JPH0211897B2 - - 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 it must have a desired dark resistance value.
It must be non-polluting to the human body and solid-state photography.
In imaging devices, afterimages can be easily removed within a predetermined time.
Characteristics such as being able to manage
In particular, electronic photocopying machines used in offices as business machines
In the case of an electrophotographic imaging member incorporated into a real device.
In some cases, non-polluting during the above use is important.
It is a point. Based on these points, light guide has recently been attracting attention.
Amorphous silicon (hereinafter referred to as a-Si) is used in electrical components.
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
If you start to experience slow development, or if you repeatedly develop at a high speed.
Inconveniences such as a gradual decrease in responsiveness when used
There were many cases where problems occurred. Furthermore, compared to the short wavelength side of the visible light region, a-Si
Therefore, the absorption in the wavelength region longer than the wavelength region on the long wavelength side is
It has a relatively small absorption coefficient and is currently in practical use.
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 structure
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 and corresponding to the sum of silicon atoms.
1~10×10^FiveAtomic ppm germanium atoms
A layer with a thickness of 30 Å to 50 μ made of amorphous material containing
provided on the first layer region (G) and the first layer region (G).
The base material is silicon atoms (germanium atoms).
Layer thickness 0.5 composed of amorphous material (not including children)
Layer thickness 1~ with second layer area (S) of ~90μ
a first layer exhibiting a photoconductivity of 100 μ;
Provided on the first layer, silicon atoms and nitrogen atoms
Composed of amorphous material containing nitrogen atom content
is 1×10^-3~60 atomic%, layer thickness 0.003~30μ
A photoreceptive layer consisting of a second layer of
A photoconductive member for child photography, The first layer contains carbon atoms and
Carbon in the layer thickness direction in order from the support side
The distribution concentrations of atoms are C(1), C(3), and C(2), respectively.
First region 1 with a layer thickness of 0.003 to 100μ, layer thickness 0.003
The third region 3 with a layer thickness of ~80μ, the second with a layer thickness of 0.003-100μ
It has region 2 and the above C(1), C(3), C(2)
are C(3)>C(1), C(3)>C(2), and C(1) and C(2)
At least one is not 0, or C(1), C(2)
are characterized by being different. It was designed to have the layer structure described above.
The photoconductive member of the present invention solves 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. Further, the photoconductive member of the present invention is formed on a support.
The photoreceptive layer itself is strong and the support
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 (G) constructed and provided on the support;
105, a silicon atom, and optionally hydrogen
Contains at least one of an atom and a halogen atom
Amorphous material (hereinafter referred to as "a-Si(H,X)")
configured and provided on the first layer region (G) 105.
In addition, a second layer region (S) 106 exhibiting photoconductivity;
has. Germanium atoms are in the first layer region (G) 105
First layer area (G) 1 so that it is evenly distributed in
It may be contained in 05, or the layer thickness
It is contained evenly in the direction, but the distribution concentration is uneven.
It may be uniform. However, in any case
In the first layer region (G) 105, the surface of the support is
Regarding the in-plane direction parallel to the plane, germanium atoms
The point is that it is uniformly distributed and evenly contained.
This is necessary from the point of view of uniformizing the characteristics in the inward direction.
be. In particular, in the layer thickness direction of the first layer ( ) 102,
is uniformly contained, and is contained evenly 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 (G)
Germanium atoms are contained in 105. In the photoconductive member of the present invention, as described above,
Germanium contained in the first layer region (G) 105
The distribution state of atoms in the layer is as described above in the layer thickness direction.
The distribution state is as follows, parallel to the surface of the support 101
It is desirable to have a uniform distribution state in the in-plane direction.
Delicious. In the present invention, on the first layer region (G) 105,
In the second layer region (S) 106 provided, a gap is formed.
This layer does not contain rumanium atoms.
By forming a first layer ( ) 102 on the structure
Comparisons are made from relatively short and long wavelengths, including the visible light region.
Photosensitivity to light of all wavelengths up to long wavelengths
An excellent photoconductive member can be obtained. Moreover, in one of the preferred embodiments, the first
of germanium atoms in the layer region (G) 105 of
The distribution state is such that germanium atoms are connected in the entire layer region.
Continuously and evenly distributed, the layer thickness of germanium atoms
The distribution density C in the direction is the second layer from the support 101 side.
A decreasing change is given toward region (S) 106.
Since the first layer region (G) 105 and the second layer
Excellent affinity with region (S) 106,
In addition, as will be described later, there is a gap at the side end of the support 101.
Extremely increase the distribution concentration C of rumanium atoms
When using a semiconductor laser, etc.
The second layer region (S) 106 absorbs most of the
Uncut long wavelength light to the first layer region (G) 105
can be virtually completely absorbed and supported.
To prevent interference due to reflection from the holder 101 surface.
I can do that. 2 to 10, the first layer region (G) 105
The amount of germanium atoms contained in the layer thickness direction
A typical example where the cloth condition is non-uniform is shown. 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_Bis support
Position of the surface of the first layer region (G) 105 on the body 101 side
,t_Tis the first layer region (G)1 on the side opposite to the support side
The position of the surface of 05 is shown. That is, germanium raw
The first layer region (G) 105 containing children is t_Bfrom the side
t_TLayering takes place towards the sides. In FIG. 2, the content contained in the first layer region (G) 105 is
The distribution state of germanium atoms in the layer thickness direction is
One typical type is shown. In the example shown in Figure 2, the germanium atom
Table in which the first layer region (G) 105 is formed
Interface position t where the plane and the surface of the support body 101 are in contact_Bmosquito
et₁Up to the position, the distribution concentration of germanium atoms is
C is C₁The first layer takes a constant value ()
contained in the position t₁to interface position t_TMinutes up to
The cloth density is C₂has been gradually and continuously decreased.
Ru. Interface position t_TIn this case, the fraction of germanium atoms is
Cloth density C is C₃It is said that In the example shown in FIG. 3, the first layer region
(G) Distribution concentration of germanium atoms contained in 105
degree C is position t_BMore position_TConcentration C up to_Fourfrom
Gradually and continuously decreasing position t_Tconcentration C at_Fiveand
The distribution state is formed as follows. In the case of FIG. 4, it is included in the first layer region (G) 105.
The distribution concentration C of germanium atoms possessed is at position t_B
More position₂It is assumed that the concentration C is a constant value up to the point t.₂
and position t_Tgradually and continuously decreased between
, position t_T, the distribution concentration C is essentially zero.
(Here, “substantially zero” means that the amount is below the detection limit.)
). In the case of FIG. 5, the first layer region (G) 105 contains
The distribution concentration C of germanium atoms possessed is at position t_B
More position_Tup to the concentration C₈more continuously and gradually
and position t_Tis virtually zero in
There is. In the example shown in FIG. 6, the first layer region (G) 1
Distribution concentration C of germanium atoms contained in 05
is the position t_Band position t₃Between, the concentration C₉constant
value and position t_TThe concentration C_Tenbe done. rank
Placement₃and position t_TThe distribution concentration C is a linear function between
position t₃More position_Thas been reduced to
Ru. In the example shown in FIG. 7, the first layer region
(G) Distribution concentration of germanium atoms contained in 105
Degree C is position t_BMore position_Fouruntil the concentration C₁₁a constant value of
take, position t_FourMore position_Tuntil the concentration C₁₂more concentrated
C₁₃It is assumed that the distribution state decreases linearly until
There is. In the example shown in FIG. 8, the first layer region (G) 1
Distribution concentration C of germanium atoms contained in 05
is position t_BMore position_Tup to the concentration C₁₄more real
decreases linearly, reaching zero. In FIG. 9, the first layer region (G) 105 includes
The distribution concentration C of germanium atoms possessed by the position
t_BMore position_Fiveuntil the concentration C₁₅More concentration C₁₆Ma
, and the position t_Fiveand position t_Tbetween
, the concentration C₁₆An example is shown in which the value is set to a constant value.
It is. In the example shown in Figure 10, the first layer region
Distribution of germanium atoms contained in region (G) 105
Concentration C is at position t_Bconcentration C at₁₇and position t₆to
Until this concentration C₁₇It decreases slowly at first.
less, t₆It decreases rapidly near the position of
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
In this case, the concentration C₂₀Figure so that it becomes more substantially zero.
It is reduced according to a curve with a shape as shown in FIG. As described above, from Figures 2 to 10, the first layer area
A layer of germanium atoms contained in region (G) 105
As we have explained some typical examples of the distribution state in the thickness direction.
In addition, in the present invention, on the support body 101 side,
Then, the part where the distribution concentration C of germanium atoms is high is
has an interface t_TOn the side, the distribution concentration C is supported
It has a part that is considerably lower than the body 101 side.
The distribution state of germanium atoms is the first layer region (G)
105 is one suitable example.
It is mentioned as. First layer constituting the photoconductive member in the present invention
Region (G) 105 is preferably a support as described above.
101 side or, on the contrary, the free surface 107
Relatively high concentration of germanium atoms on the sides
It is desirable to have a localized area A that is 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 up to 5μ thick from the interface position t.
layer area L_TIn some cases, it is considered as all of
Layer 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) 105 to be formed
It is determined as appropriate according to the characteristics required. Localized region A is the germanium contained therein.
Germanium atoms are distributed in the layer thickness direction.
Maximum value C of the distribution concentration of atoms_naxis with silicon atoms
preferably 1000 atomic ppm or more,
Preferably 5000 atomic ppm or more, optimally 1×10^Fouroriginal
So that the distribution state can be such that it is considered to be more than the child ppm.
Preferably, it is layered. That is, in the present invention, germanium atoms
The first layer region (G) 105 contained in the support 10
The layer thickness from the first side is within 5μ (t_B(from 5μ thick layer area)
The maximum value of the distribution concentration C_naxis formed so that there is
It is preferable to In the present invention, in the first layer region (G) 105,
The content of germanium atoms in
Follow the wishes so that the purpose of the invention is effectively achieved
However, for the sum with silicon atoms,
, preferably 1 to 10×10^Fivepreferable to atomic ppm
100～9.5×10^FiveAtomic ppm, optimally 500-8
×10^FivePreferably in atomic ppm. Germanium in the first layer region (G) 105
The distribution state of atoms is germanium atoms in the entire layer area.
is continuously distributed in the layer thickness direction of germanium atoms.
The distribution concentration C is from the support 101 side to the photoreceptive layer 10
4 towards the free surface 107 side, the change decreases.
given or the opposite change is given
, the rate of change curve of the distribution concentration C is desired.
by arbitrarily designing according to
The first layer region (G) 105 having the characteristics of
can be realized. For example, the gel in the first layer region (G) 105
The distribution concentration C of manium atoms is set on the support 101 side.
the free surface 1 of the photoreceptive layer 104.
On the 07 side, the distribution concentration C should be kept as low as possible.
is applied to the distribution concentration curve of germanium atoms.
By using
Compatible with light of all wavelengths from long wavelengths to relatively long wavelengths.
In addition to achieving high photosensitivity,
Effectively prevents interference with coherent light such as laser light
It can be measured. In the present invention, the layer thickness of the first layer region (G) 105 and
The layer thickness of the second layer region (S) 106 is defined as
One of the important factors for effectively achieving the purpose
Therefore, the photoconductive member formed has the desired characteristics.
When designing the photoconductive member, ensure that the charge is sufficiently
due care needs to be taken. In the present invention, the layer thickness of the first layer region (G) 105
T is preferably 30 Å to 50 μ, more preferably 40
Desired to be Å~40μ, optimally 50Å~30μ.
Yes. 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 layer
The sum of layer thicknesses T (T_B+T) is both
The properties required for the layer region and the properties required for the entire photoreceptive layer.
Based on the organic relationship between the properties of light and
Decide as appropriate when designing the layer of the conductive member according to your wishes.
be done. 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, the first layer region (G) 105 contains
The content of germanium atoms is 1×10 atoms
If it is more than ppm, the layer in the first layer region (G) 105
Thick T_BIt is desirable that the
or less than 30μ, more preferably less than 25μ, optimal
It is desirable that the thickness be 20μ or less. 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 ( ) 102 contains carbon atoms.
A layer region C is provided. The first layer ( ) 102 is as shown in FIG.
, the distribution concentration C (C) of carbon atoms in the layer thickness direction is
The first region (1) 108 having the value C(1), C(2) etc.
The second region (2) has a value of 109, and the value of C(3) is
and a third region (3) 110. In the present invention, the above-mentioned first, second, and third
Each area has these three in any area.
It does not necessarily need to contain carbon 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 carbon 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, carbon 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 the first region (1) 108 does not contain carbon 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 carbon atoms.
Design the first layer ( ) 102 as a region with no
There is a need. In the present invention, the largest of the three
The third region (3) 110 having a distribution concentration C(3) of
The first layer ()10 while maintaining good photosensitivity characteristics
When measuring the improvement of the dark resistance of 2, the distribution concentration C(3)
Set the value to a relatively low value.
The layer thickness is sufficient within the necessary range.
It is desirable to have a thickness. 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 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 carbon 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 content distribution concentration of carbon atoms C(3)
The maximum value of silicon atoms and germanium
The sum of atoms and carbon atoms (hereinafter referred to as "T (SiGeC)")
preferably 67 atom%, more preferably
is preferably 50 atom%, optimally 40 atom%.
Yes. Also, the minimum value of the distribution concentration C(3) is T(SiGeC).
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(SiGeC) 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 carbon 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 carbon 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 carbon atoms is
Degree C (C) 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 carbon atoms is
Degree C (C) is 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 carbon atoms C(C)
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 carbon atoms is
Degree C (C) is at position t_Bfrom position t₁₆Until C₂₉position
t₁₆from position t₁₇Until C₃₀position t₁₇from
position t₁₈Until C₃₁and increase stepwise, position t₁₈mosquito
ra position t_BUntil C₃₀has been reduced to. In the present invention, the first layer ( ) 102 is provided with
Layer region C containing carbon atoms (as described above)
at least two of the first, second and third regions
(consisting of regions) improves light sensitivity and dark resistance.
If the main purpose is the first layer () 10
It is set up so as to occupy the entire area of the second
() of the charge from 107 from the free surface of 102
To prevent injection, a
The density between the support 101 and the light-receiving layer 104 is increased.
When the main purpose is to improve adhesion
occupies the support side end layer region of the photoreceptive layer 104
It is set up so that In the first case, the carbon contained in layer region C
The atomic content is relatively low to maintain high photosensitivity.
and in the second case the first layer () 102
To prevent charge injection from the free surface 107 of
The content of carbon atoms is relatively high, and the third
In some cases, the adhesion with the support 101 is ensured.
In order to achieve this, the content of carbon atoms is relatively high.
is desirable. 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.
Carbon atoms are present in the surface layer region on the free surface 107 side of
The distribution of carbon atoms in layer region C
It should be formed inside. In order to prevent charge injection from the free surface 107,
In order to increase the distribution concentration of carbon atoms on the free surface 107 side,
It is desirable to form a layer region C with a large amount of C (C).
Yes. In the present invention, the first layer ( ) 102 is provided with
Carbon in layer region C containing carbon atoms
The content of atoms depends on the characteristics required for the layer region C itself.
or the layer region C directly contacts the support 101
If the support body 101 is provided as a
Organic relationships such as the relationship with the properties of the tactile surface
You can select as appropriate. Also, other layer regions are in direct contact with the layer region C.
If provided, the characteristics of the other layer regions and other
The relationship with the properties of the contact interface with the layer region is also considered.
The carbon atom content is selected accordingly. The amount of carbon atoms contained in layer region C is
depending on the characteristics required for the photoconductive member used.
silicon atoms and gel.
The sum of manium atoms and carbon atoms (hereinafter referred to as “T”)
(SiGeC)) is 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 C is the first layer ()1
Occupies the entire area of 02 or the first layer ()
Even if it does not occupy the entire area of 102, the layer thickness of layer region C
T₀The percentage of the layer thickness T of the first layer ( ) 102 of
If the carbon content is large enough, the carbon contained in the layer region N
The upper limit of the content of elementary atoms is sufficiently lower than the above value.
It is desirable that the In the present invention, the layer thickness T of layer region C₀is the first
The ratio of the layer ( ) 102 to the layer thickness T is
In the case where it is more than two-fifths, in the layer area C
The upper limit of the amount of nitrogen atoms contained is T
(SiGeC), preferably 30 atomic % or less,
More preferably 20 atom% or less, optimally 10 atoms
% or less. In the present invention, a layer region containing carbon atoms
C is on the support 101 side or/and the third side as described above.
There are relatively many carbon atoms near the second layer () 103 side.
Those with localized region B containing high concentration
It is desirable that the
The density between the support 101 and the first layer ( ) 102
To further improve adhesion and improve acceptance potential.
It can be raised. The localized region B is the support of the first layer ( ) 102.
Surfaces on the holder 101 side and the second layer ( ) 103 side
It is desirable that it be provided within 5μ from the surface. In the present invention, the localized region B is the first
of the layer () 102 from the support 101 or from the second
Layer area up to 5μ thick from the surface of layer () 103 side
Area L_TIn some cases, it is referred to as all of
L_TSometimes it is considered a part of. localized region B to layer region L_Tpart or all of
It depends on the requirements of the photoreceptive layer 104 to be formed.
It is determined as appropriate according to the characteristics to be used. Localized region B is the carbon atom contained therein.
Distribution concentration C of carbon atoms as the distribution state in the layer thickness direction
Maximum value C of (C)_naxbut preferably less than 500 atomic ppm
above, more preferably above 800 atomic ppm, optimally
The distribution state can be such that it is more than 1000 atomic ppm.
It is desirable that the layers be formed in such a manner that the That is, in the present invention, the first layer () 10
The layer region C containing carbon atoms in 2 is a support layer.
Is it the body 101 side or the surface of the second layer () 103?
The maximum value C of the distribution concentration within 5μ at the layer thickness of_naxexist
It is desirable that it be formed so as to 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
First layer region (G) 105 containing atoms or/and
and a second layer region containing no germanium atoms.
(S) 106 contains a substance D that controls the conduction characteristics.
By containing the layer region (G) or/and
The conduction properties of the layer region (S) can be controlled arbitrarily as desired.
You can control it. In the present invention, the conduction characteristics
The layer region PN containing the substance D that controls the sex is
Even if it is provided in part or all of the first layer ( ) 102
good. Or layer area PN is layer area (G) or
It may be provided in part or all of (S). The substance D that controls such conduction characteristics is
List the so-called impurities in the semiconductor field.
In the present invention, silicon atoms or
Gives p-type conductivity to germanium atoms
p-type impurity that provides n-type conduction characteristics and n-type impurity that provides n-type conduction characteristics.
I can name things. Specifically, p-type impurity
As a substance, atoms belonging to group of the periodic table (group
atoms), such as boron (B), aluminum (Al),
Gallium (Ga), Indium (In), Thallium
(Tl), etc., and those that are particularly preferably used are:
B, Ga. In addition, as an n-type impurity,
Atoms belonging to group of the periodic table (group atoms), examples
Examples: phosphorus (P), arsenic (As), antimony (Sb), vinyl
smas (Bi), etc., and are particularly preferably used.
are P and As. In the present invention, the first layer ( ) 102 contains
The content of substance D that governs the conductive properties is
conductive properties required for the first layer ( ) 102;
Alternatively, the first layer ( ) 102 is placed in direct contact with the
Characteristics at the contact interface with the supported support 101
Select as appropriate based on the organic relationship, such as the relationship with
Rukoto can. In addition, the substance D that controls the conduction characteristics is the first substance D.
For inclusion in layer () 102, the first layer
Contained locally in the desired layer region in ( ) 102
In particular, when supporting the first layer ( ) 102
When contained in the body side end layer region, the layer region
the properties of other layer regions provided in direct contact with the
Relationship with characteristics at the contact interface with other layer regions
The content of substance D that controls the conduction properties is also taken into consideration.
The amount is selected accordingly. In the present invention, the first layer ( ) 102 contains
The content of substance D that controls the conductive properties of
preferably 0.01 to 5×10^FourAtomic ppm, yo
Preferably 0.5 to 1×10^FourAtomic ppm, optimally 1~
5×10³Preferably in atomic ppm. In the present invention, the substance D that controls the conduction properties
Content of the substance D in the contained layer region PN
but preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more
Above atomic ppm, optimally above 100 atomic ppm.
In this case, the substance D controlling the conduction properties is the first
Locally contained in some layer regions of the layer ( ) 102
It is desirable that the first layer ( ) 102
It is desirable to have it unevenly distributed in the end layer region E on the side of the support.
stomach. Among the above, the support side end of the first layer ( ) 102
So that the content in the sublayer area E is higher than the above value.
Containing a substance D that controls the conduction characteristics
For example, if the substance D is the p-type impurity mentioned above,
In the case of , the free surface 107 of the photoreceptive layer 104 is
If the support 101 side is charged to + polarity,
The transfer of electrons injected into the photoreceptive layer 104 from
It can be effectively prevented, and the conduction properties can be effectively prevented.
When the dominant substance is the above n-type impurity, light
The free surface 107 of the receptive layer 104 is charged with − polarity.
When subjected to treatment, the photoreceptive layer 1 is removed from the support 101 side.
Effectively prevents the movement of holes injected into 04
Rukoto can. In this way, one side is placed in the support side end layer region E.
A field containing substance D that controls polar conduction characteristics
In this case, the remaining layer area of the first layer () 102,
That is, the portion excluding the support side end layer region (E)
In the layer region (Z) there are
It may contain a substance of the same polarity, or it may contain a substance of the same polarity.
The substance that controls the conduction properties is added to the end layer region on the side of the support.
(E) in a much smaller amount than the actual amount contained in
It may also be included. In such a case, the material contained in the layer region (Z)
As the content of substance D that governs the conduction characteristics,
is the substance contained in the support side end layer region E.
be determined as desired depending on the polarity and content of
However, preferably 0.001 to 1000
small ppm, more preferably 0.05-500 atomic ppm, optimal
It is desirable that the content be 0.1 to 200 atomic ppm. In the present invention, the support side end layer region E and the layer
Region (Z) contains a substance that controls the same kind of conductivity
In the case where the layer area (Z) of the material is
The content is preferably 30 atomic ppm or less
It is desirable to do so. In addition to the above cases,
In the present invention, in the first layer ( ) 102, one
Contains a substance that controls conductivity and has a polarity of
one polar layer region and the other polar conductivity.
in direct contact with the layer containing the substance.
to provide a so-called depletion layer in the contact layer region.
You can also do it. Clogging, e.g. first layer ( ) 102
Therein, the layer region containing the p-type impurity and the layer region containing the p-type impurity.
in direct contact with the layer region containing n-type impurities.
A depletion layer is formed by forming a so-called p-n junction.
Can be set up. In the present invention, composed of a-Ge (Si, H, X)
For example, the first layer region (G) 105 to be
Discharge method, sputtering method, or ion spray
For vacuum deposition methods that utilize discharge phenomena such as the Teing method.
It is formed as a result. For example, using the glow discharge method
A first layer composed of a-Ge (Si, H, X)
To form the region (G) 105, basically germanium
For supplying germanium atoms that can supply nium atoms
Supplying raw material gas and silicon atoms as needed
Possible raw material gas for supplying silicon atoms, hydrogen atoms
Raw material gas for introduction and/or for introduction of halogen atoms
The raw material gas is placed in a deposition chamber where the internal pressure can be reduced.
Glow is introduced into the deposition chamber at the desired gas pressure.
to cause an electrical discharge, and to
a-Ge(Si,H,X) on a given support surface.
What is necessary is to form a layer consisting of. Also, germanium
First layer region (G) 105 with atoms in a non-uniform distribution state
Distribution concentration of germanium atoms to be included in
while controlling a-Ge according to the desired rate of change curve.
A layer consisting of (Si, H, X) may be formed.
In addition, in the sputtering method, for example, Ar,
Based on inert gas such as He or other gases
composed of silicon atoms in a mixed gas atmosphere of
target, or the target and the germanium
Using two targets composed of Ni atoms
or of silicon atoms and germanium atoms
Use mixed targets to
germanium diluted with diluent gas such as He or Ar.
Raw material gas for supplying hydrogen atoms, and hydrogen if necessary
Spray gas for introducing atoms and/or halogen atoms.
Introduce the desired gas into the deposition chamber for tuttering.
The first layer region is formed by forming a lasma atmosphere.
Region (G) 105 is formed. This sputtering method
to make the distribution of germanium atoms uneven.
In case, the raw material gas for supplying germanium atoms is
control the gas flow rate of the gas according to the desired rate of change curve.
However, sputtering the target mentioned above
That's fine. 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.
This evaporation source is housed in the evaporation port as a resistor.
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, Ti₃H₈,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,SiH₆, 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
Forming a first layer region (G) 105 made of a-SiGe
I can do it. According to the glow discharge method,
When manufacturing the first layer region (G) 105, basically
is, for example, a raw material gas for supplying silicon atoms.
Raw materials for supplying silicon halide and germanium atoms
Germanium hydride as a gas, Ar, H, He, etc.
of gas, etc. to a predetermined mixing ratio and gas flow rate.
A deposition chamber in which a first layer region (G) 105 is formed.
of these gases by causing a glow discharge.
By forming a plasma atmosphere, the desired
A first layer region (G) 105 is formed on the support 101.
However, it is possible to control the introduction ratio of hydrogen atoms.
In order to make it even easier, we added further information to these gases.
Also hydrogen gas or silicon compound gas containing hydrogen atoms.
A layer may be formed by mixing desired amounts. 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) 105 formed in any case
In order to introduce a halogen atom into the
silicon compound or the above-mentioned halogen atom-containing silicon compound
A plasma of the gas is generated by introducing a gas into the deposition chamber.
It is good to create an atmosphere. In addition, hydrogen atoms are introduced into the first layer region (G) 105.
In this case, the raw material gas for hydrogen atom introduction, e.g.
Ba, H₂, or the above-mentioned silanes or/and water
For sputtering gases such as chemically oxidized germanium.
into the deposition chamber to create a plasma atmosphere of the gases.
All you have to do is form it. 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
There are also substances that are in a gaseous state or can be gasified, such as
As a starting material for forming the effective first layer region (G) 105.
I can list the following. Among these substances, halides containing hydrogen atoms
When forming the first layer region (G) 105, a halogen is added in the layer.
Electrical or photoelectric properties upon introduction of gen atoms
Hydrogen atoms, which are extremely effective in controlling
Therefore, in the present invention, a suitable source for introducing halogen is
used as a fee. Hydrogen atoms are structurally added to 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
The amount of hydrogen atoms contained in the layer region (G) 105,
or amount of halogen atoms, or hydrogen atoms and halogen
The sum of the amounts of atoms (H+X) is preferably 0.01 to
40 at%, more preferably 0.05-30 at%, optimally
is preferably 0.1 to 25 at%. Hydrogen atoms contained in the first layer region (G) 105
or/and to control the amount of halogen atoms, e.g.
For example, support temperature or/and hydrogen atoms or halo
of the starting materials used to contain the gen atoms.
Controls the amount introduced into the deposition system, the discharge force, etc.
Just do it. In the present invention, it is composed of a-Si(H,X).
The second layer region (S) 106 is
Inside the starting material () for forming layer region (G) 105
The output gas becomes the raw material gas for supplying germanium atoms.
Starting material excluding emitting material [Second layer region (S) 1
Using the starting materials for forming 06 ()], the first
The same method as in the case of forming the layer region (G) 105 of
It can be formed according to the conditions. 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, carbon is added to the first layer ( ) 102.
To provide the layer region (C) containing atoms, the first
In forming the layer 102, a starting material for introducing carbon atoms is used.
Starting material for forming the first layer ( ) 102 as described above
used with a substance to deposit its amount into the layer formed.
It is sufficient to contain it in a controlled manner. Glow discharge method is used to form layer region C
In this case, for forming the first layer ( ) 102 described above.
selected as desired from among the starting materials of
A starting material for the introduction of carbon atoms is added to. the
As a starting material for introducing carbon atoms such as
A gaseous substance whose constituent atoms are at least carbon atoms.
or the large size 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 carbon atoms, and the necessary
Construct hydrogen atoms or halogen atoms depending on
Mix with the raw material gas to form atoms at the desired mixing ratio.
or use silicon atoms as constituent atoms.
The raw material gas is composed of carbon atoms and hydrogen atoms.
The raw material gas containing atoms is also mixed in the desired manner.
or by mixing silicon atoms as constituents.
The raw material gas and silicon atoms, carbon atoms and
and hydrogen atoms as raw material gases.
can be used in combination. Also, separately, silicon atoms and hydrogen atoms are
Carbon atoms are added to the raw material gas as constituent atoms.
A mixture of raw material gases may be used. It is effective as a raw material gas for introducing carbon atoms.
, the constituent atoms are carbon atoms and hydrogen atoms.
For example, saturated hydrocarbons having 1 to 5 carbon atoms, carbon atoms
Ethylene hydrocarbons having 2 to 5 carbon atoms, carbon atoms having 2 to 4 carbon atoms
Examples include cetylenic hydrocarbons. 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), penten
(C_FiveH_Ten), and acetylene hydrocarbons include acetylene hydrocarbons.
Chyrene (C₂H₂), methylacetylene (C₃H_Four), b
Chin (C_FourH₆) etc. In addition to these, silicon atoms, carbon atoms, and hydrogen atoms
As a raw material gas whose constituent atoms are Si and
(CH₃)_Four, Si(C₂H_Five)_FourList the alkyl silicides such as
be able to. In the present invention, carbon atoms are present in the layer region C.
In order to further enhance the effect obtained, carbon atoms are
In addition, further oxygen atoms or/and nitrogen atoms
It can contain. Oxygen atoms for introducing oxygen atoms into the layer region (C)
For example, oxygen (O₂),
Ozone (O₃), nitric oxide (NO), nitrogen dioxide
(NO₂), nitrogen monoxide (N₂O), nitrogen sesquioxide
(N₂O₃), trinitrogen tetraoxide (N₂O_Four), nitrogen pentoxide
(N₂O_Five), nitrogen trioxide (NO₃), silicon atoms and acids
For example, the constituent atoms are elementary atoms and hydrogen atoms.
Disiloxane (H₃SiOSiH₃), trisiloxane
(H₃SiOSiH₂OSiH₃) and other lower siloxanes.
can be given. Nitrogen atom conductor used in forming layer region (C)
Effectively used as a necessary raw material gas
The starting material to be used is an atom containing nitrogen atoms.
Or an example where the constituent atoms are nitrogen atoms and hydrogen atoms.
For example, nitrogen (N₂), ammonia (NH₃), hydrazi
(H₂NNH₂), hydrogen azide (HN₃), Azika Asia
Ammonium (NH_FourN₃) etc. gaseous or gaseous
Nitrogenization of nitrogen, nitrides, azides, etc.
Compounds can be mentioned. In addition, nitrogen atoms
In addition to the introduction of halogen atoms, it is also possible to introduce halogen atoms.
From this point of view, nitrogen trifluoride (F₃N), nitrogen tetrafluoride
(F_FourN₂) and other halogenated nitrogen compounds.
Can be done. By sputtering method, carbon atoms containing
To form the first layer ( ) 102, a single crystal
or polycrystalline silicon wafer or graphite
wafer, or silicon atoms and carbon atoms
Target mixed wafers
As a result, these are spattered in various gas atmospheres.
This can be done by ringing. For example, if you target silicon wafers,
carbon atoms and optionally hydrogen atoms.
or/and a source for introducing halogen atoms.
Dilute the feed gas with diluent gas as necessary to
These gases are introduced into a deposition chamber for puttering.
Forming a gas plasma to remove the silicon wafer
All you have to do is sputter. Also, separately, silicon atoms and carbon atoms are
as separate targets or with silicon atoms.
Use a single target with mixed carbon atoms
Possibly dilution as a sputtering gas
in a gaseous atmosphere or at least hydrogen atoms or
is/and contains a halogen atom as a constituent atom.
by sputtering in a gas atmosphere.
It will be done. As a raw material gas for introducing carbon atoms
is the raw material gas shown in the glow discharge example mentioned above.
The raw material gas for introducing carbon atoms inside is sputtering.
It can also be used as an effective gas in the case of In the present invention, formation of the first layer ( ) 102
At this time, a layer region (C) containing carbon atoms is provided.
In this case, the distribution concentration of carbon atoms contained in the layer region (C)
By changing the degree C (C) in the layer thickness direction, the desired layer thickness can be obtained.
Layer region with directional distribution state (depthprofile)
(C) In the case of a glow discharge, the distribution
For introducing carbon atoms to change the concentration C (C)
Change the starting material gas and its gas flow rate to the desired rate of change.
Introduce the material into the deposition chamber while changing it accordingly according to the curve.
This is accomplished by entering the For normal use, e.g. manually or with an externally driven motor
The gas flow system is
Open the specified needle valve in the middle.
It is sufficient to perform an operation to gradually change the value. At this time, the flow
The rate of change in quantity need not be linear, e.g.
A rate of change curve designed in advance using a controller etc.
You can also get lines. Form layer region (C) by sputtering method
In this case, the distribution concentration C (C) of carbon atoms in the layer thickness direction is
By changing the thickness direction of the carbon atoms,
To form a depth profile, first
As with the glow discharge method, the carbon source is
The starting material for child introduction is used in a gaseous state, and the gas
Adjust the gas flow rate when introducing the material into the deposition chamber as desired.
This is done by changing the parameters as appropriate. Second, the target for sputtering,
For example, a mixture of silicon atoms and carbon atoms
If a target is used, silicon atoms and
Adjust the mixing ratio with carbon atoms in the direction of the target layer thickness.
This can be achieved by changing the
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.
Introduced with starting materials to form (S)106
Just do it. Such an output for introducing group atoms
Possible sources include gas at room temperature and pressure.
or at least easily gaseous under layer-forming conditions.
It is desirable to adopt something that can be converted into a Like that
Specifically, as a starting material for introducing group atoms,
B for introducing boron atoms₂H₆, B_FourH_Ten, B_FiveH₉,
B_FiveH₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄Boron hydride, such as
BF₃, BCl₃,BBr₃Boron halides such as
It will be done. In addition, AlCl₃, GeCl_Four,Ge(CH₃)_Four,
InCl₃, TlCl₃, etc. can also be mentioned. 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 material contains a substance that controls the conduction properties.
The layer region (PN) unevenly distributed on the 101 side
The layer thickness is the layer area (PN) and the layer area.
The first layer ( ) 102 formed on (PN)
Depending on the characteristics required for the other layer areas that make up the
It will be determined as appropriate according to your wishes, but
The lower limit is preferably 30 Å or more, more preferably
is preferably 40 Å or more, optimally 50 Å or more.
Yes. Also, contained in the layer region (PN)
The content of substances that control conduction properties is 30 atomic ppm or more.
If it is above, the upper limit of the layer area (PN) and
is preferably 10 μ or less, preferably 8 μ or less,
Optimally, 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 107 and is mainly resistant to
Humidity, continuous repeated use characteristics, electrical pressure resistance, usage
Achieves the objectives of the present invention in terms of environmental characteristics and durability.
It is established for the purpose of In addition, in the present invention, 1 of the first layer ()
02 and the second layer ( ) 103
Each material has a common component: silicon atoms
Since it has both phases ()102 and
Chemical stability at the laminated interface of ()103
have been sufficiently ensured. The second layer ( ) 103 in the present invention is made of silicon.
Con atoms, nitrogen atoms, and hydrogen atoms if necessary.
or/and an amorphous material containing a halogen atom.
(Hereafter, “a-(Si_xN_1-x)_y(H,X)_1-y”.
However, 0<x, y<1). a-(Si_xN_1-x)_y(H,X)_1-yThe second consists of
The layer ( ) 103 is formed by glow discharge method, spa
By tuttering method, electron beam method, etc.
will be accomplished. These manufacturing methods depend on manufacturing conditions and equipment.
The load level of this injection, the manufacturing scale, and the photoconductor produced
Appropriate selection depending on factors such as desired properties of the component
A light guide with the desired characteristics is
It is relatively easy to control the manufacturing conditions for manufacturing electrical parts.
It is easy to use, and together with silicon atoms, nitrogen atoms and
and halogen atoms, the second layer () 1
It has the advantage of being easy to introduce during 2003.
Glow discharge method or sputtering method is preferred.
Appropriately 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-(Si_xN_1-x)_y(H,X)_1-yformation
Add dilution gas and predetermined amount of raw material gas as necessary.
A support 101 is installed after mixing at a mixing ratio.
The gas introduced into the vacuum deposition chamber is
gas plasma by creating a low discharge
The material already formed on the support 101 is
a-(Si_xN_1-x)_y
(H,X)_1-yAll you have to do is deposit it. In the present invention, a-(Si_xN_1-x)_y(H,X)_1-y
The raw material gas for formation is silicon atoms, nitrogen
At least among atoms, hydrogen atoms, and halogen atoms
gaseous substance or gasification consisting of one atom
Most of the substances that can be gasified are
can be used. Silicon atom, nitrogen atom, hydrogen atom, halogen
As one of the atoms, silicon atom is a constituent atom.
For example, when using a raw material gas that
A raw material gas consisting of atoms and nitrogen atoms as constituent atoms.
Source gas to be made into constituent atoms and hydrogen atoms if necessary
Raw material gas or/and halogen whose constituent atoms are
The desired mixture with the raw material gas whose constituent atoms are
or use silicon atoms mixed in
Raw material gas as constituent atoms, nitrogen atoms and hydrogen
Raw material gas or/and nitrogen whose constituent atoms are
Raw materials whose constituent atoms are elementary atoms and halogen atoms
and gas, also at the desired mixing ratio.
or raw materials whose constituent atoms are silicon atoms.
Gases and silicon, nitrogen, and hydrogen atoms
Raw material gas or silico whose three constituent atoms are
It consists of three atoms: nitrogen atom, nitrogen atom, and halogen atom.
Mixing with raw material gas to form atom atoms.
Can be done. Also, separately, silicon atoms and hydrogen atoms are
Nitrogen atoms are added to the raw material gas as constituent atoms.
It is also possible to use a mixture of raw material gases.
A raw material gas whose constituent atoms are carbon atoms and halogen atoms.
A raw material gas containing nitrogen atoms is mixed into the gas.
You may also use it. Contained in the second layer ( ) 103 in the present invention
Suitable halogen atoms are fluorine and salt.
fluorine, bromine, and iodine, especially fluorine and chlorine.
It's a beautiful thing. In the present invention, the second layer ( ) 103 is formed
It can also be a raw material gas that can be effectively used to
It is a gas state at normal temperature and pressure.
or substances that can be easily gasified.
Ru. Comprising the second layer ( ) 103 and the above amorphous material.
Layer forming methods include glow discharge method,
Sputtering method, ion implantation
method, ion plating method, electrobeam
Laws etc. These manufacturing methods are
factors, level of capital investment, manufacturing scale,
Depends on factors such as the desired characteristics of the photoconductive material used.
It is selected and adopted as appropriate based on the desired characteristics.
Control of manufacturing conditions for manufacturing photoconductive members with
is relatively easy and can be combined with silicon atoms.
Elementary atoms, hydrogen atoms and halogen atoms as necessary
What is introduced into the second layer ( ) 103 to be produced is
There is a glow discharge method that has advantages such as being easy to perform.
Alternatively, a sputtering method is preferably employed. 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. a-SiN(H,X) by glow discharge method
To form the second layer ( ) 103 composed of
is basically a silicon that can supply silicon atoms.
Raw material gas for supplying nitrogen atoms and raw material for introducing nitrogen atoms
gas and/or for the introduction of hydrogen atoms if necessary.
And the raw material gas for introducing halogen atoms is
into a deposition chamber that can be reduced in pressure, and
It causes a glow discharge and is placed in a predetermined position beforehand.
a-SiN on a predetermined first layer ( ) 102
Forming a second layer ( ) 103 consisting of (H,X)
Just let it happen. In addition, the second layer () 10
3, it can be done as follows, for example:
Ru. Firstly, inert gases such as Ar, He, etc.
is a mixed gas atmosphere based on these gases.
A target composed of silicon atoms is spun inside.
Raw material gas for introducing nitrogen atoms during tuttering
for hydrogen atom introduction or/and as necessary.
and sputtering together with raw material gas for introducing halogen atoms.
It is best to introduce it into the vacuum deposition chamber where the ring is performed.
stomach. Second, it can be used as a target for sputtering.
Te Si₃N_FourA target consisting of
Target composed of silicon atoms and Si₃N_FourIt's okay
Two pieces of the target made or the silicon raw material
Child and Si₃N_FourYou can use a target made up of
Nitrogen source into the second layer ( ) 103 formed by
Children can be introduced. At this time, the nitrogen
If used together with raw material gas for atom introduction, the
in the second layer () 103 by controlling the flow rate.
The amount of nitrogen atoms introduced can be controlled arbitrarily.
It's easy. Nitrogen atoms introduced into the second layer ( ) 103
The content of the raw material gas for introducing nitrogen atoms is
control the flow rate when introduced into the nitrogen
Nitrogen source contained in the target for elementary atom introduction
Adjust the proportion of children when creating the target.
or by doing both,
It can be arbitrarily controlled as desired. For supplying silicon atoms used in the present invention
SiH is the starting material that becomes the raw material gas for_Four,
Si₂H₆,Si₃H₈,Si_FourH_Tenin a gaseous state such as
Silicon hydride (silanes) that can be converted into carbon is used.
In particular, it is easy to handle the layer creation work.
In terms of silicon atom supply efficiency, SiH_Four,
Si₂H₆are listed as preferred. These etc.
Starting materials allow for appropriate selection of layer formation conditions.
The second layer ()1 formed by selecting
Hydrogen atoms can also be introduced into 03 along with silicon atoms.
Ru. An effective source of raw material gas for supplying silicon atoms.
In addition to the silicon hydride mentioned above, halogen
Silicon compounds containing gen atoms, so-called halogen atoms
silane derivatives substituted with, specifically e.g.
SiF_Four,Si₂F₆, SiCl_Four, SiBr_FourSilicon halides such as
can be mentioned as preferred. Furthermore, SiH₂F₂,SiH₂I₂,SiH₂Cl₂, SiHCl₂,
SiH₂Br₂,SiHBr₂halogen-substituted silicon hydrides, such as
hydrogen sources in a gaseous state or capable of being gasified, such as
Halides that have halogens as one of their constituents are also effective.
Silicon atoms for forming the second layer ( ) 103
It can be mentioned as a starting material for supply. Using silicon compounds containing these halogen atoms
In this case, as mentioned above, the layer formation conditions should be
The second layer ( ) 10 formed by
Introducing halogen atoms along with silicon atoms into 3.
can do. Halogens containing hydrogen atoms among the above starting materials
The silicon oxide compound is used to form the second layer () 103.
At the same time as introducing halogen atoms into the layer,
Hydrogen is extremely effective in controlling optical and photoelectric properties.
Since atoms are also introduced, this is a preferable method in the present invention.
Used as a starting material for the introduction of halogen atoms
Ru. In the present invention, forming the second layer ( ) 103
Raw material gas for introducing halogen atoms used in
Effective starting materials include those listed above.
In addition, for example, halogen of fluorine, chlorine, bromine, and iodine
Gengas, BrF, ClF, ClF₃,BrF_Five,BrF₃,
IF₃,IF₇, interhalogen compounds such as ICl, IBr, HF,
Hydrogen halides such as HCl, HBr, HI, etc.
I can do it. used when forming the second layer ( ) 103
It can be used as a raw material gas for introducing nitrogen atoms.
The starting materials effectively used in
atoms or composed of nitrogen atoms and hydrogen atoms.
For example, nitrogen (N₂),ammonia
(NH₃), hydrazine (H₂NNH₂), hydrogen azide
(HN₃), ammonium azide (NH_FourN₃) etc.
gaseous or gasifiable nitrogen, nitrides and
Nitrogen compounds such as dilides can be mentioned. child
In addition to the introduction of nitrogen atoms, halogen atoms
As a starting material, it is possible to introduce
is nitrogen trifluoride (F₃N), nitrogen tetrafluoride (F_FourN₂)etc
Examples include halogenated nitrogen compounds. In the present invention, the second layer ( ) 103 is
-When forming by discharge method or sputtering method
The diluent gases used include so-called rare gases, e.g.
For example, He, Ne, Ar, etc. are listed as suitable ones.
be able to. The second layer ( ) 103 in the present invention is
Care must be taken to ensure that the required properties are provided as desired.
Formed intentionally. That is, silicon atoms, nitrogen atoms,
constitute hydrogen atoms and/or halogen atoms.
Substances that are made into atoms have a structural structure depending on the conditions of their creation.
takes forms ranging from crystals to amorphous, and
In terms of gas and physical properties, it ranges from conductivity to semiconductivity, and furthermore,
It exhibits properties ranging from insulating to photoconductive.
Due to its quality, it exhibits non-photoconductive properties. Therefore, the present invention
In this case, a-
(Si_xN_1-x)_y(H,X)_1-yin place so that a
The creation conditions are strictly selected according to the wishes.
Ru. For example, the second layer ( ) 103 has an electrical voltage resistance.
If the main purpose is to improve the_x
N_1-x)_y(H,X)_1-yis electrically insulated in the operating environment.
Created as an amorphous material with pronounced sexual behavior. We also aim to improve the characteristics of continuous repeated use and the usage environment.
A second layer () 103 is established with the main purpose of
If the electrical insulation is
It is moderated to a certain extent and has a certain degree of resistance to the irradiated light.
a-(Si_xN_1-x)_y
(H,X)_1-yis created. On the surface of the first layer ( ) 102, a-(Si_x
N_1-x)_y(H,X)_1-yThe second layer consisting of ()10
Support temperature during layer formation when forming 3
is important with the structure and properties of the layers formed.
This is a significant factor. In the present invention, the desired characteristics
a-(Si_xN_1-x)_y(H,X)_1-yis desired
The temperature of the support at the time of layer formation is
It is desirable to have strict control. In the present invention
The second objective is to achieve the desired objective effectively.
Optimum range as appropriate according to the method of forming the layer ( ) 103
A support temperature of is selected to form the second layer ( ) 10
3 is carried out, but the support temperature at the time of layer formation is
is preferably 20-400℃, more preferably 50-350℃
℃, ideally 100 to 300℃.
It is. 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 low discharge method or sputtering method.
However, with these layer forming methods, the second layer () 103
When forming a
The discharge power during layer formation is the same as the a-(Si_x
N_1-x)_y(H,X)_1-yimportant factors that influence the characteristics of
one of. Characteristics for achieving the object of the present invention
a-(Si_xN_1-x)_y(H,X)_1-yis more productive
As a discharge power condition to be effectively created
is preferably 1.0~300W, more preferably 2.0~
250W, ideally 5.0~200W.
It's a good thing. 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 support temperature and discharge power for
Examples of numerical ranges include the values in the ranges mentioned above.
Ru. However, these layer creation filters are independent
of the desired characteristics, rather than those that can be determined separately.
a-(Si_xN_1-x)_y(H,X)_1-yThe second layer consists of
Reciprocal organic association so that ()103 is formed
It is desirable that the optimum value be determined based on the characteristics. Second layer () 1 in the photoconductive member of the present invention
The amount of nitrogen 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 in the formation of 03.
of the nitrogen atoms contained in the second layer ( ) 103 of
The amount of the amorphous material constituting the second layer ( ) 103 is
Depending on the type of material and its characteristics,
It can be determined by That is, the general formula a-(Si_xN_1-x)_y(H,
X)_1-yAmorphous materials shown in can be broadly classified into silicon
Amorphous material composed of silicon atoms and nitrogen atoms
(Hereinafter referred to as “a-Si_aN_1-a”. However, 0<a<
1, composed of silicon atoms, nitrogen atoms, and hydrogen atoms.
The amorphous material (hereinafter referred to as “a-(Si_bN_1-b)_c
H_1-c”. However, 0<b, c<1), silico
nitrogen atom, halogen atom and as necessary
An amorphous material composed of hydrogen atoms (hereinafter referred to as "a")
−(Si_bN_1-d)_e(H,X)_1-e”. However, 0<
d and e<1). In the present invention, the second layer ( ) 103 is a-
Si_aN_1-aThe second layer ()10
The amount of nitrogen atoms contained in 3 is preferably 1×
Ten^-3~60 at%, more preferably 1-50 at%, most preferably
It is desirable that the content be suitably 10 to 45 at%.
be. That is, the previous a-Si_aN_1-aDo it with the display
For example, a is preferably 0.4 to 0.99999, more preferably
0.5-0.99, optimally 0.55-0.9. In the present invention, the second layer ( ) 103 is a-
(Si_bN_1-b)_cH_1-cThe second layer consists of
The amount of nitrogen atoms contained in ()103 is preferably
Or 1×10^-3~55 atomic%, more preferably
is 1 to 55 atom%, optimally 10 to 55 atom%.
is desirable. Furthermore, the content of hydrogen atoms
The amount is preferably 1 to 40 at%, more preferably
Preferably 2 to 35 atom%, optimally 5 to 30 atom%.
It is desirable that hydrogen atoms be included in these ranges.
The photoconductive member formed when there is a
It can be fully applied as it is excellent in terms of aspects. That is, the previous a-(Si_bN_1-b)_cH_1-cb and
If done in c display, b is preferably 0.45 to 0.99999,
More preferably 0.45 to 0.99, optimally 0.45 to 0.9.
c is preferably 0.6 to 0.99, more preferably 0.65
~0.98, optimally 0.7-0.95. The second layer ( ) 103 is a-(Si_dN_1-d)_e(H,
X)_1-e, the second layer ()1
The content of nitrogen atoms contained in 03 is as follows:
Preferably 1×10^-3~60 atom%, more preferably
It is considered to be 1 to 60 atom%, optimally 10 to 55 atom%.
is desirable. Furthermore, the halogen atom
The content is preferably 1 to 20 at%, more
Preferably 1 to 18 at%, optimally 2 to 15 at%.
It is desirable that halogen sources be
The photoconductive member made when there is a child content is
It can be fully applied in practice. difference
Furthermore, the content of hydrogen atoms may be added as necessary.
The amount is preferably 19 atomic % or less, more preferably 19 atomic % or less.
It is desirable that the content be 13 atomic % or less.
be. That is, the previous a-(Si_dN_1-d)_e(H,X)_1-eof
If expressed as d and e, d is preferably 0.4~
0.99999, more preferably 0.4-0.99, optimally 0.45
~0.9, and e is preferably 0.8~0.99999, and more
Preferably 0.82 to 0.99, optimally 0.85 to 0.98
This is desirable. The layer thickness of the second layer ( ) 103 in the present invention
The scope is defined to effectively achieve the objectives of the present invention.
This is one of the important factors. This layer thickness is
according to the intended purpose so as to effectively achieve the purpose.
can be determined as appropriate and desired. Furthermore, this layer
The thickness is determined by the nitrogen atoms contained in the layer ( ) 103.
The relationship between the amount of
Depending on the characteristics required for each layer area,
Determined as appropriate based on organic relevance and as desired.
It is necessary to Additionally, this layer thickness can be
Consideration is also given to economic efficiency, including performance and mass production.
It is desirable that The layer thickness of the second layer ( ) 103 in the present invention
is preferably 0.003 to 30μ, more preferably
The desired value is 0.004 to 20μ, optimally 0.005 to 10μ.
Delicious. 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 long as it is within the range where it can be fully utilized, it is as thin as possible.
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. FIG. 16 shows an example of a photoconductive member manufacturing apparatus. 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,
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 C₂H_FourDilution gas (99.99% purity) cylinder, 110
5 is He gas (99.999% purity) cylinder, 1106
is H₂It 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^-6To Torr
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 from gas cylinder 1102_Four/He gas, gas
GeH from cylinder 1103_Four/He gas, gas cylinder
C from Be1104₂H_Fourgas, valve 1122;
1123 and 1124 are opened and the outlet pressure gauge 112
7, 1128, 1129 pressure 1Kg/cm²adjusted to
and inlet valves 1112, 1113, 1114.
By gradually opening the mass flow control
Inflow into La 1107, 1108, 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 C₂H_FourThe ratio to the gas flow rate will be the desired value.
Sea urchin outflow valves 1117, 1118, 1119
Adjust the pressure inside the reaction chamber 1101 to the desired value.
While checking the reading of vacuum gauge 1136,
Adjust the opening of the in-valve 1134. and base
The temperature of the body 1137 is increased by the heater 1138.
that the temperature is set in the range of 50-400℃
After checking, set the power supply 1140 to the desired power.
A glow discharge is generated in the reaction chamber 1101, and the same
according to a 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 C as appropriate.₂H_Fourgas
By adjusting the flow rate of the
Distribution concentration of germanium and carbon atoms
Control C(C). 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) Form 105. First layer area (G) to desired layer thickness
At the stage when 105 is formed, the outflow valve 1
When 116 is completely closed, and if necessary, the discharge
Similar conditions and procedures were followed except for changing conditions.
The first layer region is maintained by maintaining the glow discharge for the desired time.
Substantially containing germanium atoms on region (G) 105
Forming a second layer region (S) 106 that is not
I can do that. First layer region (G) 105 and second layer region
(S) 106 contains substance D that controls conductivity.
In order to have the first layer region (G) 105 and the second layer region (G) 105,
For example, when forming the layer region (S) 106 of₂H₆,
PH₃A gas for introducing into the deposition chamber 1101
It is good to do this in addition to. 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, NH₃
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 NH₃gas, or
SiH on this_FourAdd 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. Nitrogen atoms contained in the second layer ( ) 103
For example, when using glow discharge, the amount of SiH_FourGa
and NH₃The 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 a silicon wafer and a silicon nitride wafer
Change the spatter area ratio or silicon
By changing the mixing ratio of powder and silicon nitride 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 distribution concentration of carbon atoms is
It is shown in FIG. Each sample obtained in this way was exposed to a charged exposure experimental device.
and corona discharge 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 produces 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 carbon 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. 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 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 carbon 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 carbon 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 5 The conditions for creating layer () 103 are shown in Table 9.
Samples No. 11-1 and 12- of Example 1 except for
1. Electrophotography according to the same conditions and procedures as 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
The target area ratio of silicon nitride and silicon nitride wafers was changed.
Therefore, silicon atoms and nitrogen in layer ( ) 103
The test of Example 1 was performed except that the content ratio of atoms was changed.
Image forming member
I created each of them. The image formation thus obtained
For each member, as described in Example 1,
Image creation, development, and cleaning processes are repeated approximately 50,000 times.
After returning it, I performed an image evaluation and found that it was as shown in Table 11.
We obtained the following results. Example 7 When forming layer ( ) 103, SiH_Fourgas and NH₃Ga
By changing the flow rate ratio of the
The reason is to change the content ratio of silicon atoms and nitrogen 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, NH₃By changing the gas flow rate ratio, the layer ()
Content of silicon atoms and nitrogen 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, developing line, 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 as shown in [Table].

【table】

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

【table】

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

【table】

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

【table】

【table】

【table】

【table】

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

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

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

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

[Brief explanation of drawings]

FIG. 1 is a schematic layer 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 carbon atoms, and FIGS. 12 to 15 are, respectively, FIG. 16 is an explanatory diagram for explaining the distribution state of carbon 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, 102
...First layer (), 103...Second layer (), 10
4...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and an amorphous material provided on the support and containing germanium atoms in an amount of 1 to 10 x 10 ⁵ atomic ppm based on the sum of silicon atoms. A first layer region (G) with a layer thickness of 30 Å to 50 μ made of a material and an amorphous material provided on the first layer region (G) and having silicon atoms as a matrix (does not contain germanium atoms) Layer thickness 0.5 made up of material
Layer thickness 1~ with second layer area (S) of ~90μ
A first layer exhibiting photoconductivity of 100μ, and an amorphous material provided on the first layer containing silicon atoms and nitrogen atoms, with a nitrogen atom content of 1×10 ^-3 ~60 atomic%, layer thickness 0.003~30μ
a photoconductive layer for electrophotography, wherein the first layer contains carbon atoms and carbon atoms in the layer thickness direction from the support side. A first region 1 with a layer thickness of 0.003 to 100μ, where the distribution concentration of atoms is C(1), C(3), and C(2), respectively, and a layer thickness of 0.003
It has a third region 3 with a thickness of ~80μ and a second region 2 with a layer thickness of 0.003 to 100μ, and has the above-mentioned C(1), C(3), C(2).
is C(3)>C(1), C(3)>C(2), and at least one of C(1), C(2) is not 0, or C(1), C(2)
A photoconductive member for electrophotography, characterized in that: 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. 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 a halogen atom. 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. 5. Claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is uniform.
A photoconductive member for electrophotography as described in 1. 6. The photoconductive member for electrophotography according to claim 1, wherein the first layer region (G) 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.