JPH0551908B2 - - Google Patents

Description

[Detailed description of the invention]

[Description of the field to which the invention pertains] The present invention is directed to light (here, light in a broad sense, ultraviolet light).
rays, visible light, infrared rays, x-rays, gamma rays, etc.
Ru. ) that are sensitive to electromagnetic waves such as
The present invention relates to a photographic light-receiving member. [Description of conventional technology] In the image forming field, for electrophotographic light receiving members.
As a photoconductive material forming the photoreceptor layer in
has high sensitivity and low signal-to-noise ratio [photocurrent (Ip)/dark current
(Id)] is high and the spectral characteristics of the irradiated electromagnetic waves
have absorption spectral characteristics suitable for
It has fast response, has the desired dark resistance value, and is easy to use.
No pollution to the human body during use, etc.
characteristics are required. Especially for office machines.
Electronics incorporated into electrophotographic equipment used in
In the case of photographic light-receiving materials, when using the above
The non-polluting nature of the products is an important point. Based on these points, light has recently been attracting attention.
Amorphous silicon (hereinafter referred to as A-Si) is used as a conductive material.
For example, German Publication No. 2746967
No. 2,855,718 includes a photoreceptor for electrophotography.
Its application as a container member is described. However, the conventional photoreceptor made of A-Si
An electrophotographic light-receiving member having a dark resistance layer has a dark resistance.
Electrical, optical, optical values, photosensitivity, photoresponsiveness, etc.
In terms of conductive properties and use environment characteristics, as well as aging
In terms of physical stability and durability, each
Although the characteristics have been improved, the overall characteristics
There is room for further improvement in measuring improvement.
This is the reality. For example, when applied to light-receiving members for electrophotography,
In this case, we tried to increase the Sakai light sensitivity and increase the dark resistance at the same time.
Therefore, in the past, the residual voltage was
This type of photoreceptor is often observed to remain
If the material is used repeatedly for a long period of time, it will become difficult to use it repeatedly.
This is the so-called gore that accumulates due to fatigue and causes afterimages.
There are fewer inconveniences such as the occurrence of
It was gone. In addition, when configuring the photoreceptive layer with A-Si material,
to improve its electrical and photoconductive properties.
In addition, hydrogen atoms, fluorine atoms, chlorine atoms, etc.
For control of halogen atoms and electrical conductivity type
contains boron atoms, phosphorus atoms, etc., or has other property modifications.
For good reason, other atoms each serve as a light guide.
Contained in the electric layer, but the content of these constituent atoms
Depending on the method used, the electrical properties of the formed layer may be
Otherwise, problems may occur with photoconductive properties or voltage resistance.
It was hot. That is, for example, when a formed photoconductive layer is exposed to light,
Lifespan of photocarriers generated in this layer
There may be insufficient information, or the image may not be transferred to the transfer paper.
This image is commonly called ``white blank''. local radiation
Image defects or creases that may be caused by electrical breakdown
When a blade is used for cleaning, due to its abrasion,
Seem. Missing image of what is commonly referred to as "white streaks"
Defects may occur or, for example, if the surface has a certain thickness,
a layer that is substantially transparent to the light used.
In cases where the
changes in the reflection spectrum of the surface layer, making it especially sensitive.
In cases where unfavorable changes occur over time regarding
There were many cases where this happened. Also, it can be used in a humid atmosphere.
or if left in a humid atmosphere for a long time.
If the image is blurred when used later
There were quite a few. Therefore, efforts were made to improve the properties of the A-Si material itself.
On the other hand, when designing a light-receiving member, the above-mentioned
The layer structure and each layer are designed to solve all of these problems.
It is necessary to devise the chemical composition and preparation method of
Ru. [Purpose of the invention] The present invention provides a secondary structure made of A-Si as described above.
For electrophotographic light-receiving members with conventional light-receiving layers.
The purpose is to solve various problems that
Ru. That is, the main purpose of the present invention is to
The photoconductive properties mostly depend on the usage environment.
It is virtually always stable and has excellent resistance to light fatigue.
It is durable even after repeated use without causing any deterioration phenomenon.
Excellent durability and moisture resistance, with no or almost no residual potential.
A photoreceptive layer composed of A-Si, which is rarely observed.
To provide a light receiving member for electrophotography having
be. Another object of the invention is the layer provided on the support.
and the support and between each laminated layer.
Excellent adhesion, dense and stable structure
A photoreceptive layer composed of A-Si with high layer quality.
To provide a light receiving member for electrophotography having
be. Still another object of the present invention is to provide a photoreceptor for electrophotography.
When applied as a material, it can be used as a strip for electrostatic imaging.
It has sufficient charge retention ability during electrical processing, and is
Excellent electronics to which electrophotography can be applied extremely effectively
A photoreceptive layer composed of A-Si that exhibits photographic properties.
An object of the present invention is to provide a light-receiving member for electrophotography having
Ru. Another object of the invention is to improve the image quality in long-term use.
There are no defects or blurred images, high density, and hard
High quality with clear contrast and high resolution
A for electrophotography that allows you to easily obtain images
-A light-receiving member with a light-receiving layer made of Si
It is about providing. Still another object of the present invention is to provide high photosensitivity and high SN.
Made of A-Si with specific characteristics and high electrical voltage resistance.
A light-receiving member for electrophotography having a light-receiving layer made of
Our goal is to provide the following. [Structure of the invention] The electrophotographic light-receiving member of the present invention comprises a support and a light-receiving member for electrophotography.
A small number of nitrogen atoms, oxygen atoms, and carbon atoms are added to the support.
Amorphous material containing at least one species and silicon atoms
Adhesive layer composed of silicon atoms and germanium
It is composed of an amorphous material containing umium atoms, and has a long wavelength
A long-wavelength photosensitive layer sensitive to light and a silicon raw material
It is composed of an amorphous material with a parent body, and is a member of the periodic table.
Charge containing a group or an atom belonging to a groupNote
Entry blocking layer, silicon atoms as the base material, hydrogen atoms
and a halogen atom.
Composed of amorphous materials containing as a component, photoconductive
The photoconductive layer exhibiting properties, silicon atoms and carbon atoms
It is composed of an amorphous material containing hydrogen atoms as a constituent element.
a light-receiving layer having a surface layer made of
and in the surface layer, the surface layer and the light
The concentration of carbon atoms decreases toward the interface with the conductive layer.
The concentration distribution of the constituent elements in the layer thickness direction is
is changed, and the thickness direction of the hydrogen atoms is changed.
The maximum concentration in the surface layer is 41-70 at%.
be a sign. The surface layer contains halogen atoms.
The charge injection blocking layer has a uniform thickness in the layer thickness direction.
Constituent elements are distributed in large amounts on the support side or on the side of the support.
of atoms belonging to groups or groups of the periodic table as children
It may contain substances that control conductivity, such as
stomach. The long wavelength photosensitive layer and/or the charge injection blocking layer
In addition, it is distributed uniformly in the layer thickness direction or more often on the support side.
Oxygen atoms or/and
It may contain a nitrogen atom. Also, long wavelength photosensitive layer and
and/or oxygen atoms in the charge injection blocking layer and/or
and nitrogen atoms may be present on the support side. Further, the photoconductive layer has carbon atoms as constituent atoms,
Oxygen atoms, nitrogen atoms, and substances that control conductivity
(atom belonging to group or group of the periodic table)
At least one type may be included. In the present invention, the long wavelength photosensitive layer is composed of
Required with silicon atoms and germanium atoms as children
At least one hydrogen atom and a halogen atom depending on
Amorphous materials containing seeds, so-called hydrogen
amorphous silicon germanium, halogen
amorphous silicon germanium, or
Halogen-containing hydrogenated amorphous silicon germanium
(Hereinafter, these generic notations will be referred to as “A-
It is composed of SiGe (H,
Ru. It was designed to have the layer structure described above.
The light-receiving member for electrophotography of the present invention has the above-mentioned problems.
Extremely superior electrical and optical technology that can solve all problems
Indicates optical properties, photoconductive properties, pressure resistance, and usage environment characteristics.
vinegar. In other words, it is applied as a light-receiving member for electrophotography.
In this case, the influence of residual potential on image formation is completely
It has stable electrical characteristics and high sensitivity.
It has a high signal-to-noise ratio, light fatigue resistance,
Has excellent repeatability, high concentration, and half-tone
High-quality images with clear images and high resolution.
Images can be stably and repeatedly obtained. Hereinafter, according to the drawings, the photoreceptor for electrophotography of the present invention will be described.
The members will be explained in detail. FIG. 1 illustrates the electrophotographic light receiving member of the present invention.
FIG. 2 is a schematic configuration diagram schematically shown for clarity. The light-receiving member for electrophotography shown in FIG.
The layer 100 is a support 101 for a light-receiving member.
The photoreceptive layer 100 is provided on the
Layer 107, long wavelength photosensitive layer 102, charge injection blocking
Layer 103, consisting of A-Si(H,X), photoconductive
a photoconductive layer 104 having silicon atoms and carbon atoms.
Amorphous material whose constituent elements are elementary atoms and hydrogen atoms
and the concentration of these components is at least
an optical band gear at the interface with the photoconductive layer;
The shape has changed in such a way that the consistency of the tsupu can be obtained.
and a table in which the maximum concentration of hydrogen atoms is 41 to 70 at%
It has a layer structure consisting of a surface layer 105. Below, the components constituting the electrophotographic light receiving member of the present invention are as follows.
Describe each layer. The support used in the present invention includes conductive
It may be electrically conductive or electrically insulating. conductive support
Examples of materials include NiCr, stainless steel, Al,
Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd etc.
Examples include metals and alloys thereof. 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
Mitsuku, 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, In₂O₃, SnO₂, ITO (In₂O₃+SnO₂) etc.
Conductivity is imparted by providing a thin film of
or synthetic resin film such as polyester film.
For ilms, NiCr, Al, Ag, Pb, Zn, Ni,
Gold such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc.
Vacuum evaporation, electron beam evaporation, sputtering
Provided on the surface with a ring etc., or attached with the metal mentioned above.
The surface is laminated to make it conductive.
Granted. The shape of the support body may be cylindrical or base.
It can be of any shape such as a bolt shape or a plate shape, and can be shaped as desired.
For example, the shape is determined by
In the case of copying, it should be in the form of an endless belt or a cylinder.
is desirable. The thickness of the support can be adjusted to
determined as appropriate to form a photographic light-receiving member.
However, flexibility is required as a light-receiving member for electrophotography.
If the material is
It is made as thin as possible within the specified range. death
However, in such cases, the manufacturing and
In terms of handling and mechanical strength, it is usually 10μ or more.
considered to be above. In particular, image recording using coherent light such as laser light
When recording, it is important to
Eliminates image defects caused by so-called interference fringes.
For this reason, the surface of the support may be provided with irregularities. The unevenness provided on the surface of the support is a V-shaped cut.
Cutting tools with blades using milling machines, lathes, etc.
Fixed in place on the machine tool, e.g. cylindrical support
A program designed in advance according to your wishes
Move regularly in a specified direction while rotating according to
The support surface can be precisely cut by
By doing this, the desired uneven shape, pitch, and depth can be formed.
be done. Formed by this cutting method
The inverted V-shaped linear protrusion created by the unevenness is a cylindrical support.
It has a spiral structure centered on the central axis of the holder. reverse
The spiral structure of the V-shaped protrusion has double and triple spirals.
It may be a linear structure or a crossed spiral structure.
stomach. Alternatively, in addition to the spiral structure, parallel along the central axis
A line structure may also be introduced. Vertical cross-sectional shape of the uneven convex portion provided on the support surface
The shape is the layer thickness within the microcolumn of each layer formed.
controlled heterogeneity of the support and the support
Good adhesion between directly applied layers and desired
It is shaped like an inverted V to ensure electrical contact.
but preferably substantially as shown in FIG.
Isosceles triangle, right triangle or scalene triangle
It is desirable that These shapes are especially second class.
Side triangles and right triangles are preferred. In the present invention, the surface of the support is controlled in a controlled manner.
Each dimension of unevenness provided in the
Taking these points into consideration, the purpose of the present invention can be achieved as a result.
It is set up so that it can be done. That is, the first is A-Si(H,
X) The layer is structurally sensitive to the conditions of the surface on which it is formed.
The layer quality varies greatly depending on the surface condition.
Ru. Therefore, the deterioration of the layer quality of the A-Si(H,X) layer is
An uneven design is provided on the surface of the support to prevent
It is necessary to set the image. Second, the free surface of the photoreceptor layer has extreme irregularities.
When cleaning after image formation,
You will not be able to perform the process completely. Also, when cleaning the blade,
There is a problem in that the damage to the blade accelerates. The above-mentioned layer deposition problems and the electrophotographic process
Examine process problems and conditions to prevent interference fringes.
As a result, the pitch of the recesses on the surface of the support was found to be favorable.
preferably from 500 μm to 0.3 μm, more preferably from 200 μm
It is desirable that the thickness be 1 μm, optimally 50 μm to 5 μm. Also, the maximum depth of the recess is preferably 0.1μm
~5μm, more preferably 0.3μm to 3μm, optimally
It is desirable that the thickness be 0.6 μm to 2 μm. Support surface
If the pitch and maximum depth of the recess are within the above range,
In this case, the slope of the slope of the recess (or linear protrusion) is
Preferably 1 degree to 20 degrees, more preferably 3 degrees to 15 degrees
degree, optimally 4 degrees to 10 degrees. Also, the layer pressure of each layer deposited on such a support
The maximum difference in layer thickness due to the non-uniformity of
Preferably 0.1 μm to 2 μm, more preferably 0.1 μm
~1.5μm, optimally 0.2μm to 1μm.
Delicious. Also, when using coherent light such as laser light
Another way to eliminate image defects caused by interference fringe patterns
As a method, multiple spherical trace depressions are formed on the surface of the support.
It is also possible to provide an uneven shape. That is, the surface of the support is required for electrophotographic light receiving members.
It has finer irregularities than the required resolution, and
The unevenness is due to a plurality of spherical trace depressions.
Ru. The electrophotographic light receiving member of the present invention will be described below.
The shape of the surface of the support and its preferred manufacturing example are described in this section.
As will be explained with reference to FIGS. 21 and 22, the present invention
Shape of support in light-receiving member and manufacturing method thereof
is not limited to this. FIG. 21 shows the electrophotographic light receiving member of the present invention.
A typical example of the surface shape of the support is shown below.
Partially enlarged and schematic illustration of a part of the uneven shape
It is something. In FIG. 21, 1601 is a support, 1602
is the support surface, 1603 is a rigid true sphere, and 1604 is
It shows a spherical trace depression. Furthermore, FIG. 21 shows how to obtain the surface shape of the support.
An example of a preferred manufacturing method is also shown. Immediately
In other words, the rigid true sphere 1603 is placed from the support surface 1602.
Let it fall naturally from a predetermined height to the support surface.
By colliding with 1602, the spherical depression 16
04 can be formed. And then
Using a plurality of rigid true spheres 1603 with approximately the same diameter R',
Drop them from the same height h, simultaneously or sequentially.
By lowering the support surface 1602,
A plurality of spheres having almost the same radius of curvature R and the same width D
A shaped recess 1604 can be formed. As mentioned above, there are multiple spherical trace depressions on the surface.
The following is a typical example of a support with an uneven shape formed by
It is shown in Figure 22. In the same figure, 1701 is the support
The dotted line 1702 indicates the position of the convex part of the concave and convex part.
703 indicates a rigid true sphere, and 1704 indicates a concave surface.
vinegar. By the way, the support for the electrophotographic light receiving member of the present invention
The curvature half of the uneven shape due to the spherical trace depression on the surface of the holding body
The diameter R and width D of the light receiving member of the present invention are
Effectively prevents interference fringes in
This is an important factor in achieving this goal. Inventor
As a result of various experiments, they discovered the following:
did. That is, the radius of curvature R and the width D are as follows: D/R≧0.035 If it satisfies the
0.5 or more Newton rings due to ring interference
It will exist. Furthermore, the following formula: R/D≧0.055 If it satisfies the
There is one or more Newton rings due to ring interference.
There will be. Because of these things, it occurs throughout the photoreceptor member.
Interference fringes are dispersed within each trace depression, allowing light reception.
In order to prevent the occurrence of interference fringes on parts,
The D/R should be 0.035, preferably 0.055 or more. is desirable. In addition, the width D of the unevenness due to the trace depression is at most
About 500μm, preferably 200μm or less, more preferably
The thickness is preferably 100 μm or less. Figure 23 shows the unevenness formed by the above method.
The slope of the unevenness on the support body 2301 having the shape
A photoreceptor with a photoreceptor layer 2300 along the surface.
It shows the material. At this time, the free surface 2306 is arranged
At the interface formed in the photoreceptive layer 2300
Since the degree of inclination is different, the free surface 2306 is aligned
Reflection at the interface formed in the light-receiving layer 2300
Each has a different angle of light reflection. Therefore, it corresponds to the so-called Newton ring phenomenon.
Shearing interference occurs and interference fringes are separated within the depression.
They will be scattered. This allows such light reception.
The image that appears through the container member is microscopically
Even if interference fringes appear, they cannot be seen.
It is something that cannot be grasped visually. Immediately
In other words, the support 2301 having such a surface shape
In use, a multilayered photoreceptive layer 2300 is placed thereon.
In the light-receiving member formed by forming the light-receiving layer 2
300, the light passes through the layer interface and the support surface.
formed by reflection and their interference.
To efficiently prevent images from becoming striped. In FIG. 23, 2302 is a long wavelength photosensitive layer;
2303 is a charge injection blocking layer, 2304 is a photoconductive layer
layer, 2305 is the surface layer, and 2307 is the adhesive layer.
Ru. adhesion layer In the present invention, the adhesion layer contains nitrogen atoms, oxygen atoms,
At least one carbon atom and a silicon atom are required.
At least one of a hydrogen atom and a halogen atom depending on
It is composed of an amorphous material containing. Change
The adhesion layer controls conductivity as constituent atoms.
May contain substances. In other words, it improves the adhesion between the support and the charge injection blocking layer.
The main purpose of the layer is to raise the temperature. Also, legend
By containing a substance that controls conductivity in the layer.
transports charge between the support and the charge injection blocking layer.
can be carried out more efficiently. Nitrogen atoms, oxygen atoms, and carbon atoms contained in the layer
at least one of the children and optionally contained in the layer.
At least one of a hydrogen atom or a halogen atom
All substances that control conductivity are present in the layer.
It may be finely uniform, or it may be non-uniform in the layer thickness direction.
It may be distributed in a distribution state. contained in the adhesive layer formed in the present invention.
The amount of carbon, oxygen, or nitrogen used can be adjusted as desired.
Although it must be determined as appropriate, preferably from 0.0005 to
70 at%, more preferably 0.001-50 at%, optimal
It is desirable that the content be 0.002 to 30 at%. The thickness of the adhesion layer depends on adhesion, charge transport efficiency, and production.
It can be determined appropriately considering efficiency, but preferably 0.01
~10μm, more preferably 0.02~5μm
desirable. Amount of hydrogen atoms or halogen contained in the adhesive layer
amount of hydrogen atoms or sum of amounts of hydrogen atoms and halogen atoms
is preferably 0.1 to 70 atom%, more preferably
0.5 to 50 atom%, optimally 1.0 to 30 atom%
is desirable. Long wavelength photosensitive layer The long wavelength photosensitive layer in the present invention is made of A-SiGe
(H,X) and contained in the layer
Ni atoms are uniformly distributed throughout the layer.
Or, it may be contained evenly in the layer thickness direction.
However, the distribution concentration may be non-uniform.
However, in both cases, parallel to the surface of the support
In the in-plane direction, it is uniformly distributed and evenly contained.
This makes the properties uniform in the in-plane direction.
This is also necessary from a measurement point of view. That is, the long wavelength photosensitive layer
are uniformly contained in the layer thickness direction, and the above-mentioned
The side opposite to the side where the support is provided (light-receiving side)
the free surface side of the layer) versus the support side
or,
The long wavelength photosensitive layer is
contained within. In the light receiving member of the present invention, as described above,
Germanium atoms contained in the long wavelength photosensitive layer
In the layer thickness direction, the distribution state of
The distribution state is taken in the in-plane direction parallel to the surface of the support.
It is desirable to have a uniform distribution state. Also, in one of the preferred embodiments, a long
Distribution of germanium atoms in the wavelength photosensitive layer
The state is such that germanium atoms are continuously distributed throughout the entire layer.
Evenly distributed, germanium atoms are distributed in the layer thickness direction.
The cloth density C is from the support side toward the charge injection blocking layer.
Given the decreasing change, long wavelength light sensitivity
Excellent affinity between the optical layer and the charge injection blocking layer
In addition, as will be described later, there is a gap at the end of the support.
Extremely increase the distribution concentration C of rumanium atoms
Therefore, when using a semiconductor laser, etc.,
The photoconductive layer absorbs almost no light at long wavelengths.
In the long wavelength photosensitive layer, virtually complete absorption is achieved.
interference caused by reflection from the support surface.
It can be prevented. 2 to 7 show the photoreceptor in the present invention.
Germani contained in the long wavelength photosensitive layer of the member
Typical case where the distribution state of aluminum in the layer thickness direction is non-uniform
An example is shown. In Figures 2 to 7, the horizontal axis is germanium.
The vertical axis represents the distribution concentration C of atoms in the long wavelength photosensitive layer.
indicates the layer thickness of t_Bis the long wavelength photosensitive layer on the support side.
The position of the end face is t_Tis the long wavelength on the side opposite to the support side
The position of the end face of the photosensitive layer is shown. That is, germanium
The long wavelength photosensitive layer containing mu atoms is t_BT from the side_T
Layering takes place towards the sides. Figure 2 shows the gel contained in the long wavelength photosensitive layer.
The first source of the distribution state of rumanium atoms in the layer thickness direction
A type example is shown. In the example shown in Figure 2, the germanium atom
The surface on which the contained long-wavelength photosensitive layer is formed and the corresponding
Interface position t where the long wavelength light contacts the surface_BMoret₁rank
Up to this point, the distribution concentration C of germanium atoms is C₁
Germanium atoms are formed while taking a certain value.
contained in the long wavelength photosensitive layer, located at the position t₁than
Concentration C₂The interface position t_Tgradually and continuously until
has been reduced. Interface position t_TGermani in
The distribution concentration C of um atoms is C₃It is said that In the example shown in Figure 3, the contained
The distribution concentration C of rumanium atoms is at position t_BMore position_T
Concentration C up to_Fourgradually and continuously decreasing from
position t_TConcentration C at_FiveForm a distribution state such that
are doing. In the case of Figure 4, position t_BMore position₂until then
The distribution concentration C of rumanium atoms is the concentration C₆and a constant value
and position t₂and position t_TGradually, between
Continuously decreased position t_TIn , the distribution concentration C
is substantially zero (here, substantially zero and
is below the detection limit amount. ) In the case of Figure 5, the distribution concentration of germanium atoms is
Degree C is position t_BMore position_Tup to the concentration C₈Than
Continuously gradually decreased position t_Tsubstantially in
It is said to be zero. In the example shown in Figure 6, germanium atoms
The distribution concentration C of is given by the position t_Band position t₃In between,
Concentration C₉is a constant value, and the position t_TIn the case of concentration
C_TenIt is said that position t₃and position t_TThe distribution density is
The degree C is a linear function of the position t₃More position_Tup to
has been reduced. In the example shown in FIG. 7, the position t_BMore position_T
Until , the distribution concentration C of germanium atoms is
degree C₁₁It decreases linearly to more effectively reach zero.
There are a few. As described above, from Fig. 2 to Fig. 7, long wavelength photosensitive
germanium atoms contained in the layer in the layer thickness direction
As we have explained some typical examples of distribution states, the present invention
In the light, on the support side, germanium
It has a part with a high distribution concentration C of atoms, and the interface t_Tto the side
In this case, the distribution concentration C is smaller than that on the support side.
germanium atom with a reduced portion
When the distribution state is provided in the long wavelength photosensitive layer
is cited as one of the preferred examples. Germani
germanium as the distribution state of um atoms in the layer thickness direction.
The maximum value Cmax of the distribution concentration of umium atoms is
Preferably less than 1000 atomic ppm with respect to the sum of
above, more preferably 5000 atomic ppm or more, optimally 1
×10^FourThe distribution state is such that it is said to be more than atomic ppm.
It is preferable that the layer be formed in such a manner as to obtain the desired result. In the present invention, the long wavelength photosensitive layer contains
The content of germanium atoms in the present invention is as follows:
Appropriately as desired so that the purpose is effectively achieved
However, it is preferable for the sum with silicon atoms.
Preferably 1~10×10^FiveAtomic ppm, preferably 100~
9.5×110^FiveAtomic ppm, optimally 500 to 8×10^Fiveatom
Preferably in ppm. The long wavelength photosensitive layer further controls the conductivity.
at least one of a substance, an oxygen atom, or a nitrogen atom
May contain. In addition, as the substance that controls the conductivity, semi-
In the field of conductors, we can list so-called impurities.
In the present invention, the period giving p-type conduction characteristics is
Atoms belonging to group in the Table of Contents (hereinafter referred to as "group atoms")
say. ), or periodic table number giving N-type conduction characteristics.
Atoms belonging to the group (hereinafter referred to as "group atoms")
use Specifically, as a group atom, B (boron)
element), Al (aluminum), Ga (gallium), In
(B), Tl (Thallium), etc., especially B,
Ga is preferred. As group atoms, specific
include P (phosphorus), As (arsenic), Sb (antimony), Bi
(bismuth), etc., with P and As being particularly suitable.
Ru. In the present invention, the long wavelength photosensitive layer contains
The content of the substance that controls the conduction properties is preferably
Preferably 0.01~5×10^FiveAtomic ppm, more preferably
is 0.5~1×10^FourAtomic ppm, optimally 1-5×10³
Preferably, it is expressed in atomic ppm. In the present invention, A-SiGe (H,
For example, to form a long-wavelength photosensitive layer,
-Discharge method, microwave discharge method, sputtering
Discharge phenomena such as ion plating method or ion plating method
It is made by a vacuum deposition method using . example
For example, by glow discharge method, A-SiGe(H,X)
To form a long wavelength photosensitive layer consisting of
Basically, Si supply that can supply silicon atoms (Si)
Supply raw material gas and germanium atoms (Ge) for
Feedstock gas for Ge supply and water if necessary
Raw material gas or/and halogen source for introducing elementary atoms (H)
The raw material gas for introducing the child
The gas is introduced into the deposition chamber at the desired pressure state, and then
Create a glow discharge inside the device and place it in a predetermined position.
A-SiGe (H,
It is sufficient to form a layer consisting of X). Also, Germani
In order to contain umium atoms in a non-uniform distribution state,
The desired rate of change curve for the distribution concentration of germanium atoms
from A-SiGe(H,X) while controlling according to
It is sufficient to form a layer that Also, sputtering method
For example, inert materials such as Ar, He, etc.
gas or a mixture of gases based on these gases
A target composed of Si in an atmosphere, or
This target and a target composed of Ge
or a mixed tar of Si and Ge.
He, Ar, etc. can be added as necessary using a
The raw material gas for Ge supply diluted with dilution gas is
Hydrogen atoms (H) or/and halogen atoms as necessary
The gas for introducing the child (X) into the deposition chamber for sputtering.
Introduce and form a plasma atmosphere of the desired gas
It is accomplished by Distribution of germanium atoms
In order to make the temperature uniform, the raw material gas for the Ge supply
The gas flow rate at the base is controlled according to the desired curvature of change.
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 the evaporation board as a
Thermal method, electron beam method (FB method), etc.
The flying evaporates are heated and evaporated into the desired gas.
Except for passing through the plasma atmosphere, spatter
This can be done in the same way as the ring method.
Ru. Raw material gas for supplying Si used in the present invention
SiH is a substance that can become_Four,Si₂H₆,Si₃H₈，
Si_FourH_Tensilicon hydride in a gaseous state or capable of being gasified, such as
Elements (silanes) are listed as being effectively used.
In particular, ease of handling during layer creation work and Si supply
SiH from the point of view of good feeding efficiency, etc._Four,Si₂H₆is preferable
It is mentioned as a thing. Substances that can be used as raw material gas for Ge supply include:
GeH_Four,Ge₂H₆,Ge₃H₈,Ge_FourH_Ten,Ge_FiveH₁₂，
Ge₆H₁₄,Ge₇H₁₆,Ge₈H₁₈,Ge₉H₂₀gaseous such as
germanium hydride is effective
It is used for layer creation, especially for layer creation.
Ease of handling during work, good Ge supply efficiency, etc.
So, GeH_Four,Ge₂H₆,Ge₃H₈is preferred.
can be mentioned. For introducing halogen atoms used in the present invention
Many halogenated gases are effective as raw material gases for
For example, halogen gas, halogen
compounds, interhalogens, halogen-substituted
Gaseous or gasifiable materials such as silane derivatives
Preferred examples include rogene compounds. Furthermore, silicon atoms and halogen atoms
Constituent halves in a gaseous state or capable of being gasified
Silicon hydride compounds containing rogen atoms are also effective.
In the present invention, the following can be mentioned. Halogen compounds that can be suitably used in the present invention
Specifically, the substances include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF₃，
BrF_Five,BrF₃,IF₃,IF₇, ICl, IBr, etc.
Intermediate compounds can be mentioned. Silicon compounds containing halogen atoms, so-called halogens
Examples of silane derivatives substituted with carbon atoms include
For example, SiF_Four,Fi₂F₆,SiCl_Four, SiBr_Fouretc.
Silicon rogenide is preferred.
I can do it. Adopts silicon compounds containing such halogen atoms
The characteristic light guide of the present invention is produced by the glow discharge method.
When forming electrical parts, raw material gas for Ge supply is required.
Hydrogenation as a raw material gas that can supply Si along with gas
can be deposited on the desired support without the use of silicon gas.
Long wavelength photosensitivity made of A-SiGe containing rogen atoms
A light layer can be formed. According to the glow discharge method, the length containing halogen atoms is
When manufacturing a wavelength-sensitive layer, basically, e.g.
For example, silicon halide, which is the raw material gas for Si supply, and
Germanium hydride, which is the raw material gas for Ge supply
and Ar,H₂, He and other gases at a predetermined mixing ratio.
The deposit that forms the long wavelength photosensitive layer is adjusted to the flow rate.
into the storage room and generate a glow discharge to remove these gases.
By forming a plasma atmosphere of
capable of forming a long wavelength photosensitive layer on a desired support
However, it is easier to control the ratio of hydrogen atoms introduced.
Hydrogen gas is added to these gases in order to
Alternatively, a desired amount of silicon compound gas containing hydrogen atoms may also be mixed.
They may be combined to form a layer. In addition, each gas can be used not only as a single species but also in a predetermined mixing ratio.
It is safe to use a mixture of multiple types.
Ru. Sputtering method, ion plating method
In either case, halogen atoms are added to the layer formed.
To introduce the above-mentioned halogen compounds or the above-mentioned
A silicon compound gas containing halogen atoms is introduced into the deposition chamber.
to form a plasma atmosphere of the gas.
That's fine. In addition, when introducing hydrogen atoms, hydrogen atom guide
Required raw material gas, e.g. H₂, or the above
Gases such as silanes and/or germanium hydride
The gas is introduced into a deposition chamber for sputtering of the same type.
All that is required is to form a plasma atmosphere of gases. In the present invention, raw materials for introducing halogen atoms
The halogen compounds or halogens listed above as gases
Silicon compounds containing gen are used as effective ones.
In addition, HF, HCl,
Hydrogen halides such as HBr, Hi, SiH₂F₂,SiH₂I₂，
SiH₂Cl₂,SiHCl₃,SiH₂Br₂,SiHBr₃etc. halogen
Substituted silicon hydride, and GeHF₃, GeH₂F₂，
GeH₃F, GeHCl₃, GeH₂Cl₂, GeH₃Cl,
GeHBr₃, GeH₂Br₂, GeH₃Br, GeHI₃，
GeH₂I₂, GeH₃Hydrogenated halogenated germanium such as I
Halo containing hydrogen atoms as one of its constituent elements, such as
Genide, GeF_Four, GeCl_Four, GeB_Four, GeI_Four, GeF₂，
GeCl₂, GeBr₂, GeI₂germanium halides such as
Substances that are in a gaseous state or can be gasified, such as
Listed as an effective starting material for forming long-wavelength photosensitive layers.
You can do it. Among these substances, halogenated substances containing hydrogen atoms
When forming a long-wavelength photosensitive layer, halogens are added to the layer.
Control of electrical or photoelectric properties at the same time as introducing atoms
Hydrogen atoms, which are extremely effective for control, are also introduced, so this book
In the invention, it is used as a suitable raw material for introducing halogen.
used. Hydrogen atoms are structurally introduced into the long wavelength photosensitive layer.
In addition to the above,₂, or SiH_Four,Si₂H₆，
Si₃H₈,Si_FourH_TenTo supply Ge with silicon hydride such as
germanium or germanium compound, or
is GeH_Four,Ge₂H₆,Ge₃H₈,Ge_FourH_Ten,Ge_FiveH₁₂，
Ge₆H₁₄,Ge₇H₁₆,Ge₈H₁₈,Ge₉H₂₀Hydrogenation of etc.
Silicon or silicon for supplying germanium source and Si
Discharge occurs when a silicon compound and a silicon compound coexist in the deposition chamber.
This can also be done by causing . In a preferred embodiment of the invention, the photoreceptor formed
Hydrogen atoms contained in the long wavelength photosensitive layer of the container member
The amount of (H) or the amount of halogen atom (X) or the amount of hydrogen atom and
The sum of the amounts of rogene atoms (H+X) is preferably:
0.01-40 atomic%, more preferably 0.05-30 atomic%
%, optimally 0.1 to 25 atom%.
stomach. Hydrogen atoms (H) or / contained in the long wavelength photosensitive layer
and to control the amount of halogen atoms (X), e.g.
Support temperature or/and hydrogen atom (H) or halogen
of the starting material used to contain the ion atom (X).
Controls the amount introduced into the deposition system, discharge power, etc.
Just do it. In the present invention, nitrogen atoms are added to the long wavelength photosensitive layer.
In order to contain nitrogen, nitrogen is added during the formation of the long wavelength photosensitive layer.
Long-wavelength photosensitivity using starting materials for introducing elementary atoms
used with starting materials for layer formation to form
It may be contained in the layer while controlling its amount. Forming a long wavelength photosensitive layer by glow discharge method
As a starting material for introducing nitrogen atoms,
A gaseous substance whose constituent atoms are at least nitrogen atoms.
is most of the gasified substances that can be gasified.
can be used. For example, a material whose constituent atoms are silicon atoms (Si).
Raw material gas and raw material gas whose constituent atoms are nitrogen atoms (N)
and hydrogen atoms (H) or halogen atoms as necessary.
Desired mixing ratio of raw material gas containing atoms (X)
or halogen atoms.
Raw material gas containing (Si) as a constituent atom and nitrogen atom (N)
and a raw material gas containing hydrogen atoms (H) as constituent atoms,
This can also be mixed at the desired mixing ratio or by
A raw material gas whose constituent atoms are silicon atoms (Si),
Silicon atom (Si), nitrogen atom (N) and hydrogen atom (H)
It is used by mixing with a raw material gas whose constituent atoms are
can be used. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
Nitrogen atoms (N) are formed in the raw material gas whose constituent atoms are
A mixture of raw material gases containing atoms may be used. What can be used as a raw material gas for introducing nitrogen atoms (N)
The starting materials that can be effectively used include the constituent atoms of N.
Or, for example, nitrogen containing N and H as constituent atoms.
element (N₂), ammonia (NH₃), hydrazine
(H₂NNH₂), hydrogen azide (HN₃), ammonium 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, introduction of nitrogen atom (N)
In addition to this, it is also possible to introduce halogen atoms (X).
From the point, nitrogen trifluoride (F₃N), nitrogen tetrafluoride
(F_FourN₂) and other halogenated nitrogen compounds.
I can do it. In the present invention, nitrogen is contained in the long wavelength photosensitive layer.
and/or oxygen atoms.
Ru. Acid for introducing oxygen atoms into the long wavelength photosensitive layer
For example, oxygen is used as a raw material gas for introducing elementary atoms.
(O₂), ozone (O₃), nitric oxide (NO), dioxide
Nitrogen (NO₂), nitrogen monoxide (N₂O), sesquioxide
Nitrogen (N₂O₃), nitrogen tetroxide (N₂O_Four), pentoxide
Nitrogen (N₂O_Five), nitrogen trioxide (NO₃), silicon raw material
Constituent atoms include Si (Si), oxygen atom (O), and hydrogen atom (H)
For example, disiloxane (H₃SiOSiH₃),
Trisiloxane (H₃SiOSiH₂OSiH₃) etc.
Examples include siloxane. Forming a long wavelength photosensitive layer by sputtering method
In order to form a long wavelength photosensitive layer, single crystal or
is polycrystalline Si wafer or Si₃N_Fourwafer,
Or Si and Si₃N_FourWax containing a mixture of
- These are used as targets for various gases.
This can be done by sputtering in the atmosphere.
Good. For example, using a Si wafer as a target
If so, the nitrogen atom and optionally the hydrogen atom or/
and raw material gas for introducing halogen atoms.
Dilute with diluting gas as necessary and sputter.
These gases are introduced into the deposition chamber for gas purification.
Sputtering the Si wafer by forming a zuma
Just Google it. Also, separately, Si and Si₃N_Fourtarget different from
as or Si and Si₃N_FourA single target mixed with
By using a sputter gas
in an atmosphere of diluent gas or at least water as
Elementary atoms (H) and/or halogen atoms (X) as constituent atoms
sputtering in a gas atmosphere containing
It is accomplished by As the raw material gas for introducing oxygen atoms, the above-mentioned
Nitrogen atoms in source gas shown in glow discharge example
Even if the raw material gas for introduction is sputtering,
Can be used as an effective gas. In the present invention, when forming a long wavelength photosensitive layer,
Then, the distribution concentration C(N) of nitrogen atoms contained in the layer is
Change the distribution in the layer thickness direction to obtain the desired distribution shape in the layer thickness direction.
To form a layer with a depth profile,
In the case of glow discharge, changing the distribution concentration C(N)
The starting material gas for nitrogen atom introduction to be
The gas flow rate is varied accordingly according to the desired rate of change curve.
However, this can be achieved by introducing it into the deposition chamber.
Ru. Normal use, e.g. manually or with an external drive motor
The route of the gas flow system is
Adjust the opening of the specified needle valve inside the
All you have to do is change it as needed. When formed by sputtering method, nitrogen
Change the distribution concentration C(N) of atoms in the layer thickness direction
to obtain the desired distribution state of nitrogen atoms in the layer thickness direction.
To form a (depth profile), firstly,
As with the low discharge method, for nitrogen atom introduction.
starting material is used in gaseous state and the gas is introduced into the deposition chamber.
The flow rate of gas introduced into the tank can be changed as desired.
It is achieved by making it . Second, the target for sputtering,
For example, Si and Si₃N_Fourusing a mixed target with
Si and Si₃N_FourThe mixing ratio with
The thickness of the target layer is changed in advance.
This is accomplished by Nitrogen atoms (N) contained in the long wavelength photosensitive layer
amount, or amount of oxygen atoms (O), or nitrogen atoms and oxygen atoms
The sum of the amounts (N+O) is preferably 0.01 to 40 atoms
%, more preferably 0.05 to 30 atomic %, optimally
The content is preferably 0.1 to 25 at%. A substance that controls conduction properties in the long wavelength photosensitive layer
properties, e.g. group atoms or structure of group atoms
In order to introduce
Commercially available starting materials or starting materials for the introduction of group atoms
A long-wavelength photosensitive layer is formed in the deposition chamber in a gaseous state.
It can be introduced along with other starting materials for
stomach. Such starting materials and compounds for the introduction of group atoms
Possible materials are gaseous or
can be easily gasified, at least under layer-forming conditions.
It is desirable that those with the following criteria be adopted. Such a first
Specifically, boron is used as a starting material for introducing group atoms.
For introducing atoms, B₂H₆,B_FourH_Ten,B_FiveH₉，
B_FiveH₁₁,B₆H_Ten,B₆H₁₂,B₆H₁₄Boron hydride, such as
BF₃, BCl₃,BBr₃Boron halides such as
It will be done. In addition, AlCl₃,GaCl₃, Ga(CH₃)₃，
InCl₃, HlCl₃etc. can also be mentioned. As a starting material for the introduction of group atoms,
It is effectively used for introducing phosphorus atoms.
So, PH₃,P₂H_FourHydrogenated phosphorus, PH etc._FourI, P.F.₃，
P.F._Five, PCl₃, PCl_Five, PBr₃, PBr_Five, P.I.₃etc. halogen
Examples include phosphorus chloride. In addition, AsH₃,AsF₃，
AsCl₃, AsBr₃,AsF_Five,SbH₃,SbF_Five,SbF₃，
SbCl₃,SbCl_Five, BiH₃, BiCl₃, BiBr₃etc. also group
Listed as effective starting materials for atom introduction
I can do it. In the present invention, the layer thickness of the long wavelength photosensitive layer is preferably
preferably 30 Å to 50 μm, more preferably 40 Å to
40μm, optimally 50Å to 30μm.
stomach. Charge injection blocking layer The charge injection blocking layer in the present invention is A-Si(H,
X) configured to control conductivity in the entire layer area of the layer.
distribute the substance uniformly or preferably in large quantities on the support side.
It is contained in a non-uniform state like cloth. Need more
Oxygen is added to all or part of the layer depending on the
atoms or/and nitrogen atoms uniformly or preferably
is contained in a non-uniform state so that it is mostly distributed on the support side.
By having the layer between the layer and the long wavelength photosensitive layer,
Improve adhesion and adjust band gap.
I can do that. The conductivity control layer contained in the charge injection blocking layer
The material to be controlled is the so-called in the semiconductor field.
Impurities can be mentioned, and in the present invention,
Elements belonging to group of the periodic table that give p-type conductivity
(hereinafter referred to as “Group atoms”), or N-type conduction
Atoms belonging to groups of the periodic table that give properties (hereinafter
They are called "group atoms." ) is used. group atoms and
Specifically, B (boron), Al (aluminum)
), Ga (gallium), In (indium), Tl (tali),
Among them, B and Ga are particularly suitable. No.
Specifically, the group atoms include P (phosphorus) and As (arsenic).
), Sb (antimony), Bi (bismuth), etc.
Particularly suitable are P and As. In FIGS. 8 to 12, the charge injection blocking layer contains
group atoms or the portion of group atoms in the layer thickness direction
Typical examples of cloth conditions are shown. In the examples in Figures 8 to 12, the horizontal axis is the group.
The distribution concentration C of atoms or group atoms is shown, and the vertical axis is the charge.
Indicates the layer thickness t of the injection blocking layer, t_Bis the interface on the support side
position, t_Tis the position of the interface on the opposite side from the support side.
show. That is, the charge injection blocking layer is t_BT from the side_Ttowards the side
Layer formation is then carried out. FIG. 8 shows the charge injection blocking layer containing
The distribution state of group atoms or group atoms in the layer thickness direction
One typical example is shown. In the example shown in Figure 8, the interface position t_Bthan t_Fourof
Up to the position, the group atom or the concentration of group atom
Degree C is C₁₂It is contained while taking a certain value, and the position
Placement_FourTherefore, the distribution concentration C is the interface position t_TC up to₁₃Yo
has been gradually and continuously reduced. Interface position t_Tto
In this case, the distribution concentration C is C₁₄It is said that In the example shown in FIG.
The distribution concentration C of group atoms or group atoms is at position t_BYo
position t_TC up to₁₅gradually and continuously decreasing from
and position t_TC in₁₆Shape the distribution state such that
has been completed. In the example shown in Figure 10, the group atoms or
The distribution concentration C of group atoms is given by the position t_Band position t_FiveBetween
In this case, C₁₇is a constant value, and the position t_TIn
is C₁₈It is said that position t_Fiveand position t_TThe distribution is between
The concentration C is linearly proportional to the position t_FiveMore position_Tuntil
has been reduced. In the example shown in FIG. 11, the distribution concentration C
is position t_BMore position₆Until C₁₉Take a constant value of
Placement₆More position_TUntil C₂₀More C_{twenty one}linear function up to
It is said that the distribution state decreases to . In the example shown in FIG. 12, the distribution concentration C
is position t_BMore position_Tup to C_{twenty two}takes a constant value. In the present invention, the charge injection blocking layer contains group atoms or
is due to the large distribution of group atoms on the support side.
When contained in a cloth state, group atoms or group elements
The maximum value of the distribution concentration value of the child is usually less than 50 atomic ppm.
above, preferably 80 atomic ppm or more, optimally 100 atomic ppm
In order to achieve a distribution state that is considered to be more than ppm
Preferably, it is layered. In the present invention, the charge injection blocking layer contains
The content of group atoms or group atoms is
as desired so that the purpose of light is effectively achieved.
It can be determined as appropriate, but preferably 30 to 5 x 10^Fouratom
ppm, more preferably 50-1×10^FourAtomic ppm, maximum
Suitably 1×10²~5×10³It is hoped that it will be expressed as atomic ppm.
It's a beautiful thing. As mentioned above, the charge injection blocking layer is made of oxygen atoms or
Due to the inclusion of nitrogen atoms,
Close contact between the long-photosensitive layer 102 and the charge injection blocking layer
improvement of the properties and the relationship between the charge injection blocking layer and the photoconductive layer.
Improving adhesion or adjusting the band gap of the layer
is planned. FIGS. 13 to 19 show the charge injection blocking layer.
Layer thickness direction of oxygen atoms and/or nitrogen atoms
A typical example of the distribution state of is shown. In the examples shown in Figures 13 to 19, the horizontal axis is oxygen.
The vertical axis represents the distribution concentration C of atoms and/or nitrogen atoms.
Indicates the layer thickness t of the charge injection blocking layer, t_Bis on the support side
The interface position is t_Tis the position of the interface on the opposite side from the support side.
Indicates the location. That is, the charge injection blocking layer is t_BT from the side_T~ side
Layer formation is carried out towards. Figure 13 shows the acid contained in the charge injection blocking layer.
Distribution state of elementary atoms and/or nitrogen atoms in the layer thickness direction
The first typical example is shown below. In the example shown in Fig. 13, the interface position t_BMoret₇of
Containing oxygen atoms and/or nitrogen atoms up to the position
concentration C is C_{twenty three}Although it takes a certain value,
Placement₇Therefore, the distribution concentration C is the interface position t_TC up to_{twenty four}Yo
has been gradually and continuously reduced. Interface position t_Tto
In this case, the distribution concentration C is C_{twenty five}It is said that In the example shown in FIG. 14, it contains
The distribution concentration C of oxygen atoms and/or nitrogen atoms is the position
t_BMore position_TC up to₂₆gradually and continuously decreases from
a little position t_TC in₂₇The distribution state becomes
is forming. In the case of Figure 15, position t_BMore position₈Until
The distribution concentration C of oxygen atoms and/or nitrogen atoms is C₂₈
is assumed to be a constant value, and the position t₈and position t_Tbetween
is gradually and continuously decreased, and the position t_TIn the
It is essentially zero. In the case of Figure 16, oxygen atoms or/and nitrogen
Atom is at position t_BMore position_Tuntil the distribution concentration C
is C₃₀The position t is gradually decreased more continuously_TAt
It is said that it is essentially zero. In the example shown in FIG. 17, oxygen atoms or
and the distribution concentration C of nitrogen atoms is at the position t_BMore position₉
Until C₃₁Take a constant value of and position t₇More position_Tto
is C₃₁More C₃₂A state of distribution that decreases linearly until
It is said that In the example shown in FIG.
and the distribution concentration C of nitrogen atoms is at the position t_Band position t_Tenwhile
In C₃₃is a constant value, and the position t_Tin
C₃₅It is said that position t_Tenand position t_TBetween
The distribution concentration C is linearly distributed at the position t_TenMore position_Tto
has been reduced until In the example shown in FIG. 19, the distribution concentration C
is position t_BMore position_Tup to C₃₆takes a constant value. In the present invention, the charge injection blocking layer 103 is an oxygen source.
or/and nitrogen atoms on the support 101 side.
When contained in a large distribution state, oxygen atoms
or/and distribution concentration value of nitrogen atoms or the sum of both atoms
The maximum value of is preferably 500 atomic ppm or more, preferably
800 atomic ppm or more, optimally 1000 atomic ppm or more.
Layer formation to achieve the distribution state shown above.
It is desirable that Contained in the charge injection blocking layer in the present invention
Content of oxygen atoms and/or nitrogen atoms or both
Overall, the objectives of the present invention are effectively achieved.
Although it can be determined appropriately according to the desired condition, it is preferable that
0.001-50 atomic%, more preferably 0.002-40 atomic%
%, ideally 0.003 to 30 at%.
Yes. In the present invention, the layer thickness of the charge injection blocking layer is determined as desired.
Obtaining electrophotographic properties and economical effects, etc.
From the point, preferably 0.01 to 10μ, more preferably
The desired value is 0.05~8μ, optimally 0.1~5μ.
stomach. photoconductive layer The photoconductive layer in the present invention is A-Si(H,X)
A photoconductive material that satisfies the desired electrophotographic properties.
have characteristics. In addition, a substance that controls conductivity is applied to the entire layer area.
within the range that does not impair the properties required for the layer.
May be contained. In addition, the characteristics required for the layer are provided in the entire layer area.
Carbon atoms, oxygen atoms and
It may contain at least one nitrogen atom. As the substance that controls the conductivity, the above-mentioned electrical
Similar to the charge injection blocking layer, group atoms and
can be used. Group elements are present in the entire layer region of the photoconductive layer in the present invention.
If it contains children or group atoms, it is mainly conductive.
It has the effect of controlling type and/or conductivity, and
Relatively small content of group atoms or group atoms
and preferably 1×10^-3~3×10²atomic ppm,
More preferably 5×10^-3~Ten²Atomic ppm, optimally
Ten^-2It is desirable that it be ~50 atomic ppm. Furthermore, oxygen is present in the entire layer region of the photoconductive layer in the present invention.
If it contains atoms or nitrogen atoms, it is mainly
dark resistance and the difference between the charge injection blocking layer and the photoconductive layer.
It has the effect of improving adhesion, but especially the light
Oxygen atom content to prevent deterioration of conductive properties
Although it is considered to be a relatively small amount, it is desirable. In the case of nitrogen atoms, in addition to the above points, e.g.
Increased photosensitivity in coexistence with group atoms, especially B.
You can measure the top. Contained in the photoconductive layer
Content of oxygen atoms or nitrogen atoms, or the sum of both
is preferably 1×10^-3~Ten³Atomic ppm, more preferred
5×10^-2~5×10²Atomic ppm, optimally 1×
Ten^-1~2×10²Preferably in atomic ppm. In the present invention, the purpose is effectively achieved.
It is formed on the support and constitutes a part of the photoreceptive layer.
The photoconductive layer formed has the semiconductor properties shown below,
A-Si(H,
X). p-type A-Si (H,X)...acceptor only
including. Or between donor and acceptor
Contains both and has a high relative concentration of acceptor
thing. In the type of p-type A-Si(H,X)...
If the acceptor concentration (Na) is low or
has a low relative concentration of acceptor. n-type A-Si(H,X)...contains only a donor
thing. or include both donor and acceptor.
and those with a high relative concentration of donor. In the type of n-type A-Si(H,X)...
If the donor concentration (Nd) is low or the donor
The relative concentration of - is low. i-type A-Si(H,X)……NaNdO also
or NaNd. In the present invention, the charge injection blocking layer or/and the light
Suitable as a halogen atom (X) contained in a conductive layer
These are F, Cl, Br, and I, especially F and Cl.
It is desirable. In the present invention, it is composed of A-Si(H,X).
form a charge injection blocking layer and/or a photoconductive layer
For example, glow discharge method, microwave discharge method,
Sputtering method or ion plating
It is made by a vacuum deposition method that utilizes discharge phenomena such as
be done. For example, by glow discharge method, A-Si
To form an amorphous layer composed of (H,X),
Basically, it is a Si donor that can supply silicon atoms (Si).
Along with the raw material gas for supply, there is also a gas for introducing hydrogen atoms (H).
/ and raw material gas for introducing halogen atoms (X),
The chamber is introduced into a deposition chamber in which the pressure can be reduced.
Create a glow discharge inside the device and place it in a predetermined position.
A-Si(H,X)
What is necessary is to form a layer consisting of. Also, spatsutari
For example, when forming by the heating method, Ar, He, etc.
Mixtures based on inert gases or these gases
A target composed of Si is spun in a gas atmosphere.
When sputtering, hydrogen atoms (H) or/and halo
The gas for introducing Gen atoms (X) is added to the sputtering deposit.
It would be good to introduce it to the storage room. Raw material gas for supplying Si used in the present invention
As, SiH_Four,Si₂H₆,Si₃H₈,Si_FourH_Tenmoths such as
Silicon hydride (silane) in gaseous or gasifiable form
) are mentioned as those that can be effectively used, and
In addition, it is easy to handle the layer creation work, and has good Si supply efficiency.
SiH in terms of_Four,Si₂H₆are listed as preferable.
It will be done. For introducing halogen atoms used in the present invention
Many halogenated gases are effective as raw material gases for
For example, halogen gas, halogen
compounds, interhalogens, halogen-substituted
Gaseous or gasifiable materials such as silane derivatives
Preferred examples include rogene compounds. Furthermore, silicon atoms and halogen atoms
Constituent halves in a gaseous state or capable of being gasified
Silicon compounds containing rogen atoms are also considered effective.
In the present invention, the following can be mentioned. Halogen compounds that can be suitably used in the present invention
Specifically, the substances include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF₃，
BrF_Five,BrF₃,IF₃,IF₇, ICl, IBr, etc.
Intermediate compounds can be mentioned. Silicon compounds containing halogen atoms, so-called
As silane derivatives substituted with rogene atoms,
Specifically, for example, SiF_Four,Si₂F₆,SiCl_Four, SiBr_Fouretc
Silicon halides are preferred.
I can do it. Adopts silicon compounds containing such halogen atoms
The characteristic light guide of the present invention is produced by the glow discharge method.
When forming electrical parts, raw materials that can supply Si
Even without using silicon hydride gas as a gas,
Halogen atoms as constituents on a given support
It is possible to form a layer consisting of A-Si:H containing
Ru. A layer containing halogen atoms according to the glow discharge method
When producing Si, basically the raw material gas for supplying Si is
Silicon halide gas and Ar, H₂, He et al.
Place the gas at the specified mixing ratio and gas flow rate.
Introduced into the deposition chamber to form the desired layer, glow discharge
to form a plasma atmosphere of these gases.
Form a desired layer on a given support by
Although it is possible to achieve this, in order to plan the introduction of hydrogen atoms.
In addition, silicon compounds containing hydrogen atoms in these gases
A layer may be formed by mixing a predetermined amount of gases. In addition, each gas can be used not only as a single species but also in a predetermined mixing ratio.
It is safe to use a mixture of multiple types.
Ru. Reactive sputtering method or ion platey
A layer consisting of A-Si(H,X) is formed using the
For example, in the case of sputtering method,
Using a target consisting of Si, this is
Sputtering in a gas plasma atmosphere to generate iodine
In the case of the plating method, polycrystalline silicon
Or use monocrystalline silicon as an evaporation source in a deposition boat.
This silicon evaporation source is heated using resistance heating method or
is added by electron beam method (EB method) etc.
Thermal evaporation and flying evaporates are placed in a specified gas plasma atmosphere.
This can be done by passing air through it. At this time, sputtering method, ion plate
In both cases, halogen is present in the layer formed.
In order to introduce a ion atom, the above-mentioned halogen compound or
is the silicon compound gas containing the above halogen atom.
The gas is introduced into the deposition chamber to form a plasma atmosphere.
It is good if you can do it. In addition, when introducing hydrogen atoms, hydrogen atom guide
Necessary raw material gas, e.g. H₂, or the above
In a deposition chamber for sputtering gases such as silanes.
to form a plasma atmosphere of the gas.
That's fine. In the present invention, the raw material for introducing halogen atoms
The halogen compounds or halogens listed above as gases
Silicon compounds containing gen are used as effective ones.
In addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH₂F₂，
SiH₂I₂,SiH₂Cl₂,SiHCl₃,SiH₂Br₂,SiHBr₃etc
halogen-substituted silicon hydride, etc.
Hydrogen atoms are one of the constituent elements, and can be gasified.
Halides are also effective charge injection blocking layers and light
It can be cited as a starting material for forming a conductive layer.
Ru. These halides containing hydrogen atoms are layered.
The introduction of halogen atoms into the layer formed during
At the same time, it is extremely useful for controlling electrical or photoelectric characteristics.
Since effective hydrogen atoms are also introduced, in the present invention,
is used as a suitable raw material for halogen introduction.
Ru. Hydrogen atoms are introduced structurally into the formed layer.
In addition to the above,₂, or SiH_Four,Si₂H₆，
Si₃H₈,Si_FourH_TenSupply Si with silicon hydride gas such as
coexist with a silicon compound in the deposition chamber to
This can also be done by causing electrical discharge. For example, in the case of the reactive sputtering method, Si
Gas for introducing halogen atoms using a target
and H₂If necessary, use an inert gas such as He or Ar.
A plasma atmosphere is created by introducing the
forming and sputtering the Si target.
In some cases, the substrate consists of A-Si(H,X).
A layer is formed. Furthermore, B also serves as impurity doping.₂H₆etc
It is also possible to introduce gas. In the present invention, the electrophotographic light receptor formed
Contained in the charge injection blocking layer and photoconductive layer of the member.
amount of hydrogen atoms (H) or amount of halogen atoms (X) or water
The sum of the amounts of elementary atoms and halogen atoms is preferably 1 to
40 atom%, more preferably 5 to 30 atom%
is desirable. Hydrogen atoms (H) or/
and to control the amount of halogen atoms (X), e.g.
Support temperature or/and hydrogen atom (H) or halogen
of the starting material used to contain the ion atom (X).
Controls the amount introduced into the volumetric device system, discharge power, etc.
Just do it. Group group atoms or
Group atoms, carbon atoms, oxygen atoms or nitrogen atoms
Glow discharge method or reaction spatula can be used to contain particles.
Formation of charge injection blocking layer and photoconductive layer by taring method etc.
During formation, group atoms or group atom introduction
Starting material, and for oxygen atom introduction, nitrogen introduction, charcoal
Blocking charge injection using each of the starting materials for elementary introduction
For use with starting materials for forming layers and photoconductive layers,
It can be contained in the formed layer while controlling its amount.
It is achieved by In this way, for introducing carbon atoms and for introducing oxygen atoms.
is/and the starting material for the introduction of nitrogen atoms, or group
As starting materials for introducing atoms or group atoms,
At least carbon atoms, oxygen atoms and nitrogen atoms
or a group atom or a group atom
A gaseous substance or a substance that can be gasified into atoms
Most of the gasified materials can be used.
Ru. For example, if it contains oxygen atoms, silicon
A raw material gas containing silicon atoms (Si) and an acid
Raw material gas containing elemental atoms (O) and, if necessary,
hydrogen atom (H) or halogen atom (X) as a constituent element.
Mix the raw material gas at the desired mixing ratio and use it.
or silicon atoms (Si)
A raw material gas with oxygen atoms (O) and hydrogen atoms (H)
The raw material gas, which is the constituent atoms, is also mixed in the desired manner.
Mix in a composite ratio or silicon atoms (Si)
Raw material gas with constituent atoms and silicon atoms
(Si), oxygen atom (O) and hydrogen atom (H).
It is possible to use it by mixing it with raw material gas.
come. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
Oxygen atoms (O) are formed in the raw material gas whose constituent atoms are
A mixture of raw material gases containing atoms may be used. Starting materials for introducing oxygen atoms and for introducing nitrogen atoms
Specifically, for example, oxygen
(O₂), ozone (O₃), nitric oxide (NO), dioxide
Nitrogen (NO₂), nitrogen monoxide (N₂O), sesquioxide
Nitrogen (N₂O₃), nitrogen tetroxide (N₂O_Four), pentoxide
Nitrogen (N₂O_Five), nitrogen trioxide (NO₃), nitrogen (N₂),
Ammonia (NH₃), hydrogen azide (HN₃), Hido
Radin (NH₂N.H.₂), silicon (Si) and oxygen atoms
(O) and hydrogen atom (H) as constituent atoms, for example,
Roxane (H₃SiOSiH₃), trisiloxane
(H₃SiOSiH₂OSiH₃) and other lower siloxanes.
You can get it. Carbon atom-containing compounds that serve as raw materials for introducing carbon atoms
For example, saturated hydrocarbons having 1 to 4 carbon atoms
Ethylene hydrocarbon with 2 to 4 carbon atoms, carbon number
Examples include 2 to 3 acetylene hydrocarbons. Specifically, methane is a saturated hydrocarbon.
(CH_Four), ethane (C₂H₆), propane (C₃H₈), n
-butane (n-C_FourH_Ten), pentane (C_FiveH₁₂),workman
Ethylene (C₂H_Four),
Propylene (C₃H₆), butene-1 (C_FourH₈), Butte
N-2 (C_FourH₈), isobutylene (C_FourH₈), pente
(C_FiveH_Ten), as acetylenic hydrocarbons,
Acetylene (C₂H₂), methylacetylene
(C₃H_Four), butin (C_FourH₆) etc. As a raw material gas containing Si, C, and H as constituent atoms
is Si(CH₃)4,Si(C₂H_Four)_Fouralkyl silicide such as
I can list the following. Group atoms or charges contained in group atomsNote
Glow discharge is used to form the entry blocking layer and photoconductive layer.
When using this method, the raw material gas for forming the layer is
The emitting substance is composed of the above-mentioned A-Si(H,X).
Starting materials for forming charge injection blocking layer and photoconductive layer
A group atom or a group atom selected from among
A starting material for introducing group atoms is added.
Ru. For such group atom or group atom introduction
Group atoms or group atoms are used as starting materials for
Substances in a gaseous state or capable of being gasified as constituent atoms
Any substance that has been gasified
It's okay to be hot. In the present invention, the starting material for introducing group atoms
Specifically, what can be effectively used as
B for introducing boron atoms₂H₆,B_FourH_Ten,B_FiveH₉，
B_FiveH₁₁,B₆H_Ten,B₆H₁₂,B₆H₁₄Boron hydride, such as
BF₃, BCl₃,BBr₃Boron halides such as
In addition, AlCl₃,GaCl₃，
InCl₃, TlCl₃etc. can also be mentioned. In the present invention, the starting material for introducing group atoms
Specifically, phosphorus atom conductors are effectively used as
For use, PH₃,P₂H_FourPhosphorus hydride, etc.
PH_FourI, P.F.₃,PF_Five, PCl₃, PCl_Five, PBr₃, PBr_Five，
P.I.₃Examples include halogenated phosphorus such as. In addition,
AsH₃,AsF₃,AsCl₃, AsBr₃,AsF_Five,SbH₃，
SbF₃,SbF_Five,SbCl₃,SbCl_Five, BiH₃,BiCl₃，
BiBr₃etc. can also be mentioned. Group atom or charge injection barrier containing group atom
Group atoms or group atoms introduced into the stopping layer and the photoconductive layer
The content of group atoms is determined by the initial
Group atoms or gas streams of starting materials for the introduction of group atoms
amount, gas flow rate ratio, discharge power, support temperature, deposition
Arbitrary control by controlling indoor pressure, etc.
It can be done. In order to effectively achieve the purpose of the present invention,
The support temperature is appropriately selected within the optimum range, but is preferably
preferably 50°C to 350°C, more preferably 100°C to 300°C.
It is desirable to do so. Charge injection blocking layer and photoconductive layer in the present invention
Formation involves delicate control of the composition ratio of the atoms that make up the layer.
control and layer thickness is easier than other methods
Therefore, it is difficult to adopt the glow discharge method or sputtering method.
However, these layer formation methods do not prevent charge injection.
When forming a stop layer and a photoconductive layer, the above-mentioned supporting layer is used.
Similar to the carrier temperature, the discharge power during layer formation,
gas pressure is created in the charge injection blocking layer or photoconductive layer.
It is an important factor that influences the characteristics. A charge injection having characteristics capable of achieving the object of the present invention
Entry blocking layer and photoconductive layer can be manufactured efficiently and efficiently.
Regarding the discharge power conditions when creating
is preferably 10~1000W, more preferably 20~
It is desirable to set it to 500W, and the gas in the deposition chamber
Regarding the pressure, preferably 0.01~1Torr, or more
It is preferable to set it to approximately 0.1 to 0.5 Torr. In the present invention, a charge injection blocking layer and a photoconductive
Desired support temperature and discharge power to create the layer
The preferred numerical ranges include the ranges listed above.
However, these layer formation factors are usually independent
the desired characteristics, rather than those that can be determined separately.
To form a charge injection blocking layer and a photoconductive layer with
Each layer is constructed based on mutual and organic relationships.
It is desirable to determine the optimal value of the growth factor. Contained in the photoconductive layer formed in the present invention
The amount of carbon, oxygen or nitrogen that is
It greatly influences the characteristics of photoreceptive materials.
However, it must be determined appropriately according to the wishes.
but preferably 0.0005 to 30 atom%, more preferably
0.001 to 20 at%, optimally 0.002 to 15 at%.
It is desirable to The layer thickness of the photoconductive layer has the desired spectral characteristics.
Photocarrier generated by irradiation with light
Decide as appropriate to ensure efficient transport of
usually 1 to 100μ, more preferably 2 to 50μ.
It is desirable that surface layer The surface layer formed on the photoconductive layer covers the free surface.
Mainly moisture resistance, continuous repeated use characteristics, electrical
The focus of the present invention is on pressure resistance, use environment characteristics, and durability.
It is established to achieve a goal. In the light-receiving member of the present invention, the surface layer and
At the interface with the photoconductive layer, the optical bands of both layers
Gap matching or the field between the surface layer and the photoconductive layer
enough to substantially prevent reflection of incident light on the surface.
be configured to be aligned at least once.
This is an extremely important point. At the same time, this
This has a very unique correlation with the hydrogen content.
It is also an important point to bring about favorable conditions.
It is. Furthermore, in the present invention, the surface of the surface layer
The amount of hydrogen contained in the region close to, at least on the outermost surface
It is necessary to set the concentration to a predetermined concentration. that's all
Distribution of constituent elements within the surface layer to meet the conditions
State is determined under strict condition control
There is a need. Furthermore, in addition to the above conditions, the free surface side of the surface layer
At the edge of the
Ensure that the amount of incident light reaching the photoconductive layer is sufficient.
The free surface end of the surface layer
In this case, the optical band gear of the surface layer is
Eopt can be configured to be large enough.
Both are points to consider. Then, the surface layer and light guide
Optical bandgap at the interface with the electrical layer
Configure the Eopt to match and
Optical band gear at the free surface end of the layer
If you configure Eopt to be large enough,
In this case, the optical bandgap of the surface layer is
The area that changes continuously in the thickness direction of the surface layer
configured to include at least Optical bandgap Eopt layer thickness of surface layer
To control the value in the direction as described above, the representative
In other words, it is the main tuning atom of the optical bandgap.
The amount of carbon atoms (C) contained in the surface layer of
This can be done by controlling the
Other parts of the surface layer change in response to changes in dogpup.
Water that has the function of matching properties to optimal conditions
The content is also adjusted so that the element has a specific distribution state.
control. The following is the proportion of carbon atoms and hydrogen atoms in the surface layer.
Some typical examples of cloth conditions are shown in Figures 25 to 25.
The present invention will be explained with reference to FIG.
It is not limited by. In Figures 25 to 28, the horizontal axis is the atom
Distribution concentration C of (C, Si) and atoms (H), vertical axis is surface
The layer thickness t of the layer is shown, and in the figure, t_Tis the photosensitive layer and the surface
Interface position with surface layer, t_Fis the free surface position, the solid line is the charcoal
Changes in the distribution concentration of elementary atoms (C), the chain double-dashed line is silicon
Changes in the distribution concentration of atoms (Si), and the dashed line represents water.
Each shows the change in the distribution concentration of elementary atoms (H).
Ru. Figure 25 shows carbon atoms (C) contained in the surface layer.
and layer thickness direction of silicon atoms (Si) and hydrogen atoms (H)
The first typical example of the distribution state is shown. In this example
is the interface position t_TMore position₁₁up to, the number of carbon atoms (C)
Cloth density C is less than zero₃₇linear function until
On the other hand, the distribution concentration of silicon atoms is
Concentration C₃₈From concentration C₃₉decreases linearly until
Also, the distribution concentration of hydrogen atoms is C₄₀from C₄₁becomes
increases linearly until position t₁₁from position t_Fto
Until carbon atoms (C), silicon atoms and hydrogen
The distribution concentration C of atoms is each concentration C₃₇and concentration C₃₉as well as
Concentration C₄₁maintain a constant value. For convenience of explanation,
For convenience, let the inflection point of the distribution state of each component be t₁₁It was
Even if they are shifted from each other, there is virtually no problem. In the example shown in FIG. 26, the position t_Tfrom position t_FMa
So, carbon atom (C) increases from zero to concentration C₄₂until, again,
Licon atom (Si) is C₄₃from C₄₄Until, again, hydrogen source
Child (H) is C₄₅from C₄₆up to
It's set. In this example, over the entire surface layer
Because the components change, there are no adverse effects caused by discontinuity in the components.
It is possible to improve the damage even further. Also, for example, as shown in FIGS. 27 to 28, the components
A pattern in which the rate of change of
Combinations of the typical examples described in Figures 5 to 28 are also possible.
Depending on the desired film properties or manufacturing equipment conditions, etc.
can be selected as appropriate. Furthermore, the bandgi at the interface
Yatsupu's consistency is practically sufficient as mentioned above.
In that sense, it is fine._Tamount of carbon in
is not necessarily 0, but may have a certain finite value,
In addition, the changes in the components stagnate over a certain period in the distribution region.
From this point of view, it is also permissible to do so. The surface layer is formed using glow discharge method or microwave discharge.
method, sputtering method, ion implantation method
Yon method, ion plating method, electron
This is done by the beam method, etc. How to make these
depends on manufacturing conditions, the level of capital investment, and manufacturing regulations.
It is desired for the electrophotographic light-receiving member to be produced.
be selected and adopted as appropriate depending on factors such as the characteristics
However, the electrophotographic light receiving part has the desired characteristics.
It is relatively easy to control the conditions for manufacturing materials.
be. Carbon and hydrogen atoms along with silicon atoms
can be easily introduced into the surface layer 105 to be prepared.
Glow discharge method or sputtering method has advantages such as
A method is preferably adopted. Furthermore, in the present invention, glow discharge method and spatula
surface layer 1 by combining the taring method in the same equipment system.
05 may be formed. Forming surface layer 105 by glow discharge method
is A-(Si_XC_1-X)_y:H_1-yRaw material gas for formation
Mix with dilution gas at the specified mixing ratio as necessary.
Then, the support 101 is installed on the vacuum deposition deposit.
The gas is introduced into the storage chamber and the introduced gas generates a glow discharge.
By causing gas to rise, it becomes gas plasma and the support 1
on the photoconductive layer 104 already formed on 01.
A-(Si_XC_1-X)_y:H_1-yAll you have to do is deposit it. distribution
The formation of the region is based on the component to be changed, e.g. carbon atoms.
Containing gas and silicon atom-containing gas and hydrogen atoms
etc. from the starting flow rate to the desired distribution pattern.
follow a specific sequence set to be
If you increase or decrease it, it will be ready. In the present invention, A-(Si_XC_1-X)_y:H_1-yfor forming
As the raw material gas, at least one of Si, C, and H is used.
A gaseous substance or gasified substance with one constituent atom
Most of the materials obtained by gasifying them are used.
can be used. Si is one of the constituent atoms among Si, C, and H.
For example, when using raw material gas containing Si as a component gas,
A raw material gas containing C as a constituent atom and a raw material gas containing C as a constituent atom.
A desired mixture of gas and raw material gas containing H as a constituent atom is formed.
Use by mixing in a composite ratio, or use Si as a constituent atom.
A raw material gas containing C and H as its constituent atoms
and the feed gas at the desired mixing ratio.
Or, a raw material gas containing Si as a constituent atom,
A raw material gas containing three constituent atoms: Si, C, and H.
Can be used in combination. In addition, there is also a raw material gas whose constituent atoms are Si and H.
mixed with raw material gas containing C as a constituent atom.
You may do so. In addition, in the distribution area, the above mixture
It is only necessary to change the rate according to a predetermined sequence.
stomach. In the present invention, the raw material gas for forming the surface layer 105 is
Si and H are effectively used as a
SiH as an atom_Four,Si₂H₆,Si₃H3, Si_FourH_Tenetc.
Silicon hydride gas such as silane, C and H
For example, saturated carbon having 1 to 4 carbon atoms
Hydrogen, ethylene hydrocarbons with 2 to 4 carbon atoms, carbon
Examples include acetylene hydrocarbons with a prime number of 2 to 3.
Ru. 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) etc. As a raw material gas containing Si, C, and H as constituent atoms
is Si(CH₃)_Four,Si(C₂H_Five)_FourAlkyl silicide such as
I can list them. In addition to these raw material gases, H
Of course, H is used as the raw material gas for introduction.₂is also valid
used as. Forming surface layer 105 by sputtering method
For this purpose, single crystal or polycrystalline Si wafer or
C wafer or contains a mixture of Si and C
Targeting wafers with
For sputtering in various gas atmospheres
Just turn around and go. For example, using a Si wafer as a target
Then, the raw material gas for introducing C and H is required.
Deposit for sputtering by diluting with diluent gas according to
These gases are introduced into the chamber to form a gas plasma.
If the above-mentioned Si wafer is sputtered with
good. In this case, the distribution area is, for example, a C-containing area.
The raw material gas concentration is changed according to a certain sequence.
Just let it happen. Additionally, Si and C are separate targets.
or using a single target with a mixture of Si and C.
containing at least a hydrogen atom.
by sputtering in a gas atmosphere that
It will be done. In this case, the distribution area is C or Si
Combined with a gas containing at least one of the following:
and the concentrations of these gases follow a certain sequence.
It is necessary to make changes. As the raw material gas for introducing C or H, the above-mentioned
The raw material gas shown in the glow discharge example is
It can also be used as an effective gas in the case of In the present invention, the surface layer 105 is formed by a glow discharge method.
Or used when forming by sputtering method
As the diluting gas, so-called rare gases such as He,
Ne, Ar, etc. can be cited as suitable materials.
Ru. The surface layer 105 in the present invention
carefully shaped to give the desired properties
be done. In other words, substances whose constituent atoms are Si, C, and H are
The structure varies from crystal to amorph depending on the creation conditions.
It takes the form of up to a
properties ranging from conductivity to insulating properties, and photoconductive properties.
properties ranging from non-photoconductive properties to non-photoconductive properties.
Therefore, in the present invention, desired
A-Si with characteristics_XC_1-Xin places so that
The creation conditions are strictly selected according to the wishes.
Ru. For example, the main purpose of the surface layer 105 is to improve pressure resistance.
A-(Si_XC_1-X)_y:H_1-ymessenger
Amorphous material with remarkable electrically insulating behavior in a commercial environment
Created as a material. In addition, improvements in continuous repeated use characteristics and usage environment characteristics
When the surface layer is provided primarily for the purpose of
The above degree of electrical insulation is moderated to some extent and
Amorphous that has a certain degree of sensitivity to the light that is emitted
A-Si as a quality material_XC_1-Xis created. A-(Si_XC_1-X)_yH_1-yconsists of
When forming the surface layer, the support temperature during layer formation is
Important factors that influence the structure and properties of the formed layer
In the present invention, the desired characteristics
A-(Si_XC_1-X)_yH_1-yis created as desired
The support temperature during layer creation is strictly controlled to ensure that
It is desirable that In order to effectively achieve the purpose of the present invention,
The support temperature when forming the surface layer is
The optimal range is selected according to the layer formation method,
Formation of the surface layer is carried out, preferably at 50°C
~350℃, more preferably 100℃~300℃
is desirable. To form the surface layer, layer
Subtle control of the composition ratio of constituent atoms and control of layer thickness
This is because it is relatively easy compared to other methods.
The use of glow discharge method and sputtering method is effective for this purpose.
However, the surface layer cannot be formed using these layer formation methods.
In the same way as the support temperature described above, the layer formation temperature
A-(Si_X
C_1-X)_y:H_1-yOne of the important factors that influences the characteristics of
It is one. Having the characteristics to achieve the purpose of the present invention
A-(Si_XC_1-X)_y:H_1-ybe productive and effective
The preferable discharge power conditions for creating
preferably 10-1000W, more preferably 20-500W.
It is desirable that The gas pressure in the deposition chamber is favorable
is about 0.01 to 1 Torr, more preferably about 0.1 to 0.5 Torr
It is desirable that this is done. In the present invention, the support for creating the surface layer is
The desired numerical ranges for body temperature and discharge power are
The values in the range shown are listed, but these layers cannot be created.
Factors can be determined independently and separately.
A-Si with desired characteristics_XC_1-Xsurface layer consisting of
based on mutual organic relationships so that
Therefore, the optimal value of each layer formation factor can be determined.
is desirable. Surface layer in the electrophotographic light-receiving member of the present invention
The amount of carbon atoms and hydrogen atoms contained in the surface
Where the purpose of the present invention is achieved, as well as the production conditions of the layer.
An important factor in the formation of a surface layer that provides the desired properties.
It is a child. Carbon atoms contained in the surface layer in the present invention
The amount of silicon atoms and carbon atoms in the distribution area is
Preferably from 0 to 90 atomic % based on the total amount of particles, and more
Preferably 0 to 85 atom%, optimally 0 to 80 atom%
It is desirable to vary within a certain range.
In this case, preferably 1×10^-3~90 atomic%, more
Preferably 1 to 90 atom%, optimally 10 to 80 atom%
It is desirable that this is the case. Contains hydrogen atoms
In terms of abundance, in the distribution region, the total number of constituent atoms is
Constant or constant within the range of 1 to 70 atomic% relative to the amount
It is desirable to vary the
is usually 41 to 70 atoms, at least on the outermost surface.
%, preferably 45 to 60 atomic %.
stomach. In addition to the above-mentioned amount range and the above-mentioned distribution state,
Light with a surface layer created under the stated manufacturing conditions
The receiving member is actually much superior to conventional ones.
It can be fully applied as a standard. below
The effect will be explained using a few examples. First, we will discuss the consistency aspect of the band gap.
For example, the conventional surface layer and photoisoelectric layer
If there is a clear optical interface between
Reflection of the incident light at the interface occurs. This and free table
Reflections on the surface interfere with each other, causing damage to the photoconductive layer.
There is a phenomenon where the amount of incident light is affected to some extent.
Ru. In particular, coherent light, e.g. a laser, is used as a light source.
- This tendency is noticeable when using light, etc.
Ru. On the other hand, for example, using the blade cleaning method
In the case of copiers, the surface layer may deteriorate due to long-term use.
Although some wear is inevitable, this
Changes in the film thickness of the surface layer due to abrasion result in the interference state.
effect change; i.e. light by abrasion
The fact that the amount of light incident on the conductive layer is influenced to some extent.
This means that you can see an elephant. Control of bandgap integrity in the present invention
One is that the reflection at the interface is a plane of continuity of the components.
One aspect is that it has the effect of minimizing from
Also, the band gap is changed.
Therefore, the light absorption property itself has continuity.
This produces two favorable effects: accordingly
Among the preferable electrophotographic properties already mentioned,
Outstanding effectiveness in maintaining properties during long-term use.
The noteworthy effect in this case is to show
It can be said. Next, we will discuss the role of hydrogen in the surface layer.
Defects present in the surface layer (mainly silicon atoms and carbon
Dangling bonds of elementary atoms) are photoreceptors for electrophotography.
It is known that it has an adverse effect on the properties of the container material.
For example, charging due to charge injection from the free surface
Deterioration of characteristics, usage environment, e.g. under high humidity
Fluctuations in charging characteristics due to changes in surface structure;
Furthermore, during corona charging or light irradiation, the surface of the photoconductive layer
Charge is injected into the layer and defects in the surface layer are charged.
Afterimage during repeated use due to being trapped
Examples include phenomena. However, the hydrogen content in the surface layer was reduced to 41 atomic%.
The above control greatly reduces defects in the surface layer.
As a result, all of the above problems are solved, and the special
Compared to conventional products, electrical characteristics and high-speed continuous
A dramatic improvement in usability can be achieved.
Ru. On the other hand, the hydrogen content in the surface layer is 71 atomic% or more.
As the hardness of the surface layer decreases,
Cannot withstand repeated use. Therefore, water in the surface layer
It is much easier to control the elemental content within the above range.
Very important in obtaining excellent desired electrophotographic properties
This is one of the important factors. The hydrogen content in the surface layer is
H₂Gas flow rate, support temperature, discharge power, gas
It can be controlled by pressure, etc. In addition, the consistency of the band gap and the hydrogen content
There is also a unique correlation between
Carbon atom (C), which is a typical variable component of Yatsupu
In the fabric area, the hydrogen content is
So as to optimize the structure of or dung
Its content is designed to minimize ring bonds.
and the role of hydrogen in the surface layer.
so that it has the value necessary to achieve the effect described in
In other words, at least towards the free surface side, hydrogen
The most unreasonable way to create a tendency toward increasing volume is to
It is set to no shape. Therefore, the hydrogen-containing state of the surface layer in the present invention
is the effect of bandgap integrity and hydrogen content.
The effects of itself will be maximized together.
Another goal is to match the sea urchins and sea urchins.
It can be said that it also has an effect. Halogen atoms may be included in the surface layer.
stomach. A method of containing halogen atoms in the surface layer and
For example, SiF is added to the raw material gas._Four,SiFH₃,Si₂F₆，
SiF₃SiH₃,SiCl_Foursilicon halide gas such as
Mix or/and CF_Four,CCl_Four,CH₃C.F.₃
Glow discharge by mixing halogenated carbon gas such as
It can be formed by decomposition method or sputtering method.
stomach. The numerical range of the layer thickness in the present invention is
It is one of the important factors to effectively achieve the target.
Ru. The numerical range of the layer thickness of the surface layer in the present invention is
To the intended purpose so as to effectively achieve the purpose of the invention
It can be determined as appropriate and desired. Also, the thickness of the surface layer is related to the thickness of the photoconductive layer.
Even in
Determined as appropriate based on the organic relationship between
need to be done. In addition, productivity and
Economic efficiency including productivity is also taken into consideration.
is desirable. The thickness of the surface layer in the present invention is preferably
preferably 0.003 to 30μ, more preferably 0.004 to 20μ, optimal
It is desirable that the value be 0.005 to 10μ.
Ru. Light reception of the light reception member for electrophotography according to the present invention
The thickness of the layer can be adjusted to suit the purpose and as desired.
It will be decided as appropriate. In the present invention, the layer thickness of the photoreceptive layer is as follows:
It is added to the photoconductive layer and surface layer that make up the photoreceptive layer.
The objectives of the present invention can be achieved by effectively utilizing each of the characteristics
The layer thickness relationship between the photoconductive layer and the surface layer is
It shall be decided as appropriate and according to the wishes of the concerned parties.
The thickness of the photoconductive layer is preferably smaller than that of the surface layer.
The layer thickness is several hundred to several thousand times or more.
This is preferable. As a specific value, preferably usually 3~
100μ, more preferably 5-70μ, optimally 5-50μ
It is desirable that it be within the range of . Next, the outline of the method for manufacturing the photoconductive member of the present invention will be explained.
I will explain. Figure 24 shows a manufacturing apparatus for electrophotographic light-receiving members.
An example is shown. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming each layer of the present invention is sealed.
As an example, 1102 is
SiH_Four(99.999% purity) cylinder, 1103 is H₂and rare
interpreted B₂H₆Gas (purity 99.999%, below B₂H₆/
H₂It is abbreviated as ), 1104 is H₂Gas (purity 99.99999
%) cylinder, 1105 is NO gas (purity 99.999%)
Cylinder, 1106 is CH_FourGas (99.99% purity) bottle
It is Nbe. 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 1112-1
116, outflow valves 1117-1121, auxiliary valves
Confirm that Lube 1132 and 1133 are open.
First, open the main valve 1134 to open the reaction chamber 1.
101. Evacuate the inside of the gas pipe. Next, vacuum gauge 11
36 reading is about 5×10^-6Assistance when it becomes torr
Valve 1132, 1133, outflow valve 1117
~Close 1121. Next, on the cylindrical base 1137, as shown in FIG.
When forming an electrophotographic light-receiving member with a layer structure
For example, from gas cylinder 1102
SiH_FourGas from gas cylinder 1104₂gas,
B from gas cylinder 1103₂H₆/H₂gas, gas
NO gas is supplied from cylinder 1105 to valve 112 respectively.
Open 2-1125 and check the outlet pressure gauge 1127-1
1Kg/cm for each pressure of 130²Adjust the inflow valve
Gradually open each of 1112 to 1115 and insert the mask.
flows into the controllers 1107 to 1110 respectively.
let Subsequently, the outflow valves 1117-112
0 gradually open the auxiliary valve 1132 to release each gas.
flows into the reaction chamber 1101. SiH at this time_Four
Gas flow rate and B₂H₆/H₂Gas flow rate, NO gas flow rate and
The outflow valves 1117~
1120, and also ensure that the pressure inside the reaction chamber is at the desired level.
While checking the reading of vacuum gauge 1136, make sure that the value is correct.
Adjust the opening of the in-valve 1134. and base
The temperature of the body cylinder 1137 is increased by the heating heater 11.
38, the temperature is set in the range of 50 to 350℃.
After confirming that the
A glow discharge is generated in the reaction chamber 1101 by setting the
at the same time following a pre-designed rate of change curve.
TeB₂H₆/H₂Manually control the gas and/or NO gas flow rate.
Valve by dynamic or external drive motor etc.
Operation to gradually change 1118 or/and 1120
Boron atoms contained in the layer formed by
control the distribution concentration of oxygen atoms and/or oxygen atoms in the layer thickness direction.
control As above, boron atoms and oxygen atoms are added to the desired layer thickness.
At the time when the charge injection blocking layer containing
Then close the outflow valves 1120 and 1118 and
B to reception room 1101₂H₆/H₂Gas and NO gas
At the same time, the outflow valves 1117 and 1
SiH by adjusting 119_Fourgas and H₂gas flow rate
By controlled and subsequent layer formation, oxygen
A photoconductive layer containing no atoms or boron atoms is injected with a charge.
It is formed on the entry blocking layer to a desired thickness. Also, light containing oxygen atoms and/or boron atoms
When forming a conductive layer, the outflow valve 1118 or
and/or adjust the desired flow rate instead of closing 1120.
All you have to do is adjust it. Halogen atoms in charge injection blocking layer and photoconductive layer
If the above gas contains SiF, for example,_FourGa
Further add gas and send it into the reaction chamber 1101.
nothing. Depending on the gas type selected when forming each layer, the layer
The formation speed can be further increased. For example, SiH_Four
Si instead of gas₂H₆Layer formation using gas
If so, it can be increased several times, improving productivity. A surface layer is placed on the photoconductive layer created as described above.
To form the photoconductive layer, a barrier similar to that used in forming the photoconductive layer is used.
For example, SiH_Fourgas, CH_Fourgas,
and H if necessary₂etc. to the desired flow of dilution gas.
into the reaction chamber 1101 according to the desired conditions.
This is achieved by causing a glow discharge.
Ru. The amount of carbon atoms contained in the surface layer is, for example,
SiH_FourGas and CH_FourGas is introduced into the reaction chamber 1101.
The input flow rate ratio can be arbitrarily changed as desired.
Therefore, it can be controlled as desired. Also, the amount of hydrogen atoms contained in the surface layer is
Ba, H₂A flow of gas introduced into the reaction chamber 1101
By arbitrarily changing the amount as desired,
It can be controlled accordingly. Outflow of gases other than those required to form each layer
It goes without saying that all valves should be closed, and
When forming each layer, remove the gas used to form the previous layer.
inside the reaction chamber 1101, outflow valves 1117-1
Remains in the piping from 121 to reaction chamber 1101
In order to avoid
21 and open the auxiliary valve 1132 to open the main
Fully open valve 1134 and evacuate the system to high vacuum.
Perform the operations you care about as necessary. Also, during layer formation, uniformity of layer formation
In order to achieve this, the base cylinder 1137 is connected to the motor 11
Rotate constantly at the desired speed by 39
Ru. Example 1 Using the manufacturing equipment shown in Figure 24, the manufacturing conditions shown in Table 1
on an aluminum cylinder with a mirror finish according to
A light-receiving member for electrophotography was formed. This photoreceptor
material (hereinafter referred to as drum) with a wavelength of 780 nm.
Digital exposure function using a semiconductor laser as a light source
under various conditions.
In addition, initial chargeability, residual potential, ghost electrons, etc.
After checking the photographic characteristics and after 1.5 million sheets of actual machine durability.
Investigating the decrease in charging ability, deterioration in sensitivity, and increase in image defects.
Ta. Furthermore, in a high temperature and high humidity atmosphere of 35℃ and 85%
Image flow on the drum was also evaluated. and,
Drums that have been evaluated are displayed at the top, middle, and bottom of the image area.
Cut out the corresponding part, use it as a sample, and send it to SIMS.
For quantitative analysis of hydrogen contained in the surface layer using
provided. The above evaluation results and hydrogen content in the surface layer
The maximum values of the amounts are shown in Table 2. As seen in Table 2
In particular, initial chargeability, image flow, residual potential, and
image defects, uneven light sensitivity in the generatrix direction, and poor sensitivity.
Significant superiority was recognized in each item of improvement. Comparative example 1 Example except that the manufacturing conditions were changed as shown in Table 3.
Drum and analytical sump using the same equipment and method as 1.
A sample was prepared and subjected to similar evaluation and analysis. The result
The results are shown in Table 4. As seen in Table 4, there are various differences compared to Example 1.
It was recognized that the performance was inferior in the following items. Example 2 Using the manufacturing equipment shown in Figure 24, the manufacturing conditions shown in Table 5
on an aluminum cylinder with a mirror finish according to
A light-receiving member for electrophotography was formed. This photoreceptor
material (hereinafter referred to as drum) with a wavelength of 780 nm.
Digital exposure function using a semiconductor laser as a light source
under various conditions.
In addition, initial chargeability, residual potential, ghost electrons, etc.
After checking the photographic characteristics and after 1.5 million sheets of actual machine durability.
Investigating the decrease in charging ability, deterioration in sensitivity, and increase in image defects.
Ta. In addition, the battery can be used in a high temperature and high humidity atmosphere of 35℃ and 85%.
The image flow of the ram was also evaluated. And the review
The drum that has been calibrated is placed in the top, middle, and bottom of the image area.
Cut out the corresponding part, use it as a sample, and send it to SIMS.
It can be used for quantitative analysis of hydrogen contained in the surface layer.
Also, silicon atoms (Si) in the surface layer,
Component profile of carbon atoms (C) and hydrogen atoms (H) in the layer thickness direction
I checked the file. Furthermore, a layer in the charge injection layer
Boron (B) and oxygen (O) component profile in the thickness direction
and germanium in the layer thickness direction in the long wavelength photosensitive layer.
We investigated the component profile of Ge. Up
Evaluation results and hydrogen content contained in the surface layer
Table 6 shows the maximum value of
The elementary component profile is shown in Figure 31, and the charge note
Component profile of the element in the entry blocking layer and the above
Component profile of the element in the long wavelength photosensitive layer
is shown in FIG. As seen in Table 6, especially
Initial chargeability, residual potential, ghost, image blur, image
Image defects, uneven light sensitivity in the generatrix direction, sensitivity deterioration, and image
Regarding each item of increase in image defects, and regarding interference fringes,
However, the remarkable superiority of each was recognized. Example 3 (Comparative example 2) The surface layer was prepared under several conditions shown in Table 7.
other than that, under the same conditions as Example 1.
A drum and samples for analysis were prepared. these
The drum and sample were evaluated and analyzed in the same manner as in Example 1.
As a result of analysis, the results shown in Table 8 were obtained. Example 4 Several conditions for producing the photoconductive layer are shown in Table 9.
, and the other conditions were the same as in Example 1.
I prepared several drums. Examples of these drums
As a result of the same evaluation as in 1, the results are as shown in Table 10.
Got the results. Example 5 Several conditions for preparing the charge injection blocking layer are shown in Table 11.
, and the other conditions were the same as in Example 1.
We prepared multiple drums. these drums
The results of the same evaluation as in Example 1 are shown in Table 12.
I got great results. Example 6 Table 13 shows several conditions for preparing the charge injection blocking layer.
The conditions were changed to , and the other conditions were the same as in Example 1.
We prepared multiple drums. these drums
The results of the same evaluation as in Example 1 are shown in Table 14.
I got great results. Example 7 Several conditions for producing the long wavelength photosensitive layer are shown in Table 15.
The conditions were changed to , and the other conditions were the same as in Example 1.
We prepared multiple drums. these drums
The results of the same evaluation as in Example 1 are shown in Table 16.
I got great results. Example 8 Several conditions for producing the long wavelength photosensitive layer are shown in Table 17.
, and the other conditions were the same as in Example 1.
We prepared multiple drums. these drums
The results of the same evaluation as in Example 1 are shown in Table 18.
I got great results. Example 9> Several types of fabrication strips shown in Table 19 are formed on the base cylinder.
Under certain conditions, an adhesion layer is formed and further applied on top of it.
Forming a light-receiving member under the same manufacturing conditions as Example 1
did. These light receiving members were evaluated in the same manner as in Example 1.
As a result, the results shown in Table 20 were obtained. Example 10 The mirror-finished cylinder can be viewed from various angles.
Fig. 29
Various cross-sectional putters as shown in Table 21 with cross-sectional shapes such as
We prepared multiple cylinders with a number of cylinders. The syringe
Set the printers one by one on the manufacturing equipment shown in Figure 24 and carry out the process.
The drum was manufactured under the same manufacturing conditions as Example 1.
Ta. The created drum has a wavelength of 780nm
Digital exposure function using semiconductor laser as light source
Various evaluations were performed using electrophotographic equipment, and the results shown in Table 22
I got the result. Example 11 Continue to polish the mirror-finished surface of the cylinder.
The series is exposed to the dropping of many bearing balls.
The so-called surface that causes countless dents on the surface of the
After dimple treatment, the cross-sectional shape is as shown in Figure 30.
, with various cross-sectional patterns as shown in Table 23.
I prepared several Linders. the cylinders in sequence
Set it in the manufacturing equipment shown in Fig. 24 and use the same method as in Example 1.
The drum was manufactured based on the following manufacturing conditions. made
The drum is equipped with a semiconductor laser with a wavelength of 780nm.
An electrophotographic device with a digital exposure function that uses a light source as a light source.
We conducted various evaluations and obtained the results shown in Table 24.
Ta.

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[Table] ◎...Very good ○...Good △...Practically acceptable ×...Impractical

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[Table] ◎...Very good ○...Good △...Practically acceptable ×...Impractical

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[Table] ◎...Very good ○...Good △...Practically acceptable ×...Impractical

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[Table] ◎...Very good ○...Good △...Practically acceptable ×...Impractical

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[Summary of effects of the invention]

The light-receiving member of the present invention has a photoconductive layer composed of A-Si (H, (H, etc. In addition, there is no influence of residual potential, and its electrical characteristics are stable.
The images obtained using it are of excellent quality, with high density and clear halftones. In particular, in the electrophotographic light-receiving member of the present invention, by providing a charge injection blocking layer, it has become possible to use a relatively resistive photoconductive layer that is sensitive to light in a relatively wide range of wavelengths. Furthermore, due to the specific layer structure mentioned above, a large number of charges excited by light irradiation and thermal excitation are swept out sufficiently quickly not only in the photoconductive layer but also in the charge injection blocking layer and the surface layer. Even under exposure conditions, no residual potential or ghost occurs, and high-quality images with high resolution can be stably and repeatedly obtained.

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic light-receiving member of the present invention, and FIGS. 2 to 7 show the distribution state of germanium atoms constituting the long wavelength photosensitive layer, respectively. FIGS. 8 to 12 are explanatory views for explaining the group atoms or the distribution state of the group atoms constituting the charge injection blocking layer, and FIGS. 13 to 19, respectively. teeth,
Explanatory diagram for explaining the distribution state of oxygen atoms or nitrogen atoms constituting each charge injection blocking layer, No. 20
22 are schematic diagrams for explaining the uneven shape of the surface of the support and the method for producing the uneven shape,
FIG. 23 is an explanatory diagram of another electrophotographic light-receiving member of the present invention, and FIG. 24 is an example of an apparatus for forming a light-receiving layer of the electrophotographic light-receiving member of the present invention, manufactured by a glow discharge method. FIG. 2 is a schematic explanatory diagram of the device.
25 to 28 are explanatory diagrams for explaining the distribution state of silicon atoms, carbon atoms and hydrogen atoms constituting the surface layer; FIGS. 29 and 30 are schematic diagrams showing the shape of the support; 32 are distribution diagrams showing the distribution of each atom in the layer. Regarding FIG. 1, 100...photoreceptive layer, 101
... Support, 107 ... Adhesion layer, 102 ... Long wavelength photosensitive layer, 103 ... Charge injection blocking layer, 104
... photoconductive layer, 105 ... surface layer, 106 ... free surface. Regarding figures 21 and 22, 1601, 17
01... Support, 1602, 1702... Support surface, 1603, 1703... Rigid straight ball, 160
4,1704... Spherical trace depression. Regarding FIG. 23, 2300...photoreceptive layer, 2
301... Support, 2302... Long wavelength photosensitive layer, 2303... Charge injection blocking layer, 2304...
Photoconductive layer, 2305... surface layer, 2306... free surface. Regarding FIG. 24, 1101...reaction chamber, 11
02-1106...Gas cylinder, 1107-11
11... Mass flow controller, 1112-11
16... Inflow valve, 1117-1121... Outflow valve, 1122-1126... Valve, 11
27-1131...Pressure regulator, 1132, 11
33...Auxiliary valve, 1134...Main valve, 1135...Leak valve, 1136...Vacuum gauge, 1137...Base cylinder, 1138...
…Heater, 1139…Motor, 114
0...High frequency power supply.

Claims (1)

[Scope of Claims] 1. A support, and on the support, an adhesive layer made of an amorphous material containing silicon atoms and at least one of nitrogen atoms, oxygen atoms, and carbon atoms, and silicon atoms and germanium atoms. a long-wavelength photosensitive layer that is sensitive to long-wavelength light, and an amorphous material that has silicon atoms as its matrix, and belongs to Group 3 or Group 3 of the periodic table. a charge injection blocking layer containing atoms; a photoconductive layer that exhibits photoconductivity and is composed of an amorphous material having silicon atoms as a matrix and containing at least one of hydrogen atoms and halogen atoms as a constituent element; a surface layer made of an amorphous material containing atoms, carbon atoms, and hydrogen atoms as constituent elements; The concentration distribution of the constituent elements in the layer thickness direction is changed so that the concentration of the carbon atoms decreases toward the interface with the surface layer, and the maximum concentration of hydrogen atoms in the surface layer in the layer thickness direction is 41 to 70. 1. A light-receiving member for electrophotography, characterized in that atomic percent. 2. The light-receiving member for electrophotography according to claim 1, wherein the distribution region of the constituent elements of the surface layer is present on the support side of the surface layer. 3. The light-receiving member for electrophotography according to claim 1, wherein the distribution area of the constituent elements of the surface layer extends over the entire surface layer. 4. Claims 2 and 3, wherein the surface layer contains carbon atoms in a distribution state in which carbon atoms are distributed more toward the surface side in the distribution region of the constituent elements.
2. The electrophotographic light-receiving member described in 1. 5. The light-receiving member for electrophotography according to claims 1 to 4, wherein the surface layer contains hydrogen atoms in a distribution state in which hydrogen atoms are distributed more toward the surface side in the distribution region of the constituent elements. . 6. The electrophotographic light-receiving member according to claim 1, wherein the surface layer contains halogen atoms. 7. The electrophotographic light-receiving member according to claim 1, wherein the photoconductive layer contains at least one of carbon atoms, oxygen atoms, and nitrogen atoms. 8. The electrophotographic light-receiving member according to claim 1, wherein the charge injection blocking layer contains at least one of oxygen atoms and nitrogen atoms. 9. The electrophotographic light according to claims 1 and 8, wherein the charge injection blocking layer contains atoms belonging to Group 1 or Group 3 of the periodic table in a distribution state in which the charge injection blocking layer is distributed more toward the support side. Receptive member. 10. The electrophotographic light-receiving member according to claims 8 and 9, wherein the charge injection blocking layer contains at least one of oxygen atoms and nitrogen atoms in a distribution state such that the charge injection blocking layer is distributed in large quantities on the support side. 11. The electrophotographic light-receiving member according to claims 8 to 10, wherein at least one of oxygen atoms and nitrogen atoms contained in the charge injection blocking layer is present on the support side. 12. The electron according to claims 1 to 11, wherein the long wavelength photosensitive layer contains at least one of an atom belonging to Group 1 or Group 3 of the periodic table, an oxygen atom, and a nitrogen atom. Photographic light-receiving member.