JPH0211152B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on light (here, light in a broad sense, ultraviolet light).
rays, visible rays, infrared rays, X-rays, gamma rays, etc.)
Electrophotographic photoconductive parts sensitive to electromagnetic waves such as
material (hereinafter simply referred to as photoconductive member). 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.
In addition, solid-state photography must be non-polluting to the human body.
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-mentioned use
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 present invention has been made in view of the above points, and includes a
- Regarding Si, image forming members for electrophotography and solid-state imaging devices
As a photoconductive member used in equipment, reading devices, etc.
Comprehensive and thorough from the perspective of applicability and applicability
As a result of continued research, we found that silicon atoms and germanium
hydrogen atom or halogen atom.
Amorph containing at least one of the children
As materials, so-called hydrogenated amorphous ass silicon gel
Manium, halogenated amorphous silicon gel
Manium or halogen-containing hydrogenated amorphous
silicon germanium (hereinafter referred to as a generic term)
Use “a-SiGe(H,X)” as a notation]
A light-receiving layer exhibiting photoconductivity consisting of
The configuration of the conductive member is specified as explained below.
The photoconductive members designed and created below are of great practical importance.
It not only exhibits excellent characteristics, but also surpasses conventional light guides.
Even when compared with electrical parts, it surpasses them in every respect.
It is particularly useful as a photoconductive member for electrophotography.
Possesses extremely excellent characteristics and long wavelength side
It has excellent absorption spectrum characteristics in
The present invention is based on this discovery. The present invention always has electrical, optical, and photoconductive properties.
Stable and almost unrestricted by usage environment
Compatible with all environments and has excellent photosensitivity characteristics on the long wavelength side
In addition, it has excellent resistance to light fatigue, and can withstand repeated use.
No deterioration phenomenon occurs even when the product is used, and there is no or almost no residual potential.
Our main purpose is to provide photoconductive materials that cannot be observed.
The purpose is to Another object of the present invention is to increase photosensitivity in the entire visible light range.
It has high performance and is particularly suitable for matching with semiconductor lasers.
To provide a photoconductive member that has high photoresponse and has a fast photoresponse.
It is. Still another object of the present invention is to
between the layer to be laminated and the support, or between each layer to be laminated.
Excellent adhesion, dense and stable structural arrangement
and to provide a photoconductive member with high layer quality.
It is. Still another object of the present invention is to form an image for electrophotography.
When applied as a component, the normal electrophotographic method
electrostatic imaging to the extent that it can be applied very effectively.
It has sufficient charge retention ability during charging treatment for
Almost no deterioration of its properties was observed even in a humid atmosphere.
Photoconductive member with excellent electrophotographic properties
The goal is to provide the following. Still another object of the present invention is to
High quality with clear contrast and high resolution
Photoconductive for electrophotography that makes it easy to obtain images
It is to provide parts. Still other objects of the present invention are high photosensitivity, high
Good signal-to-noise ratio characteristics and good electrical contact with the support
It is an object of the present invention to provide a photoconductive member having properties. The present invention provides a support for a photoconductive member for electrophotography; The germanium atoms are provided on the support.
1 to 10×10 for the sum with the licon atom^Fiveatomic ppm
Layer thickness 30Å to 50μ composed of amorphous material
The first layer region (G) containing silicon atoms (G)
Constructed of amorphous material (does not contain rumanium atoms)
The layer thickness provided on the first layer region (G) is 0.5~
Layer thickness 1-100μ with second layer area (S) of 90μ
a first layer exhibiting photoconductivity of
non-containing silicon atoms and carbon atoms.
A second layer with a layer thickness of 0.003 to 30μ composed of crystalline material
A photoreceptive layer consisting of;
A conductive member, In the first layer, nitrogen atoms are combined with silicon atoms.
0.01 for the sum of germanium and nitrogen atoms
Contains ~50 atom%, in the layer thickness direction of nitrogen atoms
The concentration distribution is smooth and the maximum distribution concentration of nitrogen atoms is
The maximum value is 500 atomic ppm or more, and the
It is characterized by being located inside the layer of It was designed to have the layer structure described above.
The photoconductive member of the present invention overcomes all of the above-mentioned problems.
Excellent electrical, optical, and photoconductive solutions
Indicates physical characteristics, electrical voltage resistance, and usage environment characteristics. In particular, the photoconductive member of the present invention is suitable for electrophotographic imaging.
When applied as a component for image formation,
There is no influence of residual potential and its electrical characteristics are stable.
It has high sensitivity and high signal-to-noise ratio.
It has excellent light fatigue resistance, repeated use characteristics, and high concentration.
The halftones are clear, and the resolution is high.
You can reliably obtain high-quality images over and over again.
Wear. Further, the photoconductive member of the present invention is formed on a support.
The photoreceptive layer itself is tough, and the support
It has excellent adhesion with
Can be used repeatedly. Furthermore, the photoconductive member of the present invention is transparent in the entire visible light range.
It has high photosensitivity and is especially compatible with semiconductor lasers.
It has excellent optical performance and fast photoresponse. Hereinafter, according to the drawings, the photoconductive member of the present invention will be explained.
This will be explained in detail. FIG. 1 shows the photoconductive structure of the 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
05, or in the layer thickness direction.
is contained evenly, but the distribution concentration is uneven
It's okay to be. However, in any case, the first
In the layer region (G) 105, the surface of the support and
Regarding the parallel in-plane direction, germanium atoms are
It is uniformly distributed and evenly contained within the plane.
This is necessary from the point of view of uniformity of characteristics in the direction.
Ru. 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 example 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
It forms a distribution state like this. 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 position₂until the concentration C₆is assumed to be a constant value, and the position t₂
and position t_Tgradually and continuously decreased between
, position t₇, 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_TenIt is said that
position t₃and position t_TThe distribution concentration C is a linear relationship between
numerically 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_Tuntil 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
Then, the concentration C₂₀In the figure, so that it becomes more substantially zero.
It is reduced according to a curve of the shape shown. As described above, from Figures 2 to 10, the first layer area
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 105
Relatively high concentration of germanium atoms on the sides
It is desirable to have a localized area (A) that is For example, the localized area (A) is shown in Figures 2 to 10.
Using the symbols shown, the interface position t_Bmore layers
It is desirable that the thickness be within 5 μm in the thickness direction. The above localized region (A) is located at the interface position t_Bup to 5μ thick
Layer area (L_T) in some cases, and in others,
Layer area (L_T). The localized region (A) is transformed into a layered region (L_T) or as part of
is the entire first layer region (G)1 to be formed.
It is determined as appropriate according to the characteristics required for 05. The localized region (A) is the germanium contained therein.
Germanium atoms are distributed in the layer thickness direction.
The maximum value Cmax of the distribution concentration of atoms is the same as that of silicon atoms.
preferably 1000 atomic ppm or more, with respect to the sum of
preferably 5000 atomic ppm or more, optimally 1×10^Four
It seems possible to have a distribution state that is considered to be more than atomic ppm.
It is preferable that the layer be formed in the following manner. That is, in the present invention, germanium atoms
The 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)
is formed such that there is a maximum value Cmax of the distribution concentration at
Preferably. 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^FiveAtomic ppm, more preferred
Or 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
T_Bis preferably 30Å to 50μ, more preferably 40
Desired to be Å~40μ, optimally 50Å~30μ.
Yes. Further, the layer thickness T of the second layer region (S) 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^Fiveoriginal
If it is more than 100 ppm, the first layer area (G) 105
Layer thickness T_BIt is desirable that the
Preferably 30μ or less, more preferably 25μ or less, most preferably
It is desirable that the thickness be 20μ or less. 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 photoconductive member of the present invention, high photosensitivity and
High dark resistance, and furthermore,
For the purpose of improving adhesion, the first layer ()
In 102, there is a layer region containing nitrogen atoms.
(N) is provided. Nitrogen atoms are in the first layer ()
May be evenly contained in the entire layer area of 102
Or, some layer areas of the first layer () 102
It may be contained only in the area and may be distributed ubiquitously. In the present invention, the nitrogen source in the layer region (N)
The child distribution state is such that the distribution concentration C(N) is the support 10.
Uniform in the in-plane direction parallel to the surface of 1
However, it is non-uniform in the layer thickness direction. In the example shown in Figure 11, the distribution concentration of nitrogen atoms is
The degree C(N) is the surface position of the first layer 102 on the support side.
Placement_BMore position₉In the layer region up to the concentration C_{twenty one}and
and position t₉from position t_TenIn the layer area up to
is the position t₉from position t_TenThe position increases rapidly until
t_TenThe peak value of the distribution concentration C_{twenty two}become. position t_Tenfrom
position t₁₁The distribution of nitrogen atoms in the layer region up to
Concentration C(N) is at position t₁₁decreases rapidly as it approaches
Slightly on the side of the first layer 102 opposite to the support 101
surface position t_TAt concentration C_{twenty one}becomes. In the example shown in Figure 12, the distribution concentration of nitrogen atoms is
The degree C(N) is the position t_Bfrom position t₁₂In the layer area up to
is the concentration C_{twenty three}and position t₁₂from position t₁₃layer area up to
Now position t₁₂More position₁₃The position increases rapidly until
t₁₃The peak value of the distribution concentration C_{twenty four}Take position t₁₃Kara position
Placement_TIn the layer region up to the position t_TAs you get closer to
It decreases until it reaches zero. In the example shown in Figure 13, the distribution concentration of nitrogen atoms is
The degree C(N) is the position t_Bfrom position t₁₄In the layer area up to
is C_{twenty five}from C₂₆slowly increasing until position t₁₄in
Peak value C of distribution concentration₂₆and position t₁₄from position
t_TIn the layer region up to the position t_Trapidly as it approaches
and position t_TThen the concentration C_{twenty five}becomes. In the example shown in Figure 14, the distribution concentration of nitrogen atoms is
The degree C(N) is the position t_BAt concentration C₂₇So, position t_BKara position
Placement₁₅decreases as the position approaches t₁₅At concentration C₂₈and
Become. position t₁₅from position t₁₆In the layer region up to
The distribution concentration C(N) of elementary atoms is the concentration C₂₈is constant
Ru. position t₁₆from position t₁₇In the layer area up to,
The distribution concentration of nitrogen atoms increases at position t₁₇distribution concentration at
C(N) is the peak value C₂₉Take. position t₁₇from position t_T
In the layer region up to, the distribution concentration of nitrogen atoms C
(N) decreases and position t_TAt concentration C₂₈becomes. In the present invention, the first layer ( ) 102 is provided with
Layer region containing nitrogen atoms (N)
is used when the main purpose is to improve photosensitivity and dark resistance.
occupies the entire layer area of the first layer () 102.
The charge from the free surface of the photoreceptive layer is
To prevent injection, close the interface on the free surface side.
between the support and the photoreceptive layer.
When the main purpose is to strengthen the adhesion of
, the support side end layer region of the first layer ( ) 102 is
It is set up to occupy area (E). For the first purpose above, the layer region (N) contains
The content of nitrogen atoms in the
In the case of the second purpose above,
To prevent charge injection from the free surface of the photoreceptor layer
In the case of the third purpose above,
In order to ensure strong adhesion with the support,
It is desirable that it be done more often. In addition, for the purpose of achieving the above three at the same time,
It is distributed at a relatively high concentration on the support side, and the center
It is distributed at a relatively low concentration on the free surface side.
In the interface layer region, nitrogen containing more nitrogen atoms is added.
If the distribution state of elementary atoms is formed in the layer region (N),
good. In the present invention, the first layer ( ) 102 is provided with
In the layer region (N) containing nitrogen atoms
The content of nitrogen atoms is the amount required for the layer region (N) itself.
or the layer region (N) is the support 101.
When the support 1 is provided in direct contact with the
Organic
It can be selected as appropriate depending on the relationship. In addition, other layer regions may be directly contacted with the layer region (N).
If a layer area is provided, the characteristics of the other layer area and
Relationship with characteristics at the contact interface with other layer regions
The content of nitrogen atoms is selected appropriately, taking into account
Ru. The amount of nitrogen atoms contained in the layer region (N) is
Depending on the characteristics required for the photoconductive member to be formed.
Although it can be determined as desired, silicon atoms and
The sum of germanium atoms and nitrogen atoms (hereinafter referred to as “T
(denoted as SiGeN)” preferably from 0.001 to
50 atom%, more preferably 0.002 to 40 atom%, maximum
Suitably, the content is desirably 0.003 to 30 atomic %. In the present invention, the layer region (N) is the first layer.
( ) 102 or the first
Even if it does not occupy the entire area of layer () 102, the layer area
(N) layer thickness T₀The layer thickness T of the first layer ( ) 102 of
If the proportion of the area is sufficiently large, the layer area (N)
The upper limit of the content of nitrogen atoms contained in
It is desirable that the value be sufficiently smaller than the value. In the present invention, the layer thickness T of the layer region (N)₀but
Percentage of the thickness T of the first layer ( ) 102
If the ratio is two-fifths or more, the layer area
As the upper limit of the amount of nitrogen atoms contained in (N)
is preferably 30 atom% relative to T(SiGeN)
or less, more preferably 20 atom% or less, optimally
It is desirable that the content be 10 atomic % or less. In the present invention, layer regions containing nitrogen atoms
(N) is on the support 101 side or/and as described above.
Nitrogen atoms are present in the vicinity of the second layer ( ) 103 side.
It has a localized region (B) containing relatively high concentration.
It is desirable that the
is between the support 101 and the first layer ( ) 102
to further improve the adhesion and acceptance potential of
can be improved. 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_T), or the layers
Area (L_T). The localized region (B) is transformed into a layered region (L_T) or as part of
It depends on the photoreceptive layer 104 to be formed.
It is determined as appropriate according to the required characteristics. The localized region (B) is the nitrogen atom contained therein.
Distribution concentration C of nitrogen atoms as the distribution state in the layer thickness direction
The maximum value Cmax of (N) is preferably 500 atomic ppm
or more, more preferably 800 atomic ppm or more, optimally
becomes a distribution state that is said to be more than 1000 atomic ppm.
It is preferable that the layer be formed in such a manner as to obtain the desired result. That is, in the present invention, the first layer () 10
The layer region (N) containing nitrogen atoms in 2 is
Support 101 side or surface of second layer () 103
Maximum value Cmax of distribution concentration within 5μ in layer thickness from the surface
It is desirable that the structure be formed in such a way that it exists. In the present invention, if necessary, the first layer ()
The halogen atom contained in 102 is specifically
Examples include fluorine, chlorine, bromine, and iodine.
In particular, mention fluorine and chlorine as suitable.
I can do it. In the photoconductive member of the present invention, germanium
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 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
Layer region (PN) containing the substance that controls sex (D)
is provided in part or all of the first layer () 102.
It's okay. Or, the layer area (PN) is the layer area (G) or
Alternatively, 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 the 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 governs the conduction characteristics is the first
For inclusion in layer () 102, the first layer
Locally contained in the desired layer region of ()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 the substance (D) that governs the conduction properties is also taken into account.
The amount is selected accordingly. In the present invention, the first layer ( ) 102 contains
The content of the 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 is
The content of the substance (D) in the contained layer region (PN)
The amount is preferably 30 atomic ppm or more, more preferably
is above 50 atomic ppm, optimally above 100 atomic ppm
In the case of , the substance (D) governing the conduction properties is
Locally in some layer regions of the first layer ( ) 102
It is desirable to contain, especially in the first layer () 1
It is desirable to knit it in the support side end layer region (E) of 02.
Delicious. Among the above, the support side end of the first layer ( ) 102
So that the content in the substratum area (E) is higher than the above value.
Containing a substance (D) that controls the conduction characteristics.
For example, the substance (D) may contain the above p-type impurity.
In the case of , the free surface 107 of the photoreceptive layer 104 is
When the polarity is charged, the support 101 side
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
Free surface 107 of receptive layer 104 is polarly charged.
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 a 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 the substance (D) that controls 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
child ppm, more preferably 0.05~500 atomic ppm optimally
is preferably set to 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 Akira, the first layer ( ) 102 has one side.
Contains a substance that controls polar conductivity
dominates the layer region and conductivity with the other polarity
Designed to be in direct contact with the layer area containing the substance.
Therefore, a so-called depletion layer may be provided in the contact layer region.
I can do it. Clogging, e.g. in the first layer ( ) 102
, the layer region containing the p-type impurity and the layer region containing the p-type impurity;
Direct contact with the layer region containing n-type impurities
A depletion layer is created by forming a so-called p-n junction.
I can do it. 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.
Introduce the desired gas state and release a glow into the deposition chamber.
generates electricity and is installed in a predetermined position in advance,
from a-Ge (Si, H, X) on the surface of a given support.
What is necessary is to form a layer. Also, germanium atom
in the first layer region (G) 105 in a non-uniform distribution state.
In order to contain germanium atoms, the distribution concentration of germanium atoms must be adjusted.
a-Ge (Si,
What is necessary is to form a layer consisting of H, X). Also, Su
In the puttering method, for example, Ar, He, etc.
Mixtures based on inert gases or these gases
A tar composed of silicon atoms in a gas atmosphere
target, or the target and germanium source
Using two targets made up of children,
is a mixture of silicon and germanium atoms.
If necessary, select He,
Germanium atoms diluted with diluent gas such as Ar
Raw material gas for supply, hydrogen atoms or
/ and sputtering gas for introducing halogen atoms.
plasma of the desired gas.
The first layer region (G)1 by forming an atmosphere
Form 05. This sputtering method smells
When the distribution of germanium atoms is made non-uniform by
In this step, the raw material gas for supplying the germanium atoms is
While controlling the gas flow rate according to the desired rate of change curve.
Then sputter the said target.
Good. In the case of ion plating, for example,
Crystalline silicon or single crystal silicon and polycrystalline germanium
aluminum or single crystal germanium as evaporation sources, respectively.
The evaporation source is housed in a evaporation boat as a
Thermal method or electron beam method (EB method)
evaporation by heating and vaporizing the flying vapor into the desired gaspure.
Except for passing it through the plasma atmosphere, it is sputtering.
the first layer by the same method as in the
A region (G) 105 can be formed. For supplying silicon atoms used in the present invention
As a material that can be used as a raw material gas, SiH_Four,
Si₂H₆,Si₃H₈,Si_FourH_Tengaseous state or gas such as
Silicon hydride (silanes), which can be
In particular, during layer creation work.
Ease of handling, good silicon atom supply efficiency, etc.
In SiH_Four,Si₂H₆are listed as preferred
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
In the present invention, hydrogenated compounds containing
This can be mentioned in the following. 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 hydrogen 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 material gas for supplying halide and germanium atoms
Germanium hydride, Ar, and H₂, He et al.
Gas etc. so that the specified mixing ratio and gas flow rate are achieved.
to the deposition chamber forming the first layer region (G) 105.
These gases are released by introducing a glow discharge.
By creating a lasma atmosphere, the desired support can be achieved.
A first layer region (G) 105 can be formed on the support 101.
However, the rate of introduction of hydrogen atoms must be controlled uniformly.
Add water to these gases to make the layer easier.
Also desired is elementary gas or elementary compound gas containing hydrogen atoms.
A layer may be formed by mixing 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, GeF₂,
GeCl₂, GeBr₂, GeI₂germanium halides such as
Substances that are in a gaseous state or can be gasified, such as
A starting material for forming an effective first layer region (G) 105 and
I can list it as follows. Among these substances, halogenated substances containing hydrogen atoms
When forming the first layer region (G) 105, the material is halved in the layer.
At the same time as the introduction of rogen atoms, electrical or photoelectric characteristics
Hydrogen atoms, which are extremely effective in controlling sex, are also introduced.
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 when forming the layer region (S) 106
It can be formed according to laws and conditions. That is, in the present invention, a structure composed of a-Si(H,X)
The second layer region (G) 105 formed is, for example, a glow emitter.
Electrical method, sputtering method, or ion plate method
By vacuum deposition method that utilizes discharge phenomenon such as
It is formed by For example, using the glow discharge method
A second layer region composed of a-Si(H,X)
(S) 106 is basically formed as described above.
For supplying silicon atoms that can supply silicon atoms
Along with the raw material gas, for hydrogen atom introduction as necessary.
or/and raw material gas for introducing halogen atoms,
The deposition chamber is introduced into a deposition chamber whose interior can be depressurized.
Create a glow discharge inside the device and place it in a predetermined position.
a-Si(H,X) on a given support surface
What is necessary is to form a layer consisting of. Also, spatsutari
For example, when forming by a method such as Ar, He, etc.
Mixtures based on inert gases or these gases
A tar composed of silicon atoms in a gas atmosphere
When sputtering the get, hydrogen atoms or/
and sputtering gas for introducing halogen atoms.
It is sufficient to introduce it into the deposition chamber for use. In the present invention
contained in the second layer region (S) 106 to be formed.
the amount of hydrogen atoms or the amount of halogen atoms,
Or the sum of the amounts of hydrogen atoms and halogen atoms (H+X)
is preferably 1 to 40 atom%, more preferably 5 to 40 atom%
It is desirable that the content be 30 atom%, optimally 5 to 25 atom%.
Delicious. In the present invention, the first layer () 102 contains a nitrogen source.
To provide the child-containing layer region (N), first
When forming the layer ( ) 102, a layer for introducing nitrogen atoms is added.
For forming the first layer ( ) 102 containing the starting materials
starting material to incorporate it into the formed layer.
It is sufficient to control the amount of . Glow discharge method is used to form layer region (N)
If there is, the first layer ( ) 102 type described above
selected as desired from among the starting materials for
A starting material for the introduction of nitrogen atoms is added to the material.
As a starting material for such nitrogen atom introduction, a small amount of
A gaseous substance whose constituent atoms are at least nitrogen atoms.
or a large amount of gasified substances that can be gasified.
Any of the following can be used. For example, a raw material gas whose constituent atoms are silicon atoms
, a raw material gas whose constituent atoms are nitrogen atoms, and the necessary
Consists of hydrogen atoms or/and halogen atoms depending on
By mixing the raw material gas as atoms at the desired mixing ratio.
or using silicon atoms as constituent atoms.
raw material gas and constituent atoms including nitrogen atoms and hydrogen atoms.
and the raw material gas at the desired mixing ratio.
or with silicon atoms as constituent atoms.
raw material gas, silicon atoms, nitrogen atoms and hydrogen
A raw material gas consisting of three atoms is mixed.
It can be used as Also, separately, it is composed of silicon atoms and hydrogen atoms.
Nitrogen atoms are used as constituent atoms in the raw material gas.
A mixture of raw material gases may be used. Nitrogen source used when forming layer region (N)
Effective as a raw material gas for introducing
The starting materials used include nitrogen as a constituent atom or
Or, for example, nitrogen whose constituent atoms are nitrogen and hydrogen.
(N₂), ammonia (NH₃), hydrazine
(N₂NNH₂), hydrogen azide (HN₃), ammo azide
Nium (NH_FourN₃), etc., which are gaseous or capable of being gasified.
Nitrogen compounds such as nitrogen, nitrides and azides are listed.
You can get it. In addition to this, the introduction of nitrogen atoms
In addition, it is also possible to introduce halogen atoms.
et al., nitrogen trifluoride (F₃N), nitrogen tetrafluoride (F_FourN₂)etc
Examples include halogenated nitrogen compounds. In the present invention, a nitrogen source is present in the layer region (N).
In order to further enhance the effect obtained with
In addition to oxygen atoms, it can also contain oxygen atoms.
Ru. Oxygen source for introducing oxygen atoms into the layer region (N)
For example, oxygen can be used as a raw material gas for introducing oxygen.
(O₂), ozone (O₃), nitric oxide (NO), dioxide
Nitrogen (NO₂), nitrogen monoxide (N₂O), sesquioxide
Nitrogen (N₂O₃), trinitrogen tetraoxide (N₂O_Four), pentoxide
Nitrogen (N₂O_Five), nitrogen trioxide (NO₃) silicon atom
An example where the constituent atoms are an oxygen atom and a hydrogen atom.
For example, disiloxane (H₃SiOSiH₃), trisiloxa
(H₃SiOSiH₂OSiH₃) and other lower siloxanes, etc.
can be mentioned. Shape the layer region (N) by sputtering method.
In order to form the first layer () 102,
Single crystal or polycrystalline silicon wafer or
Si₃N_FourWafer or silicon atoms and Si₃N_Fourbut
Target wafers containing mixed
As a test, these were spattered in various gas atmospheres.
This can be done by tallying. For example, if you target silicon wafers,
When used with a nitrogen atom and optionally a hydrogen atom,
or/and raw material gas for introducing halogen atoms
Dilute with diluting gas as necessary and spatter
These gases are introduced into a deposition chamber for
The silicon wafer is spun by forming a plasma.
All you have to do is tumble. Also, separately, silicon atoms and Si₃N_Fourseparate from
as a target or with silicon atoms and Si₃N_Fourof
By using a mixed burst of targets,
The atmosphere of diluent gas as sputtering gas
in air or at least hydrogen atoms or/and halogens
in a gas atmosphere containing carbon atoms as constituent atoms.
All you have to do is sputtering. Source for introducing nitrogen atoms
As the source gas, the gas shown in the glow discharge example mentioned above is used.
The raw material gas for introducing nitrogen atoms in the raw material gas is
Also used as an effective gas for sputtering.
can be done. In the present invention, formation of the first layer ( ) 102
At this time, a layer region (N) containing nitrogen atoms is established.
When the nitrogen atoms contained in the layer region (N)
By changing the distribution concentration C(N) in the layer thickness direction,
It has the desired depth profile.
To form the layer region (N), a glow discharge field is
In this case, the nitrogen distribution concentration C(N) should be changed.
The starting material gas for introducing atoms is determined by its gas flow rate.
The deposition rate is changed as appropriate according to the desired rate of change curve.
It can be installed inside the storage room. e.g. manually or externally.
Some commonly used drive motor, etc.
According to the law, a specified
Perform operations to change the opening of the needle valve as appropriate.
It's fine. At this time, for example, using a microcomputer etc.
flow according to a pre-designed rate of change curve.
You can also control the amount and obtain the desired content curve.
Ru. Form layer region (N) by sputtering method
In this case, the distribution concentration of nitrogen atoms in the layer thickness direction C(N)
by changing the thickness direction of the nitrogen atoms in the layer thickness direction.
to form the desired depth profile.
is, firstly, similar to the case using the glow discharge method.
The starting material for the introduction of nitrogen atoms is used in a gaseous state.
and the gas flow rate when introducing the gas into the deposition chamber.
This can be done by changing it appropriately as desired.
Ru. Second, it can be used as a target for sputtering.
For example, silicon atoms and Si₃N_Fourmixed with
If you use a target, silicon atoms
and Si₃N_FourAdjust the mixing ratio in the direction of the target layer thickness.
This can be achieved by changing it in advance.
Ru. In the first layer ( ) 102,
substances such as group atoms or group atoms
In order to introduce structurally, group elements must be introduced during layer formation.
Starting material for introduction of atoms or starting material for introduction of group atoms
The emitting material is placed in a gaseous state in the deposition chamber in the second layer region.
With other starting materials to form (S)106
It would be good to introduce it. For introducing group atoms like this
Possible starting materials include:
readily under gaseous or at least layer-forming conditions
It is desirable to use something that can be gasified. So
As a starting material for the introduction of group atoms such as
B is used for introducing boron atoms.₂H₆,B_FourH_Ten,
B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B₆H₁₂,B₆H₁₄Hydrogen such as
Boron oxide, BF₃, BCl₃,BBr₃Boron halides such as
etc. In addition, AlCl₃, GeCl₃, Ge
(CH₃), InCl₃, TlCl₃, etc. can also be mentioned.
Ru. As a starting material for the introduction of group atoms,
It is effectively used for introducing phosphorus atoms.
So, PH₃,P₂H_FourPhosphorus hydride, PH, etc._FourI, P.F.₃,
P.F._Five, PCl₃, PCl_Five, PBr₃, PBr_Five, P.I.₃etc. halogen
Examples include phosphorus chloride. In addition, AsH₃,AsF₃,
AsCl₃, AsBr₃,AsF_Five, SbH₃, SbF₃, SbF_Five,
SbCl₃, SbCl_Five, BiH₃, BiCl₃, 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
It is desirable that the thickness be 40 Å or more, and optimally 50 Å or more.
Delicious. 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 layer thickness of the layer region (PN)
The upper limit is preferably 10μ or less, preferably 8μ
Hereinafter, the optimum value is preferably 5μ or less. In the photoconductive member 100 shown in FIG.
is the second layer formed on the first layer ( ) 102
Layer ( ) 103 has a free surface and is mainly moisture resistant,
Continuous repeated use characteristics, electrical pressure resistance, usage environment characteristics
In order to achieve the purpose of the present invention in terms of performance and durability,
provided. Further, in the present invention, the first layer ( ) 102
and the amorphous material constituting the second layer ( ) 103
each have a common constituent element, silicon atoms.
, so both layers ()102 and ()1
Ensuring chemical stability at the laminated interface of 03
It is fully accomplished. The second layer ( ) 103 in the present invention is made of silicon.
a carbon atom, a carbon atom, and a hydrogen atom or
is/and an amorphous material containing silicon atoms (hereinafter referred to as
After that, “a-(SixC_1-x)y(H,X)_1-y”However, 0<
x, y<1). a-(SixC_1-x)y(H,X)_1-yThe first part consists of
The second layer 103() is formed by glow discharge method,
Puttering method, ion plantation method,
On-plating method, electron beam method, etc.
done by. 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
It is relatively easy to use carbon atoms together with silicon atoms.
The second layer (to make the atoms and halogen atoms)
Advantages such as ease of introduction into 103
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-(SixC_1-x)y(H,X)_1-yshape
The raw material gas for synthesis is mixed with dilution gas as required.
After mixing at a mixing ratio of
It was introduced into a deposition chamber for vacuum deposition.
gas by causing a glow discharge.
already formed on the support 101.
A-
(SixC_1-x)y(H,X)_1-yAll you have to do is deposit it. In the present invention, a-(SixC_1-x)y(H,X)_1-
yThe raw material gas for formation is silicon atoms, carbon
At least among elementary atoms, hydrogen atoms, and halogen atoms
A gaseous substance or gasification whose constituent atoms are
Most of the substances that can be gasified are
can be used. Silicon atom, carbon atom, hydrogen atom, halogen
Silicon atom is one of the constituent atoms.
For example, when using a raw material gas that
A raw material gas composed of atoms and a carbon atom composed of
Source gas to be made into constituent atoms and hydrogen atoms if necessary
Raw material gas or/and halogen source having constituent atoms
and raw material gas with constituent atoms at the desired mixing ratio.
or have silicon atoms as constituent atoms
Raw material gas, carbon atoms and hydrogen atoms as constituent atoms
Atoms constituting the raw material gas and/or halogen atoms
and the raw material gas, also at the desired mixing ratio.
Mix or use silicon atoms as constituent atoms.
raw material gas, silicon atoms, carbon atoms and water
Raw material gas or silicon that constitutes three elementary atoms
Consists of three atoms: atom, carbon atom, and halogen atom
Can be used by mixing raw material gas with atoms.
I can do it. Also, separately, it is composed of silicon atoms and hydrogen atoms.
Carbon atoms are used as constituent atoms in the raw material gas.
You can use a mixture of raw material gases, or silicon
Raw material gas whose constituent atoms are atoms and halogen atoms
A raw material gas containing carbon atoms is mixed with
May be used. In the present invention, the second layer ( ) 103 contains
Preferred halogen atoms include fluorine,
Chlorine, bromine, and iodine, especially fluorine and chlorine.
It is desirable. In the present invention, the second layer ( ) 103 is formed
It can also be a raw material gas that can be effectively used to
Examples include those that are in a gas state at room temperature and pressure, or
Substances that can be easily gasified can be mentioned. In the present invention, for forming the second layer ( ) 103
Silicon is usefully used as a raw material gas for
SiH whose constituent atoms are carbon atoms and hydrogen atoms_Four,
Si₂H₆,Si₃H₈,Si_FourH_TenSilanes, etc.
silicon hydride gas, composed of carbon atoms and hydrogen atoms
Atom, e.g. saturated hydrocarbon having 1 to 4 carbon atoms
Ethylene hydrocarbon with 2 to 4 carbon atoms, carbon number
2 to 3 acetylenic hydrocarbons, simple halogen,
Hydrogen halide, interhalogen compounds, halogenation
Silicon, halogen-substituted silicon hydride, silicon hydride, etc.
I can list many. Specifically, methane is a saturated hydrocarbon.
(CH_Four), ethane (C₂H₆), propane (C₃H₈), n
-butane (n-C_FourH_Ten), pentane (C_FiveH₁₂),workman
Ethylene (C₂H_Four),
Propylene (C₃H₆), butene-1 (C_FourH₈), Butte
N-2 (C_FourH₈), isobutylene (C_FourH₈), pente
(C_FiveH_Ten), as acetylenic hydrocarbons,
Acetylene (C₂H₂), methylacetylene
(C₃H_Four), butin (C_FourH₆), as a single halogen
is a halogen gas of fluorine, chlorine, bromine, and iodine.
Hydrogen halides include FH, HI, HCl,
HBr, interhalogen compounds include BrF, ClF,
ClF₃,ClF_Five,BrF_Five,BrF₃,IF₇,IF_Five, ICl, IBr,
SiF as silicon halide_Four,Si₂F₆, SiCl_Four,
SiCl₃Br, SiCl₂Br₂, SiClBr₃, SiCl₃I, SiBr_Four,
As halogen-substituted silicon hydride, SiH₂F₂,
SiH₂Cl₂, SiHCl₃,Si₃Cl, SiH₃Br, SiH₂Br₂,
SiHBr₃As silicon hydride, SiH_Four,Si₂H₈,
Si_FourH_TenSilanes such as
I can do that. In addition to these, CF_Four,CCl_Four, CBr_Four,CHF₃,
CH₂F₂,C.H.₃F, CH₃Cl, CH₃Br, CH₃I,
C₂H_FiveHalogen-substituted paraffinic hydrocarbons such as Cl,
science fiction_Four,SCIENCE FICTION₆Fluorinated sulfur compounds such as Si(CH₃)_Four,
Si(C₂H_Five)_FourAlkyl silicides such as SiCl(CH₃)₃,
SiCl₂(CH₃)₂, SiCl₃CH₃Halogen-containing silicification such as
Silane derivatives such as alkyl are also listed as effective.
You can get it. These second layer ( ) 103 forming substances are shaped like
In the second layer ( ) 103 formed, a predetermined composition is added.
The ratio of silicon atoms, carbon atoms and halogen atoms
the second so that a hydrogen atom is included as necessary.
selection as desired when forming the layer () 103 of
and used. For example, silicon atoms, carbon atoms, and hydrogen atoms
can be easily incorporated and a layer with desired properties can be formed.
Si(CH₃)_Fourand contains halogen atoms.
SiHCl as a material₃,SiH₂Cl₂, SiCl_Four, or
Iha SiH₃In a gas state with Cl etc. at a predetermined mixing ratio,
Introduced into the device for forming the second layer () 103
By causing a glow discharge, a-
(SixC_1-x)y(Cl+H)_1-yThe second layer consisting of ()
103 can be formed. Second layer ()10 by sputtering method
To form 3, monocrystalline or polycrystalline silicon
graphite wafer or silicon wafer
Contains a mixture of silicon atoms and carbon atoms
Target the wafers you have and use them as needed.
Construct halogen atoms and/or hydrogen atoms as necessary.
Sputtering in various gas atmospheres containing as components
This can be done by ringing. For example,
Use the recon wafer as a target.
For example, carbon atoms and hydrogen atoms or/and halogen atoms
Dilute the raw material gas to introduce it as necessary.
diluted with water and introduced into a deposition chamber for sputtering,
By forming a gas plasma of these gases, the silicon
All you have to do is sputter the con wafer.
In addition, silicon atoms and carbon atoms are separate
as a target or silicon and carbon atoms
I decided to use a single target that is a mixture of
Therefore, if necessary, hydrogen atoms or/and halogen
Sputtering in a gas atmosphere containing atoms
do it. Carbon atoms, hydrogen atoms and halogens
The above-mentioned substances are used as raw material gas for introducing atoms.
The second layer ()10 shown in the example of a glow discharge
3 This also applies when the forming material is sputtering method.
It can be used as a potent substance. In the present invention, the second layer ( ) 103 is
-When forming by discharge method or sputtering method
The diluent gas used is so-called rare gas, for example.
For example, He, Ne, Ar, etc. are listed as suitable ones.
I can do it. The second layer ( ) 103 in the present invention is
Care must be taken to ensure that the required properties are provided as desired.
deeply formed. That is, silicon atoms, carbon atoms
hydrogen atom or/and halogen atom as necessary
Substances whose constituent atoms are children depend on the conditions for their creation.
The structure ranges from crystal to amorphous.
In terms of electrical properties, it ranges from conductive to semiconducting to absolute.
properties ranging from photoconductive to non-photoconductive.
This book shows each property up to the conductive property.
In inventions, it is important to have the desired characteristics according to the purpose.
Rua-(SixC_1-x)y(H,X)_1-yis formed
The selection of the conditions for its creation is strictly according to the desired
be done. For example, if the second layer ( ) 103 is
If the main purpose is to improve pressure resistance, a-
(SixC_1-x)y(H,X)_1-ydoes not require electricity in the operating environment.
Created as an amorphous material with remarkable insulating behavior
It will be done. In addition, improvements in continuous repeated use characteristics and usage environment characteristics
A second layer () 103 is provided with the main purpose of
If the above degree of electrical insulation is
The degree of light is relaxed, and it has a certain degree of resistance to the irradiated light.
As an amorphous material with sensitivity, a-(SixC_1-x)y
(H,X)_1-yis created. On the surface of the first layer ( ) 102, a-
(SixC_1-x)y(H,X)_1-yThe second layer consisting of ()
Support during layer formation when forming 103
A temperature of 101 determines the structure and properties of the layer formed.
In the present invention, it is an important factor that influences
is a-(SixC_1-x)y
(H,X)_1-ylayered so that it can be created as desired.
It is desirable that the temperature of the support during formation be strictly controlled.
stomach. In the present invention, the desired objective is effectively achieved.
In addition to the method of forming the second layer ( ) 103 for
The optimal range is selected accordingly, and the second layer ()1
The formation of 03 is carried out, but the supporting body temperature during layer creation is
The temperature is preferably 20-400°C, more preferably 50°C.
~350℃, optimally 100-300℃
It's something new. To form the second layer () 103, the layers constituting the
Delicate control of the composition ratio of atoms and control of layer thickness are
Because it is relatively easy compared to other methods,
- It is advantageous to use the discharge method or sputtering method.
However, with these layer forming methods, the second layer () 103
When forming a
A- where the discharge power during layer formation is created
(SixC_1-x)yX_1-yimportant factors that influence the characteristics of
There is one. Having the characteristics for achieving the object of the present invention
Suru a-(SixC_1-x)yX_1-ybe productive and effective
It is preferable as a discharge power condition for creating
is 10-300W, more preferably 20-250W, optimally
It is desirable that the power be 50 to 200W. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr,
More preferably, it is about 0.1 to 0.5 Torr.
Delicious. In the present invention, the second layer ( ) 103 is created.
Desired values for support temperature and discharge power for
The range includes the values in the range mentioned above, but this
These layer creation factors are determined independently and separately.
The desired characteristic a-(SixC_1-x)
y(H,X)_1-yThe second layer () 103 consisting of
each based on mutual organic relationships as formed.
It is desirable to be able to determine the optimal value of the layer creation factor.
Yes. Second layer () 1 in the photoconductive member of the present invention
The amount of carbon atoms contained in 03 is the same as that of the second layer.
() 103, the purpose of the present invention is
A second layer ()1 that achieves the desired properties
This is an important factor for the formation of 03. Main departure
Charcoal contained in the second layer () 103 in light
The amount of elementary atoms constitutes the second layer ( ) 103
As appropriate depending on the type of amorphous material and its properties
It can be decided according to the That is, the general formula a-(SixC_1-x)y(H,X)_1-
yAmorphous materials shown in can be roughly divided into silico
An amorphous material (hereinafter referred to as
After that, “a-SiaC_1-a”. However, 0<a<1),
Composed of silicon atoms, carbon atoms, and hydrogen atoms
amorphous material (hereinafter referred to as “a-(SibC_1-bcH_1-c"and
write down However, 0<b, c<1) and silicon raw material
child, carbon atom, halogen atom and optionally hydrogen
Amorphous material composed of atoms (hereinafter referred to as “a-
(SidC_1-de(H,X)_1-e”. However, 0<d,
e<1). In the present invention, the second layer ( ) 103 is a-
SiaC_1-aThe second layer ()10
The amount of carbon atoms contained in 3 is preferably 1×
Ten^-3~90 atom%, more preferably 1-80 atom%, most preferably
It is desirable that the content be between 10 and 75 at%.
be. That is, the previous a-SiaC_1-aDo it with the display a.
For example, a is preferably 0.1 to 0.99999, more preferably
0.2-0.99, optimally 0.25-0.9. In the present invention, the second layer ( ) 103 is a-
(SibC_1-b)cH_1-cThe second layer consists of
The amount of carbon atoms contained in ()103 is preferably
Or 1×10^-3~90 atomic%, more preferably
is considered to be 1 to 90 atom%, optimally 10 to 80 atom%.
It is desirable that the content of hydrogen atoms is
is preferably 1 to 40 at%, more preferably 2
~35 atom%, optimally 5-30 atom%
Desirably, if the hydrogen content is within these ranges
Photoconductive members formed in
It can be fully applied as a standard. That is, the previous a-(SibC_1-b)H_1-cDo it with the display
bb is preferably 0.1 to 0.99999, more preferably 0.1
~0.99, optimally 0.15-0.9, c preferably 0.6
~0.99, more preferably 0.65~0.98, optimally 0.7~
A value of 0.95 is desirable. The second layer ( ) 103 is a-(SidC_1-d)e
(H,X)_1-eIf the second layer consists of
The content of carbon atoms contained in ()103 and
preferably 1×10^-3~90 atomic%, better
Suitably 1 to 90 atom%, optimally 10 to 80 atom%.
It is desirable that the content of halogen atoms is
is preferably 1 to 20 atom%, more preferably
is 1 to 18 at%, optimally 2 to 15 at%.
It is desirable that halogen atoms are contained within these ranges.
In practice, the photoconductive member created when there is a
It can be fully applied to
Accordingly, the content of hydrogen atoms is preferably
Preferably 19 atom% or less, more preferably 13 atom% or less
It is desirable that it be placed at the bottom. That is, the previous a-(SidC_1-d)e(H,X)_1-ed,
If expressed as e, d is preferably 0.1~
0.99999, more preferably 0.1-0.99, optimally 0.15
~0.9, e is preferably 0.8~0.99, more preferably
0.82 to 0.99, ideally 0.85 to 0.98
Yes. The layer thickness of the second layer ( ) 103 in the present invention
The numerical range is set to effectively achieve the objectives of the present invention.
This is one of the important factors, and is one of the important factors to effectively achieve the purpose of the present invention.
according to the desired purpose, so as to achieve the desired goals.
You can decide. In addition, the layer thickness of the second layer ( ) 103 is
The amount of carbon atoms contained in ()103 and the first
Also in relation to the layer thickness of the layer ( ) 102,
organic materials according to the characteristics required for each layer area.
It is necessary to decide as appropriate according to the desire based on the relevance.
Yes, but it is also possible to add productivity and mass production.
It is desirable that consideration be given to economic efficiency as well.
stomach. The layer thickness of the second layer ( ) 103 in the present invention
, preferably 0.003 to 30μ, more preferably
The desired value is 0.004 to 20μ, optimally 0.005 to 10μ.
It's a beautiful thing. As the support 101 used in the present invention
may be electrically conductive or electrically insulating. conductive
Examples of the support include NiCr, stainless steel,
Al, Cr, Mo, Mu, Nb, Ta, V, Ti, Pt, Pd
Metals such as these or alloys thereof can be mentioned. As the electrically insulating support, polyester, polyester, etc.
polyethylene, polycarbonate, cellulose, aluminum
acetate, polypropylene, polyvinyl chloride, polycarbonate
Polyvinylidene chloride, polystyrene, polyamide, etc.
synthetic resin film or sheet, glass, ceramic
Mixture, paper, etc. are usually used. These electricity
The insulating support preferably has at least one of the
The surface is conductive treated, and the conductive treated surface side
Preferably, other layers are provided. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Pd, In₂O₂, SnO₂, ITO (In₂O₃+SnO₂) etc.
Conductivity is imparted by providing a thin film of
or synthetic resin film such as polyester film.
For ilms, NiCr, Al, Ag, Pb, Zn, Ni,
Gold such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc.
Vacuum evaporation, electron beam evaporation, sputtering
Provided on the surface with a ring etc., or attached with the metal mentioned above.
The surface is laminated to make it conductive.
Granted. The shape of the support body 101 may be cylindrical or belt.
It can be obtained in any shape such as a shape or a plate shape, and as desired,
Although its shape is determined, for example, the light guide shown in FIG.
Using the electric member 100 as an image forming member for electrophotography
In the case of continuous high-speed copying, an endless
It is preferable to have a root-like or cylindrical shape. Support 1
The thickness of 01 is such that the desired photoconductive member is formed.
Although it is determined as appropriate to
When functionality is required, the function as a support is
As thin as possible within the range where it can be fully utilized
It will be done. However, in such cases, the manufacturing of the support and
In terms of handling, mechanical strength, etc., the support 101
The thickness is preferably 10μ or more. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be described.
Let me explain about the abbreviation. Figure 15 shows an example of a photoconductive member manufacturing apparatus.
vinegar. In the figure, the gas cylinders indicated by 1102 to 1106
is a raw material gas for forming the photoconductive member of the present invention.
For example, 1
102 is SiH diluted with He_FourGas (purity
99.999%, below SiH_Four/He is abbreviated. ) cylinder, 11
03 is GeH diluted with He_FourGas (purity 99.999
%, hereinafter GeH_Four/He is abbreviated. ) cylinder, 1104
is NH₃Gas (99.99% purity) cylinder, 1105
He gas (99.999% purity) cylinder, 1106 is H₂
It is a gas cylinder (99.999% purity). To allow these gases to flow into the reaction chamber 1101
is the valve 112 of the gas cylinders 1102 to 1106
2-1126, leak valve 1135 is closed
Also, check that the inflow valves 1112~
1116, outflow valve 1117-1121, auxiliary
Check that valves 1132 and 1133 are open.
First, open the main valve 1134 and turn off the
The reception room 1101 and each gas pipe are evacuated. Next
The reading of vacuum gauge 1136 is about 5×10^-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
NH from Be1104₃gas, valve 1122,
Open 1123 and 1124 and check the outlet pressure gauge 112
The pressure of 7,1128,1129 is 1Kg/cm²adjusted to
and inlet valves 1112, 1113, 1114.
By gradually opening the mass flow control
11071108, 1110 respectively.
Ru. Subsequently, the outflow valves 1117, 1118,
1119, gradually open the auxiliary valve 1132
Each gas is caused to flow into the reaction chamber 1101. child
SiH when_Four/He gas flow rate and GeH_Four/He gas flow
Amount and NH₃so that the ratio with the gas flow rate is the desired value.
Adjust the outflow valves 1117, 1118, 1119.
and the pressure inside the reaction chamber 1101 reaches the desired value.
While checking the reading of vacuum gauge 1136,
Adjust the opening of valve 1134. and the base
The temperature of 1137 is increased to 50 by heating heater 1138.
Make sure the temperature is set to a range of ~400°C.
After confirming, set the power supply 1140 to the desired power.
A glow discharge is generated in the reaction chamber 1101, and at the same time
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 the NH as appropriate.₃gas
By adjusting the flow rate of the
Distribution concentration of germanium and nitrogen atoms
Control C(N). Maintain the glow discharge for the desired time as described above.
to form a first layer region on the substrate 1137 to a desired layer thickness.
(G) 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 a 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, C₂H_Four
Dilute each gas with diluent gas such as He as necessary.
It is then supplied into the reaction chamber 1101 and adjusted to the desired conditions.
Therefore, it is sufficient to generate glow discharge. Contains halogen atoms in second layer () 103
For example, SiF_Fourgas and C₂H_Fourgas or
SiH on this_FourAdd gas and repeat as above for the second
What is necessary is to form the layer ( ) 103. Gas outflow valve required when forming each layer
Needless to say, close all outflow valves except for
Also, when forming each layer, there is no difference in the formation of the previous layer.
The used gas is inside the reaction chamber 1101 and the outflow valve 1
Gases leading from 117 to 1121 into the reaction chamber 1101
To avoid any residue remaining in the piping,
Close the valves 1117 to 1121, and close the auxiliary valve 11.
32, open 1133 and main valve 1134.
It is necessary to fully open the system and evacuate the system to high vacuum.
Do it accordingly. Carbon atoms contained in the second layer ( ) 103
For example, when using glow discharge, the amount of SiH_FourGa
and C₂H_FourThe gas introduced into the reaction chamber 1101
The ratio of flow rates applied can be varied as desired, or
When forming layers by sputtering, the target
When forming silicon wafer and graphite wafer
Change the spatter area ratio or silicon
By changing the mixing ratio of powder and graphite powder,
Control as desired by molding the gate
You can. Contained in the second layer ( ) 103
The amount of halogen atoms introduced is determined by the amount of halogen atoms introduced.
raw material gas for, e.g. SiF_FourThe gas is in the reaction chamber 1101
This is achieved by adjusting the flow rate when introduced into the
be done. Also, while forming layers, make sure that the layer formation is uniform.
For measurement, the base 1137 is rotated by a motor 1139.
It is desirable to rotate at a constant speed. Examples will be described below. Example 1 The manufacturing equipment shown in Fig. 15 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 17-4) were prepared respectively (Table 2). Germanium atom content distribution concentration in each sample
The degree is shown in Figure 16, and the concentration distribution of nitrogen atoms is shown in Figure 16.
It is shown in FIG. Each sample obtained in this way was placed on the surface of a charged exposure experiment.
and corona discharge for 0.3 seconds (sec) at 5.0KV.
and immediately irradiated with a light image. The light image is tungsten
Passes a light intensity of 2 lux・sec using a lamp light source.
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 a light source.
Instead of 810nm GaAs semiconductor laser (10m
Same procedure except that the electrostatic image was formed using W).
For each sample under different toner image forming conditions.
When we evaluated the image quality of toner transfer images, we found that
In the case of both samples, the resolution is excellent and the gradation reproducibility is excellent.
Good, clear, high-quality images were obtained. Example 2 The manufacturing equipment shown in Fig. 15 is used to produce a cylindrical shape.
An electrophotographic image was formed on an Al substrate under the conditions shown in Table 3.
Samples (Nos. 21-1 to 27-4) as forming members were
(Table 4). Germanium atom content distribution concentration in each sample
The degree is shown in Figure 16, and the content distribution concentration of nitrogen atoms
is shown in FIG. For each of these samples,
When I conducted an image evaluation test by Mr.
The materials also gave high quality toner transfer images. 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 Table 5 shows the conditions for creating the second layer () 103.
Sample No. 11- of Example 1 except that each condition was
Following the same conditions and procedures as 1, 12-1, 13-1
Each of the image forming members for electronic photography (sample No. 11-1
-1 to 11-1-8, 12-1-1 to 12-1-8, 13
-1-1 to 13-1-8) were created.
Ta. Each electrophotographic imaging forming member thus obtained
are individually installed in a copying machine, and each example is
Each example was tested under the same conditions as those listed in
For each compatible electrophotographic imaging member,
Evaluation of overall image quality of transferred images and repeated continuous use
The durability was evaluated by Comprehensive image quality evaluation of transferred images of each sample and repetition
Table 6 shows the results of durability evaluation after continuous use.
vinegar. Example 4 When forming the second layer ( ) 103, the silicon wafer
By changing the target area ratio of C and graphite,
Containment of silicon and carbon atoms in the layer ()
Sample No. 11- of Example 1 except for changing the quantitative ratio.
each of the imaging members in exactly the same manner as in 1.
I created this. The image forming member thus obtained
For each, as described in Example 1,
After repeating the leaning process approximately 50,000 times, the image
When the evaluation was carried out, the results shown in Table 7 were obtained. Example 5 When forming the second layer () 103, SiH_FourGa
S and C₂H_FourBy changing the gas flow rate ratio,
By changing the content ratio of silicon atoms and carbon atoms in
Exactly the same as Example 1 Sample No. 12-1 except for
Each of the imaging members was prepared by a method. For each image forming member thus obtained, Examples
The process up to transfer was repeated approximately 50,000 times using the method described in 1.
After repeating the image evaluation, Table 8
I got results like this. Example 6 When forming the second layer () 103, SiH_FourGa
SiF_Fourgas, C₂H_FourBy changing the gas flow rate ratio,
Content of silicon atoms and carbon atoms in ()
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. That of the imaging member thus obtained
For each, image formation, development, and
After repeating the cleaning process approximately 50,000 times,
When image evaluation was performed, the results shown in Table 9 were obtained. Example 7 Except for changing the layer thickness of the second layer () 103,
By exactly the same method as Sample No. 11-1 of Example 1.
Each of the image forming members was prepared using the following steps. Example 1
As mentioned above, the image creation, development, and cleaning processes are
Repeatedly obtained the results in Table 10.

【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】

【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...
200℃ Germanium atom (Ge)-free layer...about 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
11 to 1 are explanatory diagrams for explaining the distribution state of germanium atoms in the first layer (), respectively.
FIG. 4 is an explanatory diagram for explaining the distribution state of nitrogen atoms in the first layer (2), FIG. 15 is a schematic explanatory diagram of the apparatus used in the present invention, and FIG.
17 are distribution state diagrams showing the content distribution concentration state of each atom in the embodiment of the present invention. 100...Photoconductive member, 101...Support, 1
02...First layer (), 103...Second layer (), 104...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography; and a support for a photoconductive member for electrophotography; germanium atoms provided on the support at a concentration of 1 to 10×10 ⁵ atomic ppm relative to the sum of silicon atoms;
Layer thickness 30Å~50μ composed of amorphous material
a first layer region (G) and a layer formed of an amorphous material containing silicon atoms (but not germanium atoms) and provided on the first layer region (G) with a thickness of 0.5 to
Layer thickness 1-100μ with second layer area (S) of 90μ
A first layer exhibiting photoconductivity of an electrophotographic photoconductive member comprising a receptor layer, wherein the first layer contains nitrogen atoms at a ratio of 0.01 to the sum of silicon atoms, germanium atoms, and nitrogen atoms;
Contains ~50 atomic %, the concentration distribution of nitrogen atoms in the layer thickness direction is smooth, and the maximum distribution concentration of nitrogen atoms is 500 atomic ppm or more, and is located inside the first layer. A photoconductive member for electrophotography. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. 3. For electrophotography according to claim 1 or 2, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. Photoconductive member. 4. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform. 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.