layer () in the present invention
carefully shaped to give the desired characteristics.
will be accomplished. That is, Si, C, H or/and X as necessary.
The composition of the substances used as constituent atoms depends on the conditions for their creation.
Structurally, it takes forms ranging from crystals to amorphous.
In terms of electrical properties, it ranges from conductive to semiconducting to insulating.
properties ranging from photoconductive to non-photoconductive.
Since the properties up to the electrical properties are shown respectively, the present invention
In this case, a that has the desired characteristics depending on the purpose
−(Si_xC_1-x)_y(H,X)_1-yin places so that
The creation conditions are strictly selected according to the wishes.
Ru. For example, the second layer () may be used to improve electrical resistance.
In order to provide the upper main purpose, a-(Si_xC_1-x)_y
(H,X)_1-yelectrically insulating behavior in the usage environment.
It is created as a highly dynamic amorphous material. In addition, improvements in continuous repeated use characteristics and usage environment characteristics
A second layer () is provided with the main purpose of
In some cases, the degree of electrical insulation mentioned above is relaxed to some extent.
and has a certain degree of sensitivity to the light that is irradiated.
a-(Si_xC_1-x)_y(H,X)_1
-yis created. a-(Si) on the surface of the first layer ()_xC_1-x)_y(H,
X)_1-yWhen forming the second layer () consisting of the layer
The temperature of the support during formation depends on the structure of the layer being formed and
This is an important factor that influences the characteristics, and is
In this case, a-(Si_xC_1-x)_y
(H,X)_1-ylayered so that it can be created as desired.
It is desirable that the temperature of the support during formation be strictly controlled.
stomach. The desired objective of the present invention is effectively achieved.
Depending on the method of forming the second layer () for
The suitable temperature range is selected to form the second layer ()
is carried out, preferably at 20-400℃, more preferably
Suitably 50 to 350℃, optimally 100 to 300℃
is desirable. For the formation of the second layer (), the layer
Subtle control of the composition ratio of constituent atoms and control of layer thickness
Because it is relatively easy compared to other methods, etc.
The use of glow discharge method and sputtering method
Advantageously, these layering methods do not allow the formation of a second layer.
(), the above support temperature and
Similarly, the discharge power during layer formation is created a-
(Si_xC_1-x)_yX_1-yOne of the important factors that influences the characteristics of
It is one. Having the characteristics for achieving the object of the present invention
to a-(Si_xC_1-x)_yX_1-yis productive and effective.
The discharge power conditions for this are preferably 10~
300W, more preferably 20~250W, optimally 50~
It is desirable that it be 200W. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr,
More preferably, it is about 0.1 to 0.5 Torr.
Yes. In the present invention, in order to create the second layer ()
Support temperature, desired numerical range of discharge power and
The values in the range mentioned above can be mentioned, but these
Layer creation factors can be determined independently and separately
a-(Si_xC_1-x)_y(H,
X)_1-yso that a second layer () consisting of
Create factors for each layer based on mutual organic relationships
It is desirable to be able to determine the optimal value of -. The second layer () in the photoconductive member of the present invention
The amount of carbon atoms contained depends on the composition of the second layer ().
The desired features to achieve the objectives of the invention as well as the conditions for formation
The second layer (in which the properties are obtained) is formed.
It is a factor. Contained in the second layer () in the present invention
The amount of carbon atoms possessed constitutes the second layer ()
as appropriate depending on the type of amorphous material to be used and its characteristics.
It can be determined according to your wishes. That is, the general formula a-(Si_xC_1-x)_y(H,X)_1-y
Amorphous materials shown in can be roughly divided into silicon
Amorphous material composed of atoms and carbon atoms [hereinafter referred to as
After that, “a-Si_aC_1-a”. However, 0<a<1],
Composed of silicon atoms, carbon atoms, and hydrogen atoms
[hereinafter referred to as “a-(Si_bC_1-b)_cH_1-c"and
write down However, 0<b, c<1], silicon atom and
Carbon atoms, halogen atoms, and hydrogen atoms if necessary
[hereinafter referred to as "a-(Si_d
C_1-d)_e(H,X)_1-e”. However, 0<d, e<
1]. In the present invention, the second layer () is a-Si_a
C_1-acontained in the second layer ()
The amount of carbon atoms contained is preferably 1×10^-3~
90 atomic%, more preferably 1-80 atomic%, most
It is preferably 10 to 75 atomic%.
That is, the previous a-Si_aC_1-aIf we do this in the representation of a, then a
is preferably 0.1 to 0.99999, more preferably 0.2 to
0.99, optimally 0.25-0.9. In the present invention, the second layer () is a-(Si_b
C_1-b)_cH_1-cIf the second layer consists of ()
The amount of carbon atoms contained is preferably 1×10^-3
~90 atomic%, more preferably 1~
90 atomic%, optimally 10-80 atomic%
is desirable. The content of hydrogen atoms is preferably
1 to 40 atomic%, more preferably 2 to 35 atomic%
%, ideally 5 to 30 atomic%.
If the hydrogen content is within these ranges,
The resulting photoconductive member has excellent practical properties.
It can be fully applied as such. That is, the previous a-(Si_bC_1-b)_cH_1-cDo it with the display
For example, b is preferably 0.1 to 0.99999, more preferably
0.1-0.99, optimally 0.15-0.9, preferably c
0.6-0.99, more preferably 0.65-0.98, optimally 0.7
~0.95 is desirable. The second layer () is a-(Si_dC_1-d)_e(H,X)_1
-eincluded in the second layer ().
The content of carbon atoms is preferably 1×
Ten^-3~90 atomic%, more preferably 1-90 atomic
%, optimally 10 to 80 atomic% is desirable.
Yes. The content of halogen atoms is preferably 1 to
20 atomic%, more preferably 1-18 atomic%, most
It is preferable that the content be between 2 and 15 atomic%.
If the halogen atom content is within these ranges,
The produced photoconductive member can be fully applied to the actual field.
It is something that Hydrogen atoms included as necessary
The content of is preferably less than or equal to 19 atomic%, and more
Preferably, it is 13 atomic % or less. That is, the previous a-(Si_dC_1-d)_e(H,X)_1-ed,
If expressed as e, d is preferably 0.1~
0.99999, more preferably 0.1-0.99, optimally 0.15
~0.9, e is preferably 0.8~0.99, more preferably
0.82 to 0.99, ideally 0.85 to 0.98
Yes. Number range of layer thickness of the second layer () in the present invention
are important for effectively achieving the purpose of the present invention.
This is one of the factors. In order to effectively achieve the purpose of the present invention,
It can be determined as desired depending on the situation. Also, the layer thickness of the second layer () is
The amount of carbon atoms contained and the thickness of the first layer ()
Also, in relation to
According to the desired organic relationship according to the characteristics
It needs to be decided accordingly. In addition, it is possible to add a
It is also desirable to consider the cost-effectiveness. The layer thickness of the second layer () in the present invention is preferably
preferably 0.003 to 30μ, more preferably 0.004 to 20μ, most preferably
It is preferably 0.005 to 10μ. The support used in the present invention is electrically conductive.
It may also be electrically insulating. As a conductive support
For example, NiCr, stainless steel, Al, Cr,
Metals such as Mo, Au, Nb, Ta, V, Ti, Pt, Pd, etc.
Or an alloy of these may be mentioned. As the electrically insulating support, polyester, polyester, etc.
Liethylene, polycarbonate, cellulose acetate
Tate, polypropylene, polyvinyl chloride, poly
Vinylidene chloride, polystyrene, polyamide, etc.
Synthetic resin film or sheet, glass, ceramic
Tsuku, paper, etc. are usually used. electrical insulation of these
The sexual support preferably has at least one surface thereof.
is conductively treated, and the other side is on the conductively treated surface side.
Preferably, layers are provided. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Pd,In₂O₃, SnO₂,ITO(In₂O₃+SnO₂) etc.
Conductivity is imparted by providing a thin film of
or synthetic resin film such as polyester film.
For ilms, NiCr, Al, Ag, Pb, Zn, Ni,
Gold such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc.
Vacuum evaporation, electron beam evaporation, sputtering
Provided on the surface with a ring etc., or attached with the metal mentioned above.
The surface is laminated to make it conductive.
Granted. The shape of the support body may be cylindrical or base.
It can be of any shape such as a bolt shape or a plate shape, and can be shaped as desired.
For example, the shape is determined as shown in Figure 1.
The photoconductive member 100 is used as an electrophotographic image forming member.
In the case of continuous high-speed copying,
It is desirable to have an endless belt shape or a cylindrical shape. support
The thickness of the holder is determined so that the desired photoconductive member is formed.
Although it is determined as appropriate to
When functionality is required, the function as a support is
As thin as possible within the range where it can be fully utilized
It will be done. However, in such cases, the manufacturing of the support and
From the viewpoint of handling, mechanical strength, etc., it is preferable to
It is considered to be 10μ or more. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be described.
Let me explain about the abbreviation. Figure 41 shows an example of a photoconductive member manufacturing apparatus.
vinegar. Gas cylinders 202 to 206 in the diagram are
Raw material gas for forming bright photoconductive members is sealed
For example, 202 is
SiF diluted with He_FourGas (purity 99.999% or less)
SiF_Four/He) cylinder, 203 diluted with He
GeF_FourGas (purity 99.999%, hereinafter referred to as GeF)_Four/He and
abbreviated) cylinder, 204 is NH₃Gas (99.99% purity,
Below NH₃) cylinder, 205 diluted with He
B₂H₆Gas (purity 99.999%, below, B₂H₆/He
) cylinder, 206 is He gas (purity 99.999
%) It is a cylinder. To flow these gases into the reaction chamber 201
Valves 222-22 of gas cylinders 202-206
6. Check that the leak valve 235 is closed.
Also check the inlet valves 212-216 and outlet valves.
Lubes 217-221, auxiliary valves 232, 233
Make sure that the main bar is opened and
Open the tube 234 to access the reaction chamber 201 and each gas pipe.
Exhaust the inside. Next, the reading on the vacuum gauge 236 is approximately 5×
Ten^-6When it becomes torr, the auxiliary valves 232, 23
3. Close the outflow valves 217-221. Next, a light-receiving layer is formed on the cylindrical substrate 237.
To give an example of a case where the gas cylinder 202
More SiF_Four/He gas, from gas cylinder 203
GeF_Four/He gas, NH from gas cylinder 204₃Ga
H from gas cylinder 206₂gas, valve 2
Open 22, 223, 224, 226 respectively and exit
The pressure of pressure gauges 227, 228, 229, 231
1Kg/cm²and adjust the inflow valves 212, 213,
Gradually open 214 and 216 and install the mass flow controller.
Inside trollers 207, 208, 209, 211
Let each of them flow in. Subsequently, the outflow valve 21
7,218,219,221, auxiliary valve 232
are gradually opened to allow each gas to flow into the reaction chamber 201.
let SiF at this time_Four/He gas flow rate and GeF_Four/
He gas flow rate and NH₃Gas flow rate and H₂Ratio to gas flow rate
the outflow valves 217, 21 so that the value is the desired value.
8, 219, 221, and the reaction chamber 201
Adjust the vacuum gauge 236 so that the pressure inside reaches the desired value.
Adjust the opening of main valve 234 while checking the reading.
do. Then, the temperature of the base body 237 becomes higher than that of the heating heater 2.
38, the temperature is set in the range of 50 to 400℃.
After confirming that the
Glow discharge is generated in the reaction chamber 201 by setting the
to form a first layer region (G) on the base body 237.
do. The first layer region (G) is formed to a desired layer thickness.
Completely close all valves when
Ru. SiF_Four／SiH gas cylinder_Four/He(SiH_Fourpurity
99.999%) SiH instead of cylinder_Four/He gas bong
Veraine, B.₂H₆/He gas cylinder line, C₂H_Four
First layer area (G) using gas cylinder line
Perform the same valve operation as for forming the desired globules.
– Set the discharge conditions to maintain glow discharge for the desired time.
By holding the layer, a gap is formed on the first layer region (G).
a second material substantially free of rumanium atoms;
A layer region (S) can be formed. In this way, the first layer region (G) and the second layer
The first layer () consisting of the region (S) is the base
237. First layer formed to desired layer thickness as described above
() to form a second layer () on top of the first
by the same valve operation as in the formation of the layer ().
For example, SiH_Fourgas, C₂H_Fourneed gas each
Depending on the desired conditions, dilute with diluent gas such as He.
By causing a glow discharge according to
will be accomplished. Including halogen atoms in the second layer ()
For example, SiF_Fourgas and C₂H_Fourgas or this
to SiH₂2nd layer as above adding gas
This is done by forming (). Gas outflow valve required when forming each layer
Needless to say, close all outflow valves except for
Also, when forming each layer, there is no difference in the formation of the previous layer.
The used gas is inside the reaction chamber 201 and the outflow valve 21
Inside the gas piping from 7 to 221 to inside the reaction chamber 201
Outflow valve 21 to avoid residual
7 to 221, and auxiliary valves 232 and 233.
Open the main valve 234 fully and clean the system once.
Perform operations to evacuate to high vacuum as necessary. The amount of carbon atoms contained in the second layer () is
For example, in the case of glow discharge, SiH_Fourgas and
C₂H_FourFlow rate ratio of gas introduced into reaction chamber 210
be changed as desired or sputtered.
When forming a layer by
Spa of silicon wafer and graphite wafer
Change the ivy area ratio or use silicone powder and glue.
Target by changing the mixing ratio of roughite powder
Control as desired by molding
I can do it. Halogen contained in the second layer ()
The amount of halogen atoms (X) is the raw material for introducing halogen atoms.
gas, e.g. SiF_FourGas is introduced into the reaction chamber 201.
This is done by adjusting the flow rate when the water is released. Also, while forming layers, make sure that the layer formation is uniform.
For measurement, the base 237 is driven at a constant speed by a motor 239.
It is preferable to rotate it by degrees. Examples will be described below. Example 1 By the manufacturing equipment shown in Fig. 41, cylinder
For electrophotography under the conditions shown in Table 1 on an Al substrate of
Each sample was formed as an imaging member (see Table 2).
(see). Containment of impurity atoms (B or P) in each sample
The distribution concentration is shown in Figure 42, and the nitrogen atom content
The fabric density is shown in Figures 43A and 43B.
The distribution concentration of each atom predicts the flow rate ratio of each corresponding gas.
to change the rate of change according to the designed rate of change line.
I controlled it. Each sample obtained in this way was exposed to a charged exposure experimental device.
installed at 5.0 kV for 0.3 seconds,
A light image was immediately irradiated. The optical image is a tungsten run
A transmission type test using a light source with a light intensity of 2 lux sec.
It was irradiated through a tochiat. Immediately thereafter, use a charged developer (toner and
(including Yaliar) on the surface of the photoreceptive layer of each sample.
Good coverage on the photoreceptive layer surface by cladding
I got a nice toner image. Toner image on photoreceptive layer
was transferred onto transfer paper using 5.0kV corona charging.
However, each sample has excellent resolution and excellent gradation reproducibility.
A clear, high-density image was obtained. In the above, the light source is replaced by a tungsten lamp.
810nm GaAs semiconductor laser (10mW)
Same as above except that the electrostatic image was formed using
The image quality of the toner transfer image for each sample was
Upon evaluation, each sample had excellent resolution;
Clear, high-quality images with good gradation reproducibility can be obtained.
Ta. Example 2 By the manufacturing equipment shown in Fig. 41, cylinder
For electrophotography under the conditions shown in Table 3 on an Al substrate of
Each sample was formed as an image forming member (see Table 4).
(see). Concentration distribution of impurity atoms in each sample
is shown in Figure 42, and the concentration distribution of nitrogen atoms is shown in Figure 42.
This is shown in Figure 44. For each of these samples, the same procedure as in Example 1 was carried out.
When we conducted an image evaluation test, all samples showed
It gave a high quality toner transfer image. Also, for each sample
Repeatedly 200,000 times in an environment of 38℃ and 80%RH
When we conducted a usage test, all samples showed no image quality.
No deterioration in image quality was observed. Example 3 By the manufacturing equipment shown in Fig. 41, cylinder
For electrophotography under the conditions shown in Table 5 on an Al substrate of
Samples as image forming members (Sample No. 31-1 to 37-
12) respectively (Table 6). The distribution concentration of impurity atoms in each sample is
In Figure 42, the nitrogen atom content distribution concentration is shown in Figure 43.
A and 43B and 44. For each of these samples, the same procedure as in Example 1 was carried out.
When we conducted an image evaluation test, all samples showed
It gave a high quality toner transfer image. Also, for each sample
Repeatedly 200,000 times in an environment of 38℃ and 80%RH
When we conducted a usage test, all samples showed no image quality.
No deterioration in image quality was observed. Example 4 By the manufacturing equipment shown in Fig. 41, cylinder
For electrophotography under the conditions shown in Table 7 on an Al substrate of
Samples as image forming members (Sample Nos. 41-1 to 46-
16) respectively (Table 8). GeH when forming the first layer region (G)_Fourgas flow
The quantity ratio is changed according to a pre-designed change rate line.
The layer area is divided so that the Ge distribution concentration shown in Fig. 45 is obtained.
(G) and also the formation of the second layer region (S)
Time B₂H₆Gas and PH₃Design the gas flow ratio in advance
Figure 42 shows the change according to the rate of change line.
The layer region (S) is formed so that the impurity distribution concentration is as follows.
did. Also, when forming the first layer region (G), NH₃gas
The flow rate ratio is varied according to a pre-designed rate of change line.
The N distribution concentration shown in Figures 43A and 43B is
The first layer region (G) was formed so as to have the same degree. A similar picture as in Example 1 was drawn for each of these samples.
Image evaluation revealed that all samples were of high quality.
Images can be obtained. Example 5 By the manufacturing equipment shown in Fig. 41, cylinder
Example 1 and
Form an image for electrophotography by controlling the flow rate ratio of each gas in the same way.
Samples as parts (sample Nos. 51-1 to 56-12)
(Table 10). The distribution concentration of impurity atoms in each sample is
In Figure 42, the nitrogen atom content distribution concentration is shown in Figure 44.
In the figure, the content distribution concentration of germanium atoms is 45th.
As shown in the figure. For each of these samples, the same procedure as in Example 1 was carried out.
When we conducted an image evaluation test, all samples showed
It gave a high quality toner transfer image. Also, for each sample
The test was repeated 200,000 times in an environment of 38℃ and 80%RH.
When we conducted a reuse test, all samples showed
No deterioration in image quality was observed. Example 6 By the manufacturing equipment shown in Fig. 41, cylinder
Example 1 and the conditions shown in Table 11 were prepared on a shaped Al substrate.
Similarly, by controlling the flow rate ratio of each gas, it is possible to form images for electrophotography.
Samples as component parts (Sample No. 61-1 to 610-13)
(Table 12). The distribution concentration of impurity atoms in each sample is
In Figure 42, the nitrogen atom content distribution concentration is shown in Figure 43.
As shown in Figures A, 43B and 44, germanium
The concentration distribution of Ni atoms is shown in Figure 45.
Ru. For each of these samples, the same procedure as in Example 1 was carried out.
When we conducted an image evaluation test, all samples showed
It gave a high quality toner transfer image. Also, for each sample
Repeatedly 200,000 times in an environment of 38℃ and 80%RH
When we conducted a usage test, all samples showed no image quality.
No deterioration in image quality was observed. Example 7 Articles showing the conditions for creating the second layer () in Table 13
Samples No. 11-1 and 12- of Example 1 were
Electrophotography according to the same conditions and procedures as 1, 13-1
Each of the image forming members for use (sample Nos. 11-1-1 to 11-1)
-8, 12-1-1 to 12-1-8, 13-1-1 to 13
-1-8) were created. The husband of each electrophotographic image forming member thus obtained
The husband was placed separately in the copying machine and described in each example.
Under the same conditions as above,
For each electrophotographic imaging member, the transferred image
Overall image quality evaluation and durability through repeated continuous use
We conducted an evaluation. Comprehensive image quality evaluation of transferred images of each sample and repetition
Table 14 shows the results of durability evaluation after continuous use.
vinegar. Example 8 When forming the second layer (), the silicon wafer and
By changing the roughite target area ratio,
Containment of silicon and carbon atoms in the layer ()
Sample No. 11- of Example 1 except for changing the quantitative ratio.
2. Each of the image forming members is
Created. For each of the image forming members thus obtained,
image formation, development, and clearing as described in Example 1.
After repeating the cleaning process approximately 50,000 times, the image evaluation
When the test was carried out, the results shown in Table 15 were obtained. Example 9 When forming the second layer (), SiH_Fourgas and
C₂H_FourBy changing the gas flow ratio, the second layer ()
Change the content ratio of silicon atoms and carbon atoms in
Exactly the same as Sample No. 11-3 of Example 1 except for
Each of the imaging members was prepared by a method according to the following methods. For each image forming member thus obtained, Examples
The process up to transfer was repeated approximately 50,000 times using the method described in 1.
After repeating the image evaluation, Table 16
I got results like this. Example 10 When forming the second layer (), SiH_Fourgas,
SiF_Fourgas, C₂H_FourBy changing the gas flow rate ratio, the second
Containment of silicon and carbon atoms in the layer ()
Sample No. 11- of Example 1 except for changing the quantitative ratio.
4. Each of the image forming members is
Created. For each imaging member thus obtained
Imaging, development and cleaning as described in Example 1
After repeating the process approximately 50,000 times, image evaluation is performed.
The results shown in Table 17 were obtained. Example 11 Example except for changing the layer thickness of the second layer ()
The image was formed in exactly the same manner as Sample No. 11-5 in 1.
Each of the component parts was created. As described in Example 1
The process of image creation, development, and cleaning is repeated.
The results shown in Table 18 were obtained.

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【table】

【table】

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【table】

【table】

【table】

【table】

【table】

【table】

【table】

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【table】

【table】

【table】

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【table】

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use
× = Causes image defects

[Table] ◎: Very good ○: Good △: Sufficient for practical use ×: Image defects occur

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use
× = Causes image defects

[Table] Common layer forming conditions in the above embodiments of the present invention are shown below. Substrate temperature: germanium atom (Ge) containing layer
...About 200℃ Germanium atom (Ge)-free layer
...Approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member for electrophotography of the present invention, and FIGS. 2 to 10 respectively show germanium atoms in the first layer region (G). Explanatory diagram for explaining the distribution state, 1st
1 to 24 are explanatory diagrams for explaining the distribution state of impurity atoms in the first layer ( ), FIGS. 25 to 40 are explanatory diagrams for explaining the distribution state of nitrogen atoms, respectively, and FIG. 41 is an explanatory diagram for explaining the distribution state of nitrogen atoms, respectively. FIG. 42, FIG. 43A, FIG. 43B, FIG. 44, and FIG. 45 are explanatory diagrams showing the distribution state of each atom in the embodiment of the present invention, respectively. It is. 100...Photoconductive member, 101...Support, 102
...first layer (), 103...first layer region (G),
104...Second layer region (S), 105...Second layer (), 107...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography ^; a layer region (G) and a second layer region (S) having a phase thickness of 0.5 to 90 μ and made of an amorphous material containing silicon atoms (but not containing germanium atoms) are provided in order from the support side. A first layer with a layer thickness of 1 to 100 μm exhibiting the photoconductivity of the composition and a second layer with a layer thickness of 0.03 to 30 μm consisting of an amorphous material containing silicon atoms and 1×10 ⁻³ to 90 atomic % of carbon atoms. a photoreceptive layer comprising a layer of
A layer region containing 0.001 to 50 atomic% of nitrogen atoms (N) and a substance controlling conductivity (C) of 0.01 to 5 atomic%
The layer region (PN) contains ×10 ⁴ atomic ppm, and the maximum value of the distribution concentration of the conductivity controlling substance (C) is in the second layer region (S) and toward the support side. A photoconductive member for electrophotography characterized by the following. 2. The photoconductive member for electrophotography according to claim 1, wherein the first layer region (G) contains silicon atoms. 3. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform in the layer thickness direction. 4. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is uniform in the layer thickness direction. 5 First layer region (G) and second layer region (S)
The photoconductive member for electrophotography according to claim 1, wherein at least one of the above contains a hydrogen atom. 6 First layer region (G) and second layer region (G)
The photoconductive member for electrophotography according to claim 1 or 5, wherein at least one of the halogen atoms contains a halogen atom. 7. The photoconductive member for electrophotography according to claim 2, wherein the distribution state of germanium atoms in the first layer region (G) is such that more germanium atoms are distributed toward the support side. 8. The photoconductive member for electrophotography according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table. 9. The photoconductive member for electrophotography according to claim 1, wherein the substance controlling conductivity is an atom belonging to Group 3 of the periodic table.