JPH0217025B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field] 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
material (hereinafter simply referred to as photoconductive member). [Prior art] 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 has high sensitivity and
High signal-to-noise ratio [photocurrent (Ip)/dark current (Id)]
Matched to the spectral characteristics of the emitted electromagnetic waves
It has absorption spectrum characteristics and fast photoresponsiveness.
It must have a desired dark resistance value, and 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 in electrical parts.
For example, German Publication No. 2746967
Publication No. 2855718 describes an image forming unit for electrophotography.
As a material, German publication No. 2933411 describes photoelectric transformers.
The application to an exchange reading device is described. However, the conventional photoconductive layer composed of a-Si
The photoconductive member has dark resistance, photosensitivity, and photoresponse.
electrical, optical, photoconductive properties such as properties, and moisture resistance
In terms of usage environment characteristics such as durability, and stability over time,
It is necessary to aim for comprehensive improvement of characteristics in this respect.
The reality is that there are points that can be further improved.
be. 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
It starts to emit flash development. Or repeat at high speed.
Disadvantages such as gradual decrease in responsiveness when used repeatedly
There were many cases where there were points of agreement. 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.
Usually used in matching with conductor lasers.
Where the light source is a halogen lamp or fluorescent lamp.
If the
There is still room for improvement in these areas.
Ru. 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
particles, phosphorus atoms, etc., 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. Furthermore, when the layer thickness becomes more than 10 μm or more, it becomes necessary to
When left in air after being removed from the vacuum deposition chamber
Over time, the layer may lift or peel off from the surface of the support.
This may cause phenomena such as separation or cracks in the layers.
It was hot. This phenomenon occurs especially when the support is
Drum-shaped support used in the photographic field
In terms of stability over time, as often occurs in the body,
There are some points that can be resolved. 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 purpose] 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, we found that silicon atoms and germanium
hydrogen atom or halogen atom.
Amorph containing at least one of the children
As materials, so-called hydrogenated amorphous ass silicon gel
Manium, halogenated amorphous silicon gel
Manium or halogen-containing hydrogenated amorphous
silicon germanium (hereinafter referred to as a generic term)
Use “a-SiGe(H,X)” as a notation]
A light-receiving layer exhibiting photoconductivity consisting of
The configuration of the conductive member is specified as explained below.
The photoconductive members designed and created below are of great practical importance.
It not only exhibits excellent characteristics, but also surpasses conventional light guides.
Even when compared with electrical parts, it surpasses them in every respect.
It is particularly useful as a photoconductive member for electrophotography.
Possesses extremely excellent characteristics and long wavelength side
It has excellent absorption spectrum characteristics in
The present invention is based on this discovery. 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.
Our main purpose is to provide photoconductive materials that cannot be observed.
The purpose is to Another object of the present invention is to increase photosensitivity in the entire visible light range.
It has high performance and is particularly suitable for matching with semiconductor lasers.
To provide a photoconductive member that has high photoresponse and has a fast photoresponse.
It is. Still another object of the present invention is to
between the layer to be laminated and the support, or between each layer to be laminated.
Excellent adhesion, dense and stable structural arrangement
and to provide a photoconductive member with high layer quality.
It is. Still another object of the present invention is to form an image for electrophotography.
When applied as a component, the normal electrophotographic method
electrostatic imaging to the extent that it can be applied very effectively.
It has sufficient charge retention ability during charging treatment for
Almost no deterioration of its properties was observed even in a humid atmosphere.
Photoconductive member with excellent electrophotographic properties
The goal is to provide the following. Still another object of the present invention is to
High quality with clear contrast and high resolution
Photoconductive for electrophotography that makes it easy to obtain images
It is to provide parts. Still other objects of the present invention are high photosensitivity, high
Good signal-to-noise ratio characteristics and good electrical contact with the support
It is an object of the present invention to provide a photoconductive member having properties. [Structure of the invention] The present invention provides a support for a photoconductive member for electrophotography; provided on the support, silicon atoms and silicon
Content 1 to 10×10 for the sum of con atoms^Fiveatom
Constructed of an amorphous material containing ppm of germanium atoms.
a first layer region (G) with a layer thickness of 30 Å to 50 μ;
provided on the first layer region (G),
Amorphous (contains no germanium atoms)
A second layer area with a layer thickness of 0.5 to 90μ made up of the material
(S) exhibiting photoconductivity with a layer thickness of 1 to 100μ
one layer, and a silicone layer provided on the first layer.
con atom and 1×10^-3Contains ~90 atom% carbon atoms
A second layer with a thickness of 0.003 to 30 μ made of amorphous material
A photoreceptive layer consisting of a layer of
A photoconductive member for use, The first layer contains nitrogen atoms, and
The distribution concentration of nitrogen atoms in the layer thickness direction is
C(1), C(3), and C(2) with a layer thickness of 0.003 to 100μ, respectively.
1 area (1), 3rd area (3) with layer thickness 0.003~80μ, layer
The second region (2) with a thickness of 0.003 to 100μ is removed from the support side.
C(3) is a silicon atom and a germanium atom.
10 atomic ppm for the sum of Ni atoms and Ni atoms
~67 atomic%, and C(3)>C(2),C(1),
and at least one of C(1) and C(2) is 0.
It is characterized by the fact that there is no It was designed to have the layer structure described above.
The photoconductive member of the present invention overcomes all of the above-mentioned problems.
Excellent electrical, optical, and photoconductive solutions
Indicates physical characteristics, electrical voltage resistance, and usage environment characteristics. In particular, the photoconductive member of the present invention is suitable for electrophotographic imaging.
When applied as a component for image formation,
There is no influence of residual potential and its electrical characteristics are stable.
It has high sensitivity and 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. Moreover, the photoconductive member of the present invention is formed on a support.
The photoreceptive layer itself is strong and the support
It has excellent adhesion with
Can be used repeatedly. Furthermore, the photoconductive member of the present invention is transparent in the entire visible light range.
It has high photosensitivity and is especially compatible with semiconductor lasers.
It has excellent optical performance and fast photoresponse. [Example] Hereinafter, according to the drawings, the photoconductive member of the present invention will be explained.
This will be explained in detail. FIG. 1 shows a photoconductor of a first embodiment of the present invention.
FIG. 2 is a schematic configuration diagram for explaining the layer configuration of the member.
Ru. The photoconductive member 100 shown in FIG.
a support 101 for use, and a support 101 on which
A first layer () 102 provided and a first layer
Second layer ()10 provided on ()102
3. First layer () 102 and second layer
() 103 constitutes the photoreceptive layer 104.
Ru. The first layer ( ) 102 has germanium atoms
and silicon atoms, hydrogen atoms, and hydrogen atoms as necessary.
Amorphous containing at least one of the rogene atoms
The material (hereinafter referred to as "a-Ge (Si, H, X)")
a first layer region configured and provided on a support;
(G)105, a silicon atom, and if necessary,
At least one of a hydrogen atom and a halogen atom
(hereinafter referred to as “a-Si(H,X)”)
) on the first layer region (G) 105.
a photoconductive second layer region (S) provided;
106. Germanium atoms are present in the first layer region (G) 10
The first layer area is evenly distributed throughout the layer.
(G) may be contained in 105 or in a layer
Although it is evenly contained in the thickness direction, the distribution concentration is
may be non-uniform. However, in any case
Also, in the first layer region (G) 105, the support
Regarding the in-plane direction parallel to the surface of the holding body, germanium
U atoms are uniformly distributed and evenly contained.
Is it a point to make the characteristics uniform in the in-plane direction?
It is necessary. In particular, in the layer thickness direction of the first layer ( ) 102,
is uniformly contained, and is contained in the support 101.
The side opposite to the side where the photoreceptive layer 104 is provided
the free surface 107 side) of the support 1
01 side (interface side between the photoreceptive layer and the support 101)
or
The first layer region is
(G) 105 contains germanium atoms. In the photoconductive member of the present invention, as described above,
Germa contained in the first layer region (G) 105
The distribution state of Ni atoms is as follows in the layer thickness direction:
Taking the above-mentioned distribution state, the surface of the support 101 and
In the parallel in-plane direction, the distribution state is assumed to be uniform.
is desirable. In the present invention, the first layer region (G) 105
In the second layer region (S) 106 provided above
does not contain germanium atoms, and this
Forming the first layer (I) 102 in a similar layer structure
Depending on the
For light of all wavelengths from to relatively long wavelengths,
A photoconductive member with excellent sensitivity can be obtained.
Ru. Or, in one of the preferred embodiments,
Germanium in the first layer region (G) 105
The distribution state of atoms is such that germanium atoms are present in the entire layer region.
The atoms are continuously and evenly distributed, and germanium atoms
distribution concentration C in the layer thickness direction from the support 101 side.
The change decreases toward the second layer region (S) 106.
Given, the first layer region (G) 105
and the second layer region (S) 106
It has excellent properties, and as described later, the side end of the support 101
The distribution concentration C of germanium atoms is extremely
By increasing the size, semiconductor lasers etc. can be used.
In this case, in the second layer region (S) 106, almost no
The light on the long wavelength side that cannot be completely absorbed is absorbed into the first layer region.
(G) Substantially completely absorbed in 105
It is possible to prevent drying due to reflection from the support 101 surface.
It is possible to prevent interference. 2 to 10, the first layer region (G) 1
Layer thickness direction of germanium atoms contained in 05
A typical example is shown where the distribution state of
Ru. In Figures 2 to 10, the horizontal axis is germanium.
The distribution concentration C of nium atoms is shown, and the vertical axis shows the photoconductivity.
Indicates the layer thickness of the first layer region (G) 105, and t_Bteeth
Table of first layer region (G) 105 on support 101 side
The position of the surface is t_Tis the first layer on the side opposite to the support side
The position of the surface of region (G) 105 is shown. In other words, game
First layer region containing rumanium atoms (G)
105 is t_Bt from the side_Tlayer formation towards the side
Ru. In FIG. 2, the first layer region (G) 105 includes
Distribution state of germanium atoms in the layer thickness direction
A first typical example is shown. In the example shown in Figure 2, the germanium atom
A first layer region (G) 105 containing
The interface position where the surface of the support 101 and the surface of the support 101 contact each other
t_BFrom t₁Up to the position, germanium atoms are distributed
concentration C is C₁The first layer takes a certain value
contained in (), position t₁to interface position t_Tleading to
The distribution concentration is up to C₂more gradually and continuously decreased
It is. Interface position t_TIn the germanium field
The distribution density C of children is C₃It is said that In the example shown in FIG. 3, the first layer region
(G) Germanium atoms contained in 105
Cloth density C is at position t_BMore position_TConcentration C up to_Fourmosquito
Gradually and continuously decreases from position t_Tconcentration C at_Five
The distribution state is formed as follows. In the case of FIG. 4, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in
Placement_BMore position₂until the concentration C₆is assumed to be a constant value, and the position
Placement₂and position t_Tgradually and continuously decreased between
little and position t₇, the distribution concentration C₁₉is substantially
(here, essentially zero is the detection limit).
below the critical mass). In the case of FIG. 5, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in
Placement_BMore position_Tup to the concentration C₈more continuously
Gradually decreased position t_Tvirtually zero in
It is. In the example shown in FIG. 6, the first layer region
(G) Germanium atoms contained in 105
The cloth density C is at the position t_Band position t₃In between, the concentration
C₉is a constant value, and the position t_TThe concentration C_Tendifference
It will be done. position t₃and position t_TBetween, the distribution concentration C is
Position t linearly₃More position_Tdecreased up to
It is. In the example shown in FIG. 7, the first layer region
(G) Germanium atoms contained in 105
Cloth density C is at position t_BMore position_Fouruntil the concentration C₁₁constant
Takes the value and position t_FourMore position_Tuntil the concentration C₁₂darker
Degree C₁₃It is assumed that the distribution decreases linearly until
ing. In the example shown in FIG. 8, the first layer region
(G) Germanium atoms contained in 105
Cloth density C is at position t_BMore position_Tup to the concentration C₁₄
It decreases in a linear manner so as to reach more practically zero.
There is. In FIG. 9, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in
position t_BMore position_Fiveuntil the concentration C₁₅more concentrated
C₁₆is linearly decreased until the position t_Fiveand position t_Tand
Between, the concentration C₁₆An example of a constant value of
It is shown. In the example shown in Figure 10, the first layer region
of germanium atoms contained in region (G) 105
The distribution concentration C is at the position t_Bconcentration C at₁₇and rank
Placement₆This concentration C until it reaches₁₇It's slow at first
t₆Near the position of
Reduced position t₆Then the concentration C₁₈It is said that 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 Figures 2 to 10, the first layer area
Germanium atoms contained in region (G) 105
Explain some typical examples of the distribution state in the layer thickness direction.
Similarly, in the present invention, on the support body 101 side,
, and the part where the distribution concentration C of germanium atoms is high
has an interface t_TOn the side, the distribution concentration C is supported.
It has a part that is considerably lower than the holder 101 side.
The distribution state of germanium atoms is the first layer region.
(G) A preferred example is when it is provided in 105.
It is mentioned as one of the. First layer constituting the photoconductive member in the present invention
Region (G) 105 is preferably supported as described above.
on the support body 101 side or, on the contrary, on the free surface 1
There is a relatively high concentration of germanium atoms on the 07 side.
It is desirable to have a localized region (A) containing
Yes. For example, localized region A is shown in FIGS. 2 to 10.
Using the symbols shown, the interface position t_Bmore layers
It is desirable that the thickness be within 5μ in the thickness direction. The above localized region A is at the interface position t_Bup to 5μ thick
layer area L_TIn some cases, it may be considered as all of the
area L_TSometimes it is considered a part of. localized region A to layer region L_Tpart or all of
The first layer region (G) 1 to be formed
It is determined as appropriate according to the characteristics required for 05. Localized region A is the germanium contained therein.
Germanium atoms are distributed in the layer thickness direction.
The maximum value Cmax of the distribution concentration of atoms is the same as that of silicon atoms.
preferably 1000 atomic ppm or more, with respect to the sum of
preferably 5000 atomic ppm or more, optimally 1×10^Four
It seems that the distribution state can be such that it is more than atomic ppm.
It is preferable that the layer be formed in the following manner. That is, in the present invention, germanium atoms
The contained first layer region (G) 105 is a support
The layer thickness from the 101 side is within 5μ (t_BFrom 5 μ thick layer area
The shape is such that the maximum value Cmax of the distribution concentration exists in
It is preferable that the In the present invention, in the first layer region (G) 105
As the content of germanium atoms contained in
is desired so that the object of the present invention can be effectively achieved.
The sum with silicon atoms can be determined as appropriate according to
, preferably 1 to 10×10^FiveFrom atomic ppm
Preferably 100-9.5×10^FiveAtomic ppm, optimally,
500～8×10^FivePreferably in atomic ppm. Germani in the first layer region (G) 105
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
The distribution concentration C in the direction is from the support 101 side to the light receiving layer.
The change decreases toward the free surface 107 of 104.
change is given or vice versa.
If the rate of change curve of the distribution concentration C is
by arbitrarily designing according to your wishes.
The first layer region (G) 105 has the characteristics of
It can be realized as desired. For example, in the first layer region (G) 105
The distribution concentration C of germanium atoms is on the support 101 side.
In this case, the free surface of the photoreceptive layer 104 is sufficiently raised.
On the surface 107 side, the distribution density should be kept as low as possible.
The change in degree C is expressed as the distribution concentration curve of germanium atoms.
Comparison, including the visible light range, by giving
Light of all wavelengths from short wavelength to relatively long wavelength
In addition to achieving high photosensitivity for
Effective in preventing interference with coherent light such as laser light
It can be measured accurately. In the present invention, the first layer region (G) 105
Layer thickness T_Bis preferably 30 Å to 50 μ, more preferably
is 40Å to 40μ, optimally 50Å to 30μ.
desirable. Further, the layer thickness T of the second layer region (S) 106 is preferably
Preferably 0.5 to 90μ, more preferably 1 to 80μ,
The optimum thickness is preferably 2 to 50μ. Layer thickness T of first layer region (G) 105_Band the second
The sum of the layer thicknesses T of the layer region (S) 106 (T_B+T) is
Characteristics required for both layer regions and requirements for the entire photoreceptive layer
Based on the organic relationship between the characteristics
When designing the layers of the photoconductive member, it can be determined as appropriate.
determined. 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, the above
layer thickness T_Band layer thickness T is preferably T_B/T≦1
to each of them as appropriate to satisfy the following relationship.
It is desirable to select a value that is reasonable. Layer thickness T in the above case_Band the value of layer thickness T
More preferably, in the selection of 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.
It's a good thing. In the present invention, in the first layer region (G) 105
The content of germanium atoms contained in is 1×10
In the case of atomic ppm or more, the first layer region (G) 1
05 layer thickness T_BIt is desirable that the
preferably 30μ or less, more preferably 25μ or less
The optimum thickness is preferably 20μ or less. In the present invention, the layer of the first layer region (G) 105
The thickness and the layer thickness of the second layer region (S) 106 are
important factors for effectively achieving the objectives of
Because there is only one photoconductive member, the desired characteristics can be imparted to the formed photoconductive member.
When designing the photoconductive member, ensure that sufficient
Sufficient attention needs to be paid to In the photoconductive member of the present invention, high photosensitivity and
High dark resistance, furthermore, support and first layer () 1
In order to improve the adhesion between the
The first layer (I) 102 contains nitrogen atoms.
A layer region (N) is provided. The first layer ( ) 102 is as shown in FIG.
The distribution concentration C(N) of nitrogen atoms in the layer thickness direction is
The first region (1) with the value C(1)108, C(2) etc.
The second region (2) with the value 109,C(3)
and a third region (3) 110. In the present invention, the above-mentioned first, second, and third
Each area is in any of these three areas.
It does not necessarily need to contain nitrogen atoms.
However, the distribution concentration C(3) is the same as the distribution concentration C(1) and C(2).
larger than the deviation, and the distribution concentrations C(1) and C(2)
At least one of them is not 0 or the distribution density is
Degrees C(1) and C(2) must not be equal. Either distribution concentration C(1) or C(2) is 0
In this case, the first layer ( ) 102 contains nitrogen atoms.
The first area (1) 108 or
has a second region (2) 109 and a higher part
It has a third region (3) having a cloth density C(3). In this case, nitrogen atoms are contained in a relatively high concentration.
from the free surface 107 into the first layer ( ) 102
This is to ensure that the effect of preventing charge injection is obtained.
If so, the first region (1) 108 should not contain nitrogen atoms.
It is necessary to design the first layer ( ) 102 as a
Also, on the contrary, from the support 101 side, the light-receiving layer
Prevention of charge injection into 104 and support 101
This aims to improve the adhesion between the photoreceptive layer 104.
If so, the second region (2) 109 contains nitrogen atoms.
Design the first layer ( ) 102 as a region with no
There is a need. In the present invention, the maximum distribution concentration among the three
The third region (3) 110 having C(3) has good photosensitivity.
The dark resistance of the first ()102 while maintaining the characteristic of
When measuring the improvement of the distribution concentration C(3),
is set to a relatively low value, and the layer thickness is
The thickness should be sufficient within the necessary range.
is desirable. Also, set the value of distribution concentration C(3) to a relatively high value.
By doing so, charge is injected by the third region (3) 110.
If you expect a preventive effect, the third area (3) 1
With a layer thickness of 10, the effect of blocking charge injection can be sufficiently obtained.
In addition to making it as thin as possible within the range of
The free surface 107 side of the second layer ( ) 103 or the support
A third
It is desirable to provide region (3) 110. In this case, the third region (3) 110 supports
When provided closer to the body 101 side
The first region (1) 108 has its layer thickness within the required range.
The support 101 and the light-receiving
It is designed mainly to improve the adhesion between layer 104.
I get kicked. The third region (3) 110 is toward the free surface 107 side.
If provided closer together, the second region (2)
109 is the third area (3) 110 is exposed to a humid atmosphere.
It is mainly provided for the purpose of preventing accidents. In the present invention, the first region (1) and the second region
The layer thickness of (2) is related to the distribution concentration C(1) and C(2).
Although it is determined as appropriate and desired, it is preferable to
preferably 0.003 to 100μ, more preferably 0.004 to 80μ,
Optimally, 0.005 to 50μ is desirable. Further, the layer thickness of the third region (3) 110 is equal to the distribution concentration C
(3) will be determined as appropriate, but preferably
is 0.003~80μ, more preferably 0.004~50μ, optimal
It is desirable that the value be 0.005 to 40μ. The third region (3) 110 is provided as a charge injection blocking layer.
If the main function is to have a function, the first layer ()1
02 to the support 101 side or free surface 107 side.
The layer thickness is preferably 30μ.
Below, more preferably 20μ or less, optimally 10μ or less
It is desirable to do so. At this time, the third area (3) 11
0 on the side of the support body 101 provided close to each other.
1 region (1) 108 or the first region on the free surface 107 side
The layer thickness of the second region (2) 109 is the same as that of the third region (3) 110
Value and production of distribution concentration C(3) of nitrogen atoms contained in
This can be determined appropriately depending on the economic efficiency, but it is preferable.
Preferably 5μ or less, more preferably 3μ or less, optimal
It is desirable that the thickness be 1μ or less. In the present invention, the nitrogen atom content distribution concentration C(3)
The maximum value of silicon atoms and germanium
The sum of atoms and nitrogen atoms (hereinafter referred to as "T (SiGeN)")
preferably 67 atom%, more preferably
The preferred value is 50 atom%, and optimally 40 atom%.
Delicious. Also, the minimum value of the distribution concentration C(3) is T(SiGeN).
preferably 10 atomic ppm, more preferably 15
Atomic ppm, ideally 20 atomic ppm
Yes. If the distribution concentrations C(1) and C(2) are not 0, then
The minimum value of T(SiGeN) is preferably
or 1 atomic ppm, more preferably 3 atomic ppm,
The optimum level is preferably 5 atomic ppm. In the present invention, the distribution state of nitrogen atoms is
In the entire layer ( ) 102, as described above,
Although it is non-uniform in the layer thickness direction, the first, second, and third
In each region, the thickness is uniform in the layer thickness direction. 12 to 15, the first layer () 1
02 Typical example of the overall distribution of nitrogen atoms
is shown. Used without permission in explaining these figures.
The symbols shown are used in Figures 2 to 10.
It has the same meaning as what you did. In the example shown in Figure 12, the distribution concentration of nitrogen atoms is
degree C(N) is at position t_BMore position₉Until C_{twenty one}Toshi, place
Placement₉from position t₁₁Until C_{twenty two}and position t₁₁from position
t_TUntil C_{twenty one}It is said that In the example shown in Figure 13, the distribution concentration of nitrogen atoms is
degree C(N) is at position t_Bfrom position t₁₂Until C_{twenty three}Toshi, place
Placement₁₂from position t₁₃Until C_{twenty four}and stepwise increase,
position t₁₃from position t_TUntil C_{twenty five}and is decreasing. In the example of FIG. 14, the distribution concentration of nitrogen atoms C(N)
is position t_Bfrom position t₁₄up to C₂₆and position t₁₄Kara position
Placement₁₅Until C₂₇and stepwise increase, position t₁₅from
position t_Tup to a concentration less than the initial concentration C₂₈year
ing. In the example shown in Figure 15, the distribution concentration of nitrogen atoms is
degree C(N) is at position t_Bfrom position t₁₆Until C₂₉position
t₁₆from position t₁₇Until C₃₀position t₁₇from
position t₁₈Until C₃₁and stepwise increase, position t₁₈mosquito
ra position t_BUntil C₃₀has been reduced to. In the present invention, the first layer ( ) 102 is provided with
Layer region containing nitrogen atoms (N)
(at least of the first, second, and third areas mentioned above)
(consisting of two regions) is the light sensitivity and dark resistance.
If the main purpose is improvement, the first layer
() 102 is provided so as to occupy the entire layer area,
The electric current from the free surface 107 of the first layer ( ) 102
In order to prevent load injection, it is necessary to
between the support 101 and the light-receiving layer 104
When the main purpose is to strengthen the adhesion of
occupies the end layer region of the light-receiving layer 104 on the side of the support.
It is set up so that it can be used. In the first case, the layer area
The content of nitrogen atoms contained in (N) is
The second
If from the free surface 107 of the first layer ( ) 102
In order to prevent charge injection, the content of nitrogen atoms is
In the third case, the support 10
In order to ensure stronger adhesion with 1, the nitrogen atom
It is desirable that the content be relatively large. In addition, for the purpose of achieving the first three at the same time, supporting
Nitrogen atoms are relatively highly concentrated on the supporting body 101 side.
distributed in the center of the first layer ( ) 102
The first layer ( ) 102 is distributed at a relatively low concentration.
Nitrogen atoms are present in the surface layer region on the free surface 107 side of
The layer region has a distribution state of nitrogen atoms that increases the number of nitrogen atoms.
(N) may be formed inside. In order to prevent charge injection from the free surface 107,
In order to increase the distribution concentration of nitrogen atoms on the free surface 107 side,
Forming a layer region (N) with a large amount of C (N) is
desirable. In the present invention, the first layer ( ) 102 is provided with
In the layer region (N) containing nitrogen atoms
The content of nitrogen atoms is the amount required for the layer region (N) itself.
or the layer region (N) is the support 101.
When the support 1 is provided in direct contact with the
Organic
It can be selected as appropriate depending on the relationship. 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 as desired, silicon atoms and
The sum of germanium atoms and nitrogen atoms (hereinafter referred to as “T
(denoted as SiGeN)” preferably 0.001
~50 at%, more preferably 0.002-40 at%,
Optimally, it is desirable that the content be between 0.003 and 30 at%.
stomach. In the present invention, the layer region (N) is the first layer.
( ) 102 or the first
Even if it does not occupy the entire area of layer () 102, the layer area
(N) layer thickness T₀The layer thickness T of the first layer ( ) 102 of
If the proportion of the area is sufficiently large, the layer area (N)
The upper limit of the content of nitrogen atoms contained in
It is desirable that the value be sufficiently smaller than the value. In the present invention, the layer thickness T of the layer region (N)₀but
Percentage of the thickness T of the first layer ( ) 102
If the ratio is two-fifths or more, the layer area
As the upper limit of the amount of nitrogen atoms contained in (N)
is preferably 30 atom% relative to T(SiGeN)
or less, more preferably 20 atomic % or less, optimally
It is desirable that the content be 10 atomic % or less. In the present invention, layer regions containing nitrogen atoms
(N) is on the support 101 side or/and as described above.
Nitrogen atoms are present in the vicinity of the second layer ( ) 103 side.
It has a localized region (B) containing relatively high concentration.
It is desirable that the
In this case, the support 101 and the first layer ( ) 102
To further improve the adhesion between
Potential can be improved. The localized region (B) is the first layer () 102
Support body 101 side and second layer ( ) 103 side
It is desirable that the surface be provided within 5μ from the surface. In the present invention, the localized region (B) is
of the first layer () 102, from the support 101 or
From the surface of the second layer ( ) 103 side to a thickness of 5μ
Layer area (L_T) in some cases, and in others,
Layer area (L_T). The localized region (B) is transformed into a layered region (L_T) as part of
The photoreceptive layer 10 to be formed
It can be determined as appropriate according to the characteristics required for 4. 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 degree C(N) is preferably 500 atoms.
ppm or more, more preferably 800 atomic ppm or more, maximum
The distribution state is preferably 1000 atomic ppm or more.
It is desirable that the layers be formed as desired. That is, in the present invention, the first layer () 10
The layer region (N) containing nitrogen atoms in 2 is
Support 101 side or surface of second layer () 103
Maximum value Cmax of distribution concentration within 5μ in layer thickness from the surface
It is desirable that the structure be formed in such a way that it exists. In the present invention, if necessary, the first layer ()
The halogen atom contained in 102 is specifically
Examples include fluorine, chlorine, bromine, and iodine.
In particular, mention fluorine and chlorine as suitable.
I can do it. In the photoconductive member of the present invention, germanium
Atom-containing first layer region (G) 105 or
is/and a second one that does not contain germanium atoms.
In the layer region (S) 106, there is a substance that controls the conduction characteristics.
By containing quality (D), the layer region
(G) or/and the desired conductive properties of the layer region (S)
It can be arbitrarily controlled according to. To the present invention
In this case, the inclusion of a substance (D) that controls the conduction properties
The layer area (PN) is the first layer ( ) 102
It may be provided in part or all of. Or layer area
(PN) is a part or part of the layer region (G) or (S).
may be provided for all. As a substance (D) that controls such conduction characteristics,
Lists the so-called impurities in the semiconductor field.
In the present invention, silicon atoms or
or germanium atoms with p-type conductivity.
p-type impurity to give and n-type to give n-type conduction characteristics
Impurities can be mentioned. Specifically, p-type
Impurities include atoms belonging to group 1 of the periodic table (group 3).
group atoms), e.g. boron (B), aluminum
(Al), gallium (Ga), indium (In), tali
(Tl) etc., which are particularly suitable for use.
are B, Ga. In addition, as an n-type impurity,
Atoms belonging to a group of the periodic table (group atoms), e.g.
For example, phosphorus (P), arsenic (As), antimony (Sb),
Bismuth (Bi), etc., and is particularly preferably used.
The results are P and As. In the present invention, the first layer ( ) 102 contains
The content of the substance (D) that governs the conductive properties of
is the conduction property required for the first layer ( ) 102.
or the first layer ( ) 102 is in direct contact with the
At the contact interface with the support 101 provided with
Appropriately selected based on organic relationships such as relationship with characteristics.
You can choose. In addition, the substance (D) that controls the conduction characteristics is
The first layer ( ) 102 contains the first layer ( ) 102 .
locally in the desired layer region of layer () 102 of
In particular, when the first layer () 102 contains
When contained in the support side end layer region, the layer
Characteristics of other layer regions provided in direct contact with the region
and the characteristics at the contact interface with other layer regions.
The relationship between the substances that govern the conduction properties is also taken into account.
The content of (D) is selected as appropriate. In the present invention, the first layer ( ) 102 contains
The content of the substance (D) that governs the conductive properties of
is preferably 0.01 to 5×10^Fouratomic ppm,
More preferably 0.5 to 1×10^FourAtomic ppm, optimally 1
~5×10³Preferably in atomic ppm. In the present invention, the substance that controls the conduction characteristics
(D) in the layer region (PN) containing it
The content of quality (D) is preferably 30 atomic ppm or less.
above, more preferably 50 atomic ppm or above, optimally,
When the concentration is 100 atomic ppm or more, the above conduction properties are not supported.
The disposed substance (D) is one of the first layers () 102.
It is desirable to locally contain it in the layer region of the
Especially the support side end layer region of the first layer ( ) 102
It is desirable to have it unevenly distributed in (E). Among the above, the support side end of the first layer ( ) 102
The content in the substratum region (E) is higher than the above value.
Contains a substance (D) that controls the conduction properties as described above.
For example, the substance (D) can be
In the case of a p-type impurity of
Support when surface 107 undergoes polar charging treatment
The electric current injected into the photoreceptive layer 104 from the body 101 side
It can effectively prevent the movement of children, and
The substance that controls the conduction characteristics is the n-type impurity mentioned above.
In some cases, the free surface 107 of the photoreceptive layer 104 is
When subjected to polar charging treatment, whether the support 101 side
The movement of holes injected into the photoreceptive layer 104 from
It can be effectively prevented. In this way, the end layer region (E) on the side of the support is uniformly
Contains a substance (D) that controls the conduction characteristics of one polarity.
If the remaining layer of the first layer () 102 is
The layer region, that is, the support side end layer region (E)
The removed layer region (Z) has conduction of other polarity.
It may contain a substance that controls its properties, or it may contain
is the support material that governs the conduction properties of the same polarity.
than the actual amount contained in the side edge layer region (E).
It may be contained in a much smaller amount. In such a case, the material contained in the layer region (Z)
the content of the substance (D) that governs the conduction properties; and
is contained in the support side end layer region (E).
It can be applied as desired depending on the polarity and content of the substance.
Preferably, it is 0.001.
~1000 atomic ppm, more preferably 0.05-500 atomic
ppm, ideally 0.1 to 200 atomic ppm.
Delicious. In the present invention, the support side end layer region (E) and
and layer region (Z) with the same type of material that controls the conductivity.
When it is contained, it is added to the layer area (Z) of the substance concerned.
Preferably, the content is 30 atomic ppm
The following is desirable. In addition to the above cases,
In the present invention, in the first layer ( ) 102,
Contains a substance that controls conductivity with one polarity
layer region with polarity and supporting conductivity with the other polarity.
Direct contact with the layer area containing the substance to be applied
so as to provide a so-called depletion layer in the contact layer region.
You can also do that. Clogging, e.g. first layer ()1
02, the layer region containing the p-type impurity and
Direct contact with the layer region containing the n-type impurity
A so-called p-n junction is formed by forming a depletion
layers can be provided. In the present invention, composed of a-Ge (Si, H, X)
The first layer region (G) 105 to be
Low discharge method, sputtering method, or ion beam
Vacuum deposition using discharge phenomena such as rating method
formed by law. For example, in the glow discharge method
Therefore, the first one composed of a-Ge (Si, H, X)
To form the layer region (G) 105, basically
is a germanium source that can supply germanium atoms.
Raw material gas for feeding children and silicon raw material as needed.
Raw material gas for supplying silicon atoms that can supply silicon atoms
and raw material gas or/and halogen for hydrogen atom introduction.
It is possible to reduce the internal pressure of the raw material gas for introducing
The gas is introduced into the deposition chamber at the desired pressure, and the
Create a glow discharge in the stacking chamber and place it in a predetermined position in advance.
a-Ge on a given support surface
A layer consisting of (Si, H, X) may be formed. or,
First layer of germanium atoms with non-uniform distribution
In order to contain germanium in the region (G) 105,
The distribution concentration of mu atoms is controlled according to the desired rate of change curve.
Form a layer consisting of a-Ge (Si, H, X) while controlling
Just let it happen. Also, in the sputtering method
For example, inert gas such as Ar, He, etc.
Silico in a gas-based mixed gas atmosphere
A target composed of carbon atoms or
A target composed of a target and germanium atoms
or silicon atoms and gel.
Using a mixed target of manium atoms
If necessary, dilute with diluent gas such as He or Ar.
The raw material gas for supplying germanium atoms and the necessary
Introducing hydrogen atoms and/or halogen atoms as necessary
Introduce the gas for sputtering into the deposition chamber for sputtering,
by creating a plasma atmosphere of the desired gas.
Thus, a first layer region (G) 105 is formed. this
In the sputtering method, germanium atoms are
If the distribution is non-uniform, the germanium
Change the gas flow rate of the raw material gas for atomic supply to the desired rate of change.
While controlling according to the curve, the target is
It's better to do it by pattering. 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 a evaporation boat 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,
First, by doing the same as in the case of the talling method.
A layer region (G) 105 can be formed. For supplying silicon atoms used in the present invention
As a material that can be used as a raw material gas, SiH_Four,
Si₂H₆,Si₃H₈,Si_FourH_Tengaseous state or gas such as
Silicon hydride (silanes), which can be
In particular, during layer creation work.
Ease of handling, good silicon atom supply efficiency, etc.
In SiH_Four,Si₂H₆, are listed as preferable.
Ru. Can be used as raw material gas for supplying germanium atoms
As a substance, GeH_Four, Ge₂H₆, Ge₃H₈,
Ge_FourH_Ten, Ge_FiveH₁₂, Ge₆H₁₄, Ge₇H₁₆, Ge₈H₁₈,
Ge₉H₂₀Gaseous or gasifiable hydrogenation, such as
Germanium is listed as an effective use.
In particular, ease of handling during layer preparation work, gelatin
GeH_Four,
Ge₂H₆, Ge₃H₈are listed as preferred
Ru. 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. Also, furthermore
The constituent elements are silicon atoms and halogen atoms.
Halogen atoms in a gaseous state or capable of being gasified
Silicon hydride compounds containing
It can be mentioned in Ming. 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, Si₂F_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, germanium protons
Can supply silicon atoms together with raw material gas
Eliminates the use of silicon hydride gas as a raw material gas
also contains a halogen atom on the desired support 101
The first layer region (G) 105 made of a-SiGe is
It can be formed. According to the glow discharge method,
When manufacturing the first layer region (G) 105, the basic
For example, it is used as a raw material gas for supplying silicon atoms.
Sources for supplying silicon halide and germanium atoms
Germanium hydride and Ar, H, He as feed gas
etc. at a specified mixing ratio and gas flow rate.
A first layer region (G) 105 is formed in such a manner as to
into the deposition chamber and generate a glow discharge to remove these
By forming a gas plasma atmosphere,
First layer region (G) 10 on desired support 101
5, but the introduction ratio of hydrogen atoms is
In order to make it easier to control the
Silicon compound containing hydrogen gas or hydrogen atoms in the gas
A layer may also be formed by mixing a desired amount of gases. 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
First layer region (G) 1 formed in any case
In order to introduce a halogen atom into 05, the above-mentioned halogen atom is introduced.
Silicon containing a halogen compound or the above-mentioned halogen atom
The gas of the compound is introduced into the deposition chamber and the plasma of the gas is removed.
It would be a good idea to create a Zuma atmosphere. Further, hydrogen atoms are added in the first layer region (G) 105.
When introducing hydrogen atoms, raw material gas for introducing hydrogen atoms,
For example, H₂, or the above-mentioned silanes and/or
Sputtering gases such as germanium hydride and germanium hydride.
The plasma atmosphere of the gases is introduced into the deposition chamber for deposition.
All you have to do is create a surrounding environment. 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, HBr,
Hydrogen halides such as HI, SiH₂F₂,SiH₂I₂,
SiH₂Cl₂, SiHCl₃,SiH₂Br₂,SiHBr₃etc. halogen
Substituted silicon hydride, and GeHF₃, GeH₂F₂,
GeH₃F, GeHCl₃, GeH₂Cl₂, GeH₃Cl,
GeHBr₃, GeH₂Br₂, GeH₃Br, GeHI₃,
GeH₂I₂, GeH₃Hydrogenated halogenated germanium such as I
Halogen containing hydrogen atoms as one of its constituent elements, such as
GeF_Four, GeCl_Four, GeBr_Four, GeI_Four, GeF_Four,
GeCl₂, GeBr₂, GeI₂germanium halides such as
Substances that are in a gaseous state or can be gasified, such as
Starting material for forming effective first layer region (G) 105
It can be mentioned as a quality. Among these substances, halogenated substances containing hydrogen atoms
When forming the first layer region (G) 105, the material is
At the same time as introducing halogen atoms into
Hydrogen atoms, which are extremely effective in controlling physical properties, have also been introduced.
Therefore, in the present invention, a suitable method for introducing halogen is
used as raw material. Structure hydrogen atoms in the first layer region (G) 105
In addition to the above, H₂, or SiH_Four,
Si₂H₆,Si₃H₈,Si_FourH_TenGerma silicon hydride etc.
germanium or gel to supply nium atoms
Manium compound or GeH_Four, Ge₂H₆,
Ge₃H₈, Ge_FourH_Ten, Ge_FiveH₁₂, Ge₆H₁₄, Ge₇H₁₆,
Ge₈H₁₈, Ge₉H₂₀germanium hydride and silica, etc.
Silicon or siliconization to supply con atoms
and the compound coexist in the deposition chamber to generate electric discharge.
It can also be done by In a preferred embodiment of the invention, the first
of the hydrogen atoms contained in the layer region (G) 105 of
amount, or the amount of halogen atoms, or the amount of hydrogen atoms and halogen atoms.
The sum of the amounts of gene atoms (H+X) is preferably
0.01 to 40 atom%, more preferably 0.05 to 30 atom%,
The optimum content is preferably 0.1 to 25 at%. Hydrogen contained in the first layer region (G) 105
To control the amount of atoms and/or halogen atoms
is, for example, the support temperature or/and hydrogen atom, or
is the starting material used to contain the halogen atom
The amount of material introduced into the deposition system, the discharge force, etc.
It's better to control it. In the present invention, it is composed of a-Si(H,X).
The second layer region (S) 106 is
In the starting material () for forming layer region (G) 105
It becomes a raw material gas for supplying germanium atoms.
Starting material excluding starting material [second layer region (S)
106 using the starting materials ()]
Same as when forming the first layer region (G) 105
It can be formed according to the method and conditions of. That is, in the present invention, a structure composed of a-Si(H,X)
The second layer region (S) 106 made of
- Discharge method, sputtering method, or ion preparative method
Vacuum deposition method that utilizes discharge phenomena such as taing method
formed by. For example, the glow discharge method
Therefore, the second layer region composed of a-Si(H,X)
In order to form the region (S) 106, basically the above-mentioned
Silicon atom supply that can supply silicon atoms
Hydrogen atoms are introduced as necessary along with the raw material gas for
and/or raw material gas for introducing halogen atoms
is introduced into a deposition chamber whose interior can be depressurized, and the
Create a glow discharge in the stacking chamber and place it in a predetermined position in advance.
a-Si(H,
What is necessary is to form a layer consisting of X). Also, spats
When forming by the taring method, for example, Ar, He
or based on inert gases such as
composed of silicon atoms in a mixed gas atmosphere
When sputtering a target, hydrogen atoms or
/ and sputtering gas for introducing halogen atoms.
It is sufficient to introduce it into the deposition chamber for processing. In the present invention, the second layer region formed
(S) The amount of hydrogen atoms contained in 106, or
Amount of halogen atoms, or hydrogen atoms and halogen atoms
The sum of the amounts (H+X) is preferably 1 to 40 atoms
%, more preferably 5 to 30 atomic %, optimally 5 to 25
It is preferable to express it in atomic percent. In the present invention, nitrogen is added to the first layer ( ) 102.
In order to provide the layer region (N) containing atoms,
For introducing nitrogen atoms when forming the first layer ( ) 102
Formation of the first layer ( ) 102 using the starting materials of
in the formed layer.
It is sufficient to control the amount and include it. Glow discharge method is used to form layer region (N)
If there is, the first layer ( ) 102 type described above
selected as desired from among the starting materials for
A starting material for the introduction of nitrogen atoms is added to the material.
As a starting material for such nitrogen atom introduction, a small amount of
A gaseous substance whose constituent atoms are at least nitrogen atoms.
or a large amount of gasified substances that can be gasified.
Any of the following can be used. For example, a raw material gas whose constituent atoms are silicon atoms
, a raw material gas whose constituent atoms are nitrogen atoms, and the necessary
Consists of hydrogen atoms or/and halogen atoms depending on
By mixing the raw material gas as atoms at the desired mixing ratio.
or using silicon atoms as constituent atoms.
raw material gas and constituent atoms including nitrogen atoms and hydrogen atoms.
and raw material gas at the desired mixing ratio.
or with silicon atoms as constituent atoms.
raw material gas, silicon atoms, nitrogen atoms and hydrogen
A raw material gas consisting of three atoms is mixed.
It can be used as Also, separately, it is composed of silicon atoms and hydrogen atoms.
Nitrogen atoms are used as constituent atoms in the raw material gas.
A mixture of raw material gases may be used. Nitrogen source used when forming layer region (N)
Effective as a raw material gas for introducing
The starting materials used include nitrogen as a constituent atom or
Or, for example, nitrogen whose constituent atoms are nitrogen and hydrogen.
(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 azide
I can list them. In addition, the introduction of nitrogen atoms
In addition to this, halogen atoms can also be introduced.
From, nitrogen trifluoride (F₃N), nitrogen tetrafluoride (F_FourN₂)
Nitrogen halides such as
Ru. In the present invention, a nitrogen source is present in the layer region (N).
In order to further enhance the effect obtained with
In addition to oxygen atoms, it can also contain oxygen atoms.
Ru. Oxygen source for introducing oxygen atoms into the layer region (N)
For example, oxygen can be used as a raw material gas for introducing oxygen.
(O₂), ozone (O₃), nitric oxide (NO), dioxide
Nitrogen (NO₂), nitrogen monoxide (N₂O), sesquioxide
Nitrogen (N₂O₃), nitrogen tetroxide (N₂O_Four), pentoxide
Nitrogen (N₂O_Five), nitrogen trioxide (NO₃) silicon atom
An example where the constituent atoms are an oxygen atom and a hydrogen atom.
For example, disiloxane (H₃SiOSiH₃), trisiloxa
(H₃SiOSiH₂OSiH₃) and other lower siloxanes, etc.
can be mentioned. Shape the layer region (N) by sputtering method.
In order to form the first layer () 102,
Single crystal or polycrystalline silicon wafer or
Si₃N_FourWafer or silicon atoms and Si₃N_Fourbut
Target wafers containing mixed
As a test, these were spattered in various gas atmospheres.
This can be done by tallying. For example, if you target silicon wafers,
When used with a nitrogen atom and optionally a hydrogen atom,
or/and raw material gas for introducing halogen atoms
Dilute with diluting gas as necessary and spatter
These gases are introduced into a deposition chamber for
The silicon wafer is spun by forming a plasma.
All you have to do is tumble. Also, separately, silicon atoms and Si₃N_Fourseparate from
as a target or with silicon atoms and Si₃N_Fourof
By using a mixed target
The atmosphere of diluent gas as sputtering gas
in air or at least hydrogen atoms or/and halogens
in a gas atmosphere containing carbon atoms as constituent atoms.
All you have to do is sputtering. Source for introducing nitrogen atoms
As the source gas, the gas shown in the glow discharge example mentioned above is used.
The raw material gas for introducing nitrogen atoms in the raw material gas is
Also used as an effective gas for sputtering.
can be done. In the present invention, formation of the first layer ( ) 102
At this time, a layer region (N) containing nitrogen atoms is established.
When the nitrogen atoms contained in the layer region (N)
By changing the distribution concentration C(N) in the layer thickness direction,
Has the desired distribution state (depth profile) in the layer thickness direction
To form the layer region (N), in the case of glow discharge
The nitrogen source whose distribution concentration C(N) should be changed is
The starting material gas for introduction of the particles is adjusted to the specified gas flow rate.
Deposition while changing the rate of change appropriately according to the desired rate of change curve.
It can be installed indoors. e.g. manually or externally
Some commonly used method such as a drive motor
Due to the
- Perform operations to change the opening of the dollar valve as appropriate.
Good. At this time, for example, using a microcomputer etc.
Flow rate according to pre-designed rate of change curve
It is also possible to control and obtain a desired content curve. Form layer region (N) by sputtering method
In this case, the distribution concentration of nitrogen atoms in the layer thickness direction C(N)
by changing the thickness direction of the nitrogen atoms in the layer thickness direction.
to form the desired depth profile.
is, firstly, similar to the case using the glow discharge method.
The starting material for the introduction of nitrogen atoms is used in a gaseous state.
and the gas flow rate when introducing the gas into the deposition chamber.
This can be done by changing it appropriately as desired.
Ru. Second, it can be used as a target for sputtering.
For example, silicon atoms and Si₃N_Fourmixed with
If you use a target, silicon atoms
and Si₃N_FourAdjust the mixing ratio in the direction of the target layer thickness.
This can be achieved by changing it in advance.
Ru. In the first layer ( ) 102,
substances such as group atoms or group atoms
In order to introduce structurally, group elements must be introduced during layer formation.
Starting material for introduction of atoms or starting material for introduction of group atoms
The emitting material is placed in a gaseous state in the deposition chamber in the second layer region.
With other starting materials to form (S)106
It would be good to introduce it. For introducing group atoms like this
Possible starting materials include:
readily under gaseous or at least layer-forming conditions
It is desirable to use something that can be gasified. So
As a starting material for the introduction of group atoms such as
B is used for introducing boron atoms.₂H₆, B_FourH_Ten,
B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄Hydrogen such as
Boron oxide, BF₃, BCl₃,BBr₃Boron halides such as
etc. In addition, AlCl₃, GeCl₃, Ge
(CH₃), InCl₃, TlCl₃, etc. can also be mentioned.
Ru. As a starting material for the introduction of group atoms,
It is effectively used for introducing phosphorus atoms.
So, PH₃,P₂H_Four, etc. Phosphorus hydride, PH_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, BiBr₃, etc.
Listed as effective starting materials for the introduction of group atoms
Rukoto can. In the present invention, the first layer ( ) 102 is composed of
The support 1 contains a substance that controls the conduction properties.
Layer of the layer region (PN) provided unevenly on the 01 side
The thickness is the layer area (PN) and the layer area (PN).
constitutes the first layer ( ) 102 formed on top.
as desired depending on the properties required for other layer regions.
The lower limit shall be determined as appropriate.
preferably 30 Å or more, more preferably 40 Å or less.
The optimum thickness is preferably 50 Å or more.
Also, the conductive properties contained in the layer region (PN)
The content of substances that dominate the
In the case of
preferably less than 10μ, preferably less than 8μ, most preferably
It is desirable that the thickness be 5μ or less. In the photoconductive member 100 shown in FIG.
is the second layer formed on the first layer ( ) 102
Layer ( ) 103 has a free surface and is mainly moisture resistant,
Continuous repeated use characteristics, electrical pressure 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 amorphous material constituting the second layer ( ) 103
each have a common constituent element, silicon atoms.
, so both layers ()102 and ()1
Ensuring chemical stability at the laminated interface of 03
It is fully accomplished. The second layer ( ) 103 in the present invention is made of silicon.
a carbon atom, a carbon atom, and a hydrogen atom or
is/and amorphous material containing halogen atoms (hereinafter referred to as
After that, “a-(SixC₁-x)y(H,X)₁-y” However,
0<x, y<1). a-(SixC₁-x)y(H,X)₁-y
The formation of the second layer 103 ( ) is performed by glow discharge.
method, sputtering method, ion plantation
method, ion plating method, electron beam method
This can be done by the ``mu'' method, etc. These manufacturing methods are
construction conditions, level of capital investment, manufacturing scale,
depending on factors such as the desired properties of the photoconductive member to be produced.
Therefore, it is selected and adopted as appropriate, but depending on the desired characteristics.
Manufacturing conditions for manufacturing photoconductive materials with
It is relatively easy to control, and carbon can be used together with silicon atoms.
Second layer to create elementary atoms and halogen atoms
() 103, etc.
Glow discharge method or sputtering method with points
is preferably adopted. Furthermore, in the present invention, glow discharge method and spa
The second method can be used in combination with the tuttering method within the same equipment system.
A layer ( ) 103 may also be formed. The second layer ( ) 103 is formed by glow discharge method.
To form a-(SixC₁-x)y(H,X)₁−
y-forming raw material gas with diluting gas as necessary.
After mixing at a predetermined mixing ratio, the support 101 is installed.
It is introduced into a deposition chamber for vacuum deposition, which has been
by causing a glow discharge in the gas
Already on the support 101 by turning it into gas plasma
A-
(SixC₁-x)y(H,X)₁-y should be deposited.
stomach. In the present invention, a-(SixC₁-x)y(H,
X)₁-The raw material gas for forming y is silicon raw material.
atom, carbon atom, hydrogen atom, halogen atom
A gaseous substance consisting of at least one atom or
Most of the substances that can be gasified are gasified.
can be used. Silicon atom, carbon atom, hydrogen atom, halogen
Silicon atom is one of the constituent atoms.
For example, when using a raw material gas that
A raw material gas composed of atoms and a carbon atom composed of
Source gas to be made into constituent atoms and hydrogen atoms if necessary
Raw material gas or/and halogen source having constituent atoms
with the raw material gas whose constituent atoms are atoms at the desired mixing ratio.
Use in mixtures or use silicon atoms as constituent materials.
The raw material gas is composed of carbon atoms and hydrogen atoms.
Source gas and/or halogen atoms as constituent atoms
The raw material gas, which is the constituent atoms, is also
Mixed in a mixing ratio or composed of silicon atoms
Raw material gas to be made into atoms, silicon atoms, carbon atoms
and a raw material gas constituting three hydrogen atoms, or
3 silicon atoms, carbon atoms and halogen atoms
It is used by mixing with a raw material gas whose constituent atoms are
Rukoto can. Also, separately, it consists of silicon atoms and hydrogen atoms.
Carbon atoms are used as constituent atoms in the raw material gas.
You can use a mixture of raw material gases, or silicon
Raw material gas whose constituent atoms are atoms and halogen atoms
A raw material gas containing carbon atoms is mixed with
May be used. In the present invention, the second layer ( ) 103 contains
Preferred halogen atoms include fluorine,
Chlorine, bromine, and iodine, especially fluorine and chlorine.
It is desirable. In the present invention, the second layer ( ) 103 is formed
It can also be a raw material gas that can be effectively used to
Examples include those that are in a gas state at room temperature and pressure.
can list substances that can be easily gasified.
Ru. In the present invention, for forming the second layer ( ) 103
Silicon is effectively used as a raw material gas for
SiH whose constituent atoms are carbon atoms and hydrogen atoms_Four,
Si₂H₆,Si₃H₈,Si_FourH_TenSilanes, etc.
silicon hydride gas, composed of carbon atoms and hydrogen atoms
Atom, e.g. saturated hydrocarbon having 1 to 4 carbon atoms
Ethylene hydrocarbon with 2 to 4 carbon atoms, carbon number
2 to 3 acetylenic hydrocarbons, simple halogen,
Hydrogen halide, interhalogen compounds, halogenation
Silicon, halogen-substituted silicon hydride, silicon hydride, etc.
I can list many. 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,C.H.₃F, 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. The substances forming these second layers ( ) 103 are:
In the second layer ( ) 103 to be formed, a predetermined set of
Silicon atoms, carbon atoms and halogen atoms in composition ratio
and a hydrogen atom as necessary.
When forming the second layer ( ) 103, select as desired.
selected and used. 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_Four, or
Iha SiH₃In a gas state with Cl etc. at a predetermined mixing ratio,
Introduced into the device for forming the second layer () 103
By causing a glow discharge, a-
(SixC₁-x)y(Cl+H)₁- the second layer consisting of y
( ) 103 can be formed. Second layer ()10 by sputtering method
3, monocrystalline or polycrystalline silicon
Wafer or graphite wafer or silicon
Contains a mixture of carbon atoms and carbon atoms.
The target is the wafer that is needed.
Consists of halogen atoms or/and hydrogen atoms depending on
Sputtering in various gas atmospheres including as elements
This can be done by searching. For example, Siri
If you use Conwafer as a target,
Introducing carbon atoms and hydrogen atoms or/and halogen atoms
If necessary, dilute the raw material gas for
Dilute it and introduce it into the deposition chamber for sputtering.
the silicon by forming a gas plasma of gases such as
Just sputter the wafer. Also, another
has separate targets for silicon and carbon atoms.
or as a mixture of silicon and carbon atoms.
By using a single target
hydrogen atoms or/and halogen atoms as necessary.
sputtering in a gas atmosphere containing particles.
Bye. Carbon, hydrogen and halogen atoms
The materials mentioned above are used as the raw material gas for the introduction of
The second layer ( ) 103 type shown in the example of glow discharge
It is also effective when using the sputtering method.
Can be used as a substance. In the present invention, the second layer ( ) 103 is
-When forming by discharge method or sputtering method
The diluent gas used is so-called rare gas, for example.
For example, He, Ne, Ar, etc. are listed as suitable ones.
I can do it. The second layer ( ) 103 in the present invention is
Care must be taken to ensure that the required properties are provided as desired.
deeply formed. That is, silicon atoms, carbon atoms
hydrogen atom or/and halogen atom as necessary
Substances whose constituent atoms are children depend on the conditions for their creation.
The structure ranges from crystal to amorphous.
In terms of electrical properties, it ranges from conductive to semiconducting to absolute.
properties ranging from photoconductive to non-photoconductive.
This book shows each property up to the conductive property.
In inventions, it is important to have the desired characteristics according to the purpose.
Rua-(SixC₁-x)y(H,X)₁-y is formed
Therefore, the selection of the production conditions is strictly according to the desired
be accomplished. For example, if the second layer ( ) 103 is
To provide the main purpose of improving air pressure resistance,
a-(SixC₁-x)y(H,X)₁-y depends on the usage environment
It is an amorphous material with remarkable electrically insulating behavior.
Created by In addition, improvements in continuous repeated use characteristics and usage environment characteristics
A second layer () 103 is provided with the main purpose of
If the above degree of electrical insulation is
The degree of light is relaxed, and it has a certain degree of resistance to the irradiated light.
As an amorphous material with sensitivity, a-(SixC₁-x)
y(H,X)₁-y is created. On the surface of the first layer () 102, a-(SixC₁
-x)y(H,X)₁- the second layer consisting of y ()
Support during layer formation when forming 103
A temperature of 101 determines the structure and properties of the layer formed.
In the present invention, it is an important factor that influences
is a-(SixC₁-x)
y(H,X)₁- so that y can be created as desired
It is desirable that the support temperature be tightly controlled during layer formation.
Delicious. In the present invention, the desired purpose can be effectively achieved.
The method of forming the second layer ( ) 103 to be achieved
At the same time, the optimal range is selected as appropriate, and the second layer
( ) 103 is executed, but at the time of layer creation
The support temperature is preferably 20 to 400°C, more preferably
Suitably 50 to 350℃, optimally 100 to 300℃
is desirable. To form the second layer () 103, the layers constituting the
Delicate control of the composition ratio of atoms and control of layer thickness are
Because it is relatively easy compared to other methods,
- It is advantageous to use the discharge method or sputtering method.
However, with these layer forming methods, the second layer () 103
When forming a
A- where the discharge power during layer formation is created
(SixC₁−x)yX₁-Important factors that influence the characteristics of y
One of the children. Having the characteristics for achieving the object of the present invention
Suru a-(SixC₁−x)yX₁-y is highly productive and effective
This is a favorable discharge power condition for
preferably 10-300W, more preferably 20-250W, optimal
It is desirable that the power be 50 to 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.
Delicious. In the present invention, the second layer ( ) 103 is created.
Desired values for support temperature and discharge power for
The range includes the values in the range mentioned above, but this
These layer creation factors are determined independently and separately.
The desired characteristic a-(SixC₁−
x)y(H,X)₁- the second layer consisting of y ()1
03 is formed based on mutual organic relationships.
The optimal value of each layer creation factor can be determined by
is desirable. Second layer () 1 in the photoconductive member of the present invention
The amount of carbon atoms contained in 03 is the same as that of the second layer.
() 103, the purpose of the present invention is
A second layer ()1 that achieves the desired properties
This is an important factor for the formation of 03. Main departure
Charcoal contained in the second layer () 103 in light
The amount of elementary atoms constitutes the second layer ( ) 103
As appropriate depending on the type of amorphous material and its characteristics
It can be decided according to the That is, the general formula a-(SixC₁-x)y(H,
X)₁The amorphous material indicated by -y can be roughly divided into:
Amorphous material composed of silicon atoms and carbon atoms
fee (hereinafter referred to as “a-SiaC₁-a”. However, 0
<a<1), silicon atom, carbon atom, and hydrogen atom
An amorphous material composed of (hereinafter referred to as “a-(SibC₁
-b) cH₁-c”. However, 0<b, c<
1), and silicon atoms, carbon atoms, and halogens
Amorphous consisting of atoms and optionally hydrogen atoms
quality material (hereinafter referred to as “a-(SidC₁-d) e(H,X)₁−
It is written as "e". However, it is classified as 0<d, e<1).
Ru. In the present invention, the second layer ( ) 103 is a-
SiaC₁-a, the second layer ()1
The amount of carbon atoms contained in 03 is preferably 1
×10^-3~90 atom%, more preferably 1-80 atom%,
The optimal content is preferably 10 to 75 atomic%.
It is. That is, the previous a-SiaC₁- In the representation of a of a
If carried out, a is preferably 0.1 to 0.99999, more preferably
0.2 to 0.99, optimally 0.25 to 0.9. In the present invention, the second layer ( ) 103 is a-
(SibC₁-b) cH₁-c, the second
The amount of carbon atoms contained in the layer ( ) 103 is preferably
Preferably 1×10^-3~90 atomic%, more preferable
The temperature is preferably 1 to 90 atomic%, and the optimal value is 10 to 80 atomic%.
It is desirable that the content of hydrogen atoms is
is preferably 1 to 40 at%, more preferably 2
~35 atom%, optimally 5-30 atom%
Desirably, if the hydrogen content is within these ranges
Photoconductive members formed in
It can be fully applied as a standard. That is, the previous a-(SibC₁-b)H₁-c display
If carried out, b is preferably 0.1 to 0.99999, more preferably
is 0.1 to 0.99, optimally 0.15 to 0.9, preferably c
is between 0.6 and 0.99, more preferably between 0.65 and 0.98, optimally
A value of 0.7 to 0.95 is desirable. The second layer ( ) 103 is a-(SidC₁-d)
e(H,X)₁-e, the second
Content of carbon atoms contained in layer ( ) 103
is preferably 1×10^-3~90 atomic%, more
Preferably 1 to 90 atom%, optimally 10 to 80 atom%.
It is desirable that the
The amount is preferably 1 to 20 atom%, more preferably
1 to 18 at%, optimally 2 to 15 at%.
It is desirable that halogen atoms be included in these ranges.
Photoconductive members made when there is a
It can be applied sufficiently to the surface, and furthermore, the necessary
The content of hydrogen atoms according to
Preferably 19 atom% or less, more preferably 13 atom%
The following is desirable. That is, the previous a-(SidC₁-d) e(H,X)₁-e
If it is expressed as d and 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. The layer thickness of the second layer ( ) 103 in the present invention
The numerical range is set to effectively achieve the objectives of the present invention.
This is one of the important factors, and is one of the important factors to effectively achieve the purpose of the present invention.
according to the desired purpose, so as to achieve the desired goals.
You can decide. In addition, the layer thickness of the second layer ( ) 103 is
The amount of carbon atoms contained in ()103 and the first
Also in relation to the phase thickness of the layer ( ) 102,
organic materials according to the characteristics required for each layer area.
It is necessary to decide as appropriate according to the desire based on the relevance.
Yes, but it is also possible to add productivity and mass production.
It is also desirable to take into consideration the gender aspect. The layer thickness of the second layer ( ) 103 in the present invention
is preferably 0.33 to 30μ, more preferably
The desired value is 0.004 to 20μ, optimally 0.005 to 10μ.
It's a beautiful thing. As the support 101 used in the present invention
may be electrically conductive or electrically insulating. conductive
Examples of the support include NiCr, stainless steel,
Al, Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd
Metals such as these or alloys thereof can be mentioned. As the electrically insulating support, polyester, polyester, etc.
polyethylene, polycarbonate, cellulose, aluminum
acetate, polypropylene, polyvinyl chloride, polycarbonate
Polyvinylidene chloride, polystyrene, polyamide, etc.
synthetic resin film or sheet, glass, ceramic
Mixture, paper, etc. are usually used. These electricity
The insulating support preferably has at least one of the
The surface is conductive treated, and the conductive treated surface side
Preferably, other layers are provided. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Pd, In₂O₂, 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 101 may be cylindrical or belt.
It can be obtained in any shape such as a shape or a plate shape, and as desired,
Although its shape is determined, for example, the light guide shown in FIG.
Using the electric member 100 as an image forming member for electrophotography
In the case of continuous high-speed copying, an endless
It is preferable to have a root-like or cylindrical shape. Support 1
The thickness of 01 is such 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
In terms of handling, mechanical strength, etc., the support 101
The thickness is preferably 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 16 shows an example of a photoconductive member manufacturing apparatus.
vinegar. In the figure, the gas cylinders indicated by 1102 to 1106
is a raw material gas for forming the photoconductive member of the present invention.
For example, 1
102 is SiH diluted with He_FourGas (purity
99.999%, below SiH_Four/He is abbreviated. ) cylinder, 11
03 is GeH diluted with He_FourGas (purity 99.999
%, hereinafter GeH_Four/He is abbreviated. ) cylinder, 1104
is NH₃Gas (99.99% purity) cylinder, 1105
He gas (99.999% purity) cylinder, 1106 is H₂
It is a gas cylinder (99.999% purity). To allow these gases to flow into the reaction chamber 1101
is the valve 112 of the gas cylinders 1102 to 1106
2-1126, leak valve 1135 is closed
Also, check that the inflow valves 1112~
1116, outflow valve 1117-1121, auxiliary
Check that valves 1132 and 1133 are open.
First, open the main valve 1134 and turn off the
The reception room 1101 and each gas pipe are evacuated. Next
The reading of vacuum gauge 1136 is about 5×10^-6Torr
At the point when the auxiliary valves 1132 and 1133 leak
Close valves 1171-1121. Next, a cylindrical base 1137 as a support
An example of forming a photoreceptive layer on top is as follows:
SiH gas cylinder 1102_Four/He gas, gas bottle
GeH from Nbe1103_Four/He gas, gas cylinder
NH from 1104₃gas, valve 1122,
Open 1123 and 1124 and check the outlet pressure gauge 112
The pressure of 7,1128,1129 is 1Kg/cm²adjusted to
and inlet valves 1112, 1113, 1114.
By gradually opening the mass flow control
Inflows into La 1107, 1108, and 1110 respectively.
let Subsequently, the outflow valves 1117, 111
8,1119, gradually open the auxiliary valve 1132
the respective gases are caused to flow into the reaction chamber 1101.
SiH at this time_Four/He gas flow rate and GeH_Four/He gas
Flow rate and NH₃The ratio to the gas flow rate becomes the desired value.
Outflow valve 1117, 1118, 1119
Also, the pressure inside the reaction chamber 1101 is adjusted to the desired value.
While checking the reading of vacuum gauge 1136 to ensure the correct value.
Adjust the opening of main valve 1134. and
The temperature of the base 1137 is controlled by the heating heater 1138.
The temperature must be set within the range of 50 to 400℃.
After checking, set the power supply 1140 to the desired power.
to generate a glow discharge in the reaction chamber 1101,
At the same time, according to the pre-designed rate of change curve
GeH_Four/He gas and manual or external drive motor
The valves 1118 to 1120 are
Perform operations to change the opening of the NH as appropriate.₃gas
By adjusting the flow rate of the
Distribution concentration of germanium and nitrogen atoms
Control C(N). Maintain the glow discharge for the desired time as described above.
to form a first layer region on the substrate 1137 to a desired layer thickness.
(G) 105 forms. First layer area to desired layer thickness
At the stage when area (G) 105 was formed, the outflow
When valve 1116 is fully closed, and if necessary
Similar conditions and procedures were used, except for changing the discharge conditions.
By maintaining the glow discharge for the desired time according to the
Germanium atoms are formed on the first layer region (G) 105.
Second layer region (S) 106 that is substantially free of
can be formed. First layer region (G) 105 and second layer region
(S) In 106, substance (D) that controls conductivity
In order to contain
For example, when forming the second layer region (S) 106
BaB₂H₆,PH₃etc. is introduced into the deposition chamber 1101.
Just add it to the gas you are putting in. Thus, on the substrate 1137 the first layer ( ) 1
02 is formed. First layer formed to desired layer thickness as described above
Forming a second layer ( ) 103 on ( ) 102
In order to form the first layer 102(),
For example, SIH_Fourgas, C₂H_Four
Dilute each gas with diluent gas such as He as necessary.
It is then supplied into the reaction chamber 1101 and adjusted to the desired conditions.
Therefore, it is sufficient to generate glow discharge. Contains halogen atoms in second layer () 103
For example, SiF_Fourgas and C₂H_Fourgas, or
SiH on this₂Add gas and repeat as above.
A second layer ( ) 103 may be formed. 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 1101 and the outflow valve 1
Gases leading from 117 to 1121 into the reaction chamber 1101
To avoid any residue remaining in the piping,
Close the valves 1117 to 1121, and close the auxiliary valve 11.
32, open 1133 and main valve 1134.
It is necessary to fully open the system and evacuate the system to high vacuum.
Do it accordingly. Carbon atoms contained in the second layer ( ) 103
For example, when using glow discharge, the amount of SiH_FourGa
and C₂H_FourThe gas introduced into the reaction chamber 1101
The ratio of flow rates applied can be varied as desired, or
When forming layers by sputtering, the target
When forming silicon wafer and graphite wafer
Change the spatter area ratio or silicon
By changing the mixing ratio of powder and graphite powder,
Control as desired by molding the gate
You can. Contained in the second layer ( ) 103
The amount of halogen atoms introduced is determined by the amount of halogen atoms introduced.
raw material gas for, e.g. SiF_FourThe gas is in the reaction chamber 1101
This is achieved by adjusting the flow rate when introduced into the
be done. Also, while forming layers, make sure that the layer formation is uniform.
For measurement, the base 1137 is rotated by a motor 1139.
It is desirable to rotate at a constant speed. Examples will be described below. Example 1 The manufacturing equipment shown in Fig. 16 is used as a support.
The strips shown in Table 1 were applied to the cylindrical Al substrate.
Sample as an image forming member for electrophotography (Sample No.
11-1 to 17-6) were prepared respectively (Table 2). Germanium atom content distribution concentration in each sample
The degree is shown in Figure 17, and the concentration distribution of nitrogen atoms is shown in Figure 17.
It is shown in FIG. Each sample obtained in this way was exposed to a charged exposure experimental device.
and corona charging for 0.3 seconds (sec) at 5.0KV.
and immediately irradiated with a light image. The light image is tungsten
Transmission type using a light source with a light intensity of 2 lux・sec
It was irradiated through a test chart. Immediately thereafter, use a charged developer (toner and
sample (imaging member) table
By cascading the planes, the sample (image
A good toner image was obtained on the surface of the forming member. trial
The toner image on the paper is transferred using 5.0KV corona charging.
When transferred onto photographic paper, no solution was found in any sample.
Clear, high-density images with excellent image power and good gradation reproducibility
The image was obtained. In the above, a tungsten lamp is used as the light source.
810nm GaAs semiconductor laser (10mW) instead
The same procedure was carried out except that the electrostatic image was formed using
Under the toner image forming conditions, apply toner for each sample.
- When we evaluated the image quality of the transferred images, we found that none of the
Even for samples, it has excellent resolution and good gradation reproducibility.
Clear, high-quality images were obtained. Example 2 The manufacturing equipment shown in Fig. 16 is used to produce a cylinder shape.
An electrophotographic image was formed on an Al substrate under the conditions shown in Table 3.
Samples as forming members (Sample Nos. 21-1 to 27-6)
were created for each (Table 4). Germanium atom content distribution concentration in each sample
The degree is shown in Figure 17, and the content distribution concentration of nitrogen atoms
is shown in FIG. For each of these samples,
When I conducted an image evaluation test by Mr.
The materials also gave high quality toner transfer images. Mama, each
Tested the sample 200,000 times in an environment of 38℃ and 80%RH.
After repeated use tests, we found that none of the
No deterioration in image quality was observed in the sample. Example 3 The manufacturing equipment shown in Fig. 16 is used to produce a cylinder shape.
An electrophotographic image was formed on an Al substrate under the conditions shown in Table 5.
Samples as forming members (Sample Nos. 31-1 to 37-6)
(Table 6). Germanium atom content distribution in each sample
The concentration is shown in Figure 17, and the nitrogen atom content distribution concentration is shown in Figure 17.
The degree is shown in FIG. For each of these samples,
When I conducted an image evaluation test by Mr.
The materials also gave high quality toner transfer images. Also, each
Tested the sample 200,000 times in an environment of 38℃ and 80%RH.
After repeated use tests, we found that none of the
No deterioration in image quality was observed in the sample. Example 4 By the manufacturing equipment shown in Fig. 16, the 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 47-
6) were prepared respectively (Table 8). Germanium atom content distribution in each sample
The concentration is shown in Figure 17, and the nitrogen atom content distribution concentration is shown in Figure 17.
The degree is shown in FIG. For each of these samples,
When I conducted an image evaluation test by Mr.
The materials also gave high quality toner transfer images. Also, each
The sample was subjected to 200,000 repetitions at 38℃ and 80% environment.
After repeated use tests, none of the samples
No deterioration in image quality was observed. Example 5 The conditions for creating layer () 103 are shown in Table 9.
Samples No. 11-1 and 12- of Example 1 except for
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
24 samples (13-1-8) were created. The structure of each electrophotographic image forming member thus obtained
Install each separately on a copying machine and record it in each example.
Corresponds to each example under the same conditions as listed.
For each of the electrophotographic imaging members,
Through comprehensive image quality evaluation of transferred images and repeated continuous use.
The durability was evaluated. Comprehensive image quality evaluation of transferred images of each sample and repetition
Table 10 shows the results of durability evaluation after continuous use.
vinegar. Example 6 When forming the layer ( ) 103, the silicon wafer and
By changing the target area ratio of graphite and
of silicon atoms and carbon atoms in ()103
Sample No. 11 of Example 1 except for changing the content ratio
- that of the imaging member by exactly the same method as in 1.
I created each. The image forming member thus obtained
For each, imaging as described in Example 1;
The development and cleaning process was repeated approximately 50,000 times.
After that, when we performed image evaluation, the results were as shown in Table 11.
I got it. Example 7 When forming layer ( ) 103, SiH_Fourgas and C₂H_FourGa
By changing the flow rate ratio of the
The reason is to change the content ratio of silicon atoms and carbon atoms.
Other than that, the method was exactly the same as that for sample No. 12-1 in Example 1.
Each of the imaging members was prepared by. 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 process, image evaluation was performed and Table 12
I got results like this. Example 8 When forming layer ( ) 103, SiH_Fourgas,
SiF_Fourgas, C₂H_FourBy changing the gas flow rate ratio, the layer ()
Content of silicon atoms and carbon atoms in 103
Sample No. 13-1 of Example 1 except for changing the ratio.
each of the imaging members in exactly the same manner as
It was created. Regarding each image forming member thus obtained,
Imaging, development, and cleaning as described in Example 1
After repeating the process approximately 50,000 times, image evaluation was performed.
As a result, we obtained the results shown in Table 13. Example 9 Example except for changing the layer thickness of layer ( ) 103
The image was formed using exactly the same method as Sample No. 11-1 in 1.
Each of the component parts was created. As mentioned in Example 1
Repeat the process of image creation, development, and cleaning.
The results shown in Table 14 were obtained.

[Table] The flow rate ratio was changed by adjusting the ratio.

【table】

[Table] The flow rate ratio was changed by adjusting the ratio.

【table】

【table】

[Table] The flow rate ratio was changed by adjusting.

【table】

【table】

[Table] The flow rate ratio was changed by adjusting.

【table】

【table】

【table】

【table】

【table】

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

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

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

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

[Brief explanation of drawings]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of the light guide member of the present invention, and FIGS. 2 to 10 are
FIG. 11 is an explanatory diagram for explaining the distribution state of germanium atoms in the first layer ( ), FIG. 11 is a configuration diagram of a layer region containing nitrogen atoms, and FIGS. 12 to 15 are respectively, FIG. 16 is an explanatory diagram for explaining the distribution state of nitrogen atoms in the first layer ().
Schematic explanatory diagram of the device used in the present invention, No. 17
18 are distribution state diagrams showing the content distribution concentration state of each atom in the example of the present invention. 100...Photoconductive member, 101...Support, 1
02...First layer (), 103...Second layer (), 104...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, provided on the support and having a content of 1 to 10×10 ⁵ atoms relative to the sum of silicon atoms.
a first layer region (G) with a layer thickness of 30 Å to 50 μ made of an amorphous material containing ppm of germanium atoms; a photoconductive first layer with a layer thickness of 1 to 100 μm with a second layer region (S) of a layer thickness of 0.5 to 90 μm composed of an amorphous material (not containing atoms); provided on the layer,
A photoreceptive layer made of an amorphous material containing silicon atoms and 1×10 ^-3 to 90 atom % of carbon atoms and having a thickness of 0.003 to 30 μm, for electrophotography. A photoconductive member, wherein the first layer contains nitrogen atoms, and
A first region (1) with a layer thickness of 0.003 to 100μ, where the distribution concentration of nitrogen atoms in the layer thickness direction is C(1), C(3), and C(2), respectively, and a third region with a layer thickness of 0.003 to 80μ. A region (3) and a second region (2) with a layer thickness of 0.003 to 100μ are formed in this order from the support side, and the C(3) has a thickness of 10 to the sum of silicon atoms, germanium atoms, and nitrogen atoms. atomic ppm
~67 atomic%, and C(3)>C(2),C(1),
A photoconductive member for electrophotography, wherein at least one of C(1) and C(2) is not 0. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. 3. For electrophotography according to claims 1 and 2, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. Photoconductive member. 4. 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. 5. 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. 6. The photoconductive member for electrophotography according to claim 1, wherein the first layer contains a substance that controls conductivity. 7. The photoconductive member for electrophotography according to claim 6, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 8. The photoconductive member for electrophotography according to claim 6, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table.