JPS63200157A - Photoreceptive member for electrophotography - Google Patents

Abstract

PURPOSE:To improve the initial electrification, the continuously repeated usage property, the withstand voltage property, the usage environmental property and the durability of the titled member by constituting the layer having a functional separation type by specific CTL and CGL. CONSTITUTION:The titled material has a photoreceptive layer 102 laminated the electric charge transfer layer (CTL) 103, the electric charge generating layer (CGL) 104 and a surface layer 105 in this order on a substrate 101, and the CGL 104 and CTL 103 contain a silicon atom as a host, and is composed of a non-monocrystalline material contg. any one of hydrogen atom and halogen atom. And, the CTL contains at least one kind of the atoms selected from carbon atom, nitrogen atom and oxygen atom, and has a part which contains an atom belonging to group V atoms of the periodic table as a substance capable of controlling a conductive property, in an inhomogeneous distribution state and the direction of the film thickness. Thus, the titled member having substantially and always stability, without depending the electric, optical and photoconductive characteristics of the titled member on the usage surroundings is obtd.

Description

[Detailed description of the invention] [Description of the field to which the invention pertains] The present invention relates to light (here, light in a broad sense, meaning ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, etc.). The present invention relates to an electrophotographic light-receiving member that is sensitive to electromagnetic waves.

[Description of prior art]

In the image forming field, high sensitivity, SN
The ratio [photocurrent (Ip) / dark current (Id)) is high (, has absorption spectrum characteristics that match the spectral characteristics of the electromagnetic wave to be irradiated, has fast photoresponsiveness (, has a desired dark resistance value), Characteristics such as being non-polluting to the human body during use are required.In particular, in the case of electrophotographic light-receiving members incorporated into electrophotographic devices used in offices as business machines, the above-mentioned characteristics are required. The non-polluting property during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as A-3i) is a photoconductive material that has recently attracted attention.
Application as a light-receiving member for electrophotography is described in JP 855718 and the like.

However, electrophotographic light-receiving members having a light-receiving layer made of conventional A-3i have poor electrical and optical properties such as dark resistance, photosensitivity, and photoresponsiveness.

Individual improvements have been made in terms of photoconductive properties, use environment properties, stability over time, and durability, but further improvements have been made to improve overall properties. The reality is that there is room for improvement.

For example, when applied to light-receiving members for electrophotography, when trying to achieve high photosensitivity and high dark resistance at the same time, it has often been observed in the past that residual potential remains during use; When used repeatedly for a long period of time, there are many disadvantages such as the accumulation of fatigue due to repeated use and the generation of afterimages, or the so-called ghost phenomenon.

In addition, when forming a photoreceptive layer using A-3i material, in order to improve its electrical and photoconductive properties, hydrogen atoms (H) or halogen atoms (X) such as fluorine atoms and chlorine atoms are added. , boron atoms, phosphorus atoms, etc. to control the electrical conductivity type, or other atoms to improve other properties are contained in the photoconductive layer as constituent atoms, respectively.
Depending on the manner in which these constituent atoms are contained, problems may arise in the electrical or photoconductive properties or electrical withstand voltage of the formed layer.

That is, for example, the lifetime of photocarriers generated in the photoconductive layer formed by light irradiation may not be sufficient, or the image transferred to the transfer paper may have localized areas commonly called "white spots". When a blade is used as a cleaning means, there are image defects that are thought to be caused by discharge breakdown phenomena, and image defects that are commonly referred to as "white streaks" that are thought to be caused by the rubbing of the blade. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of images often occurs.

Therefore, while efforts are being made to improve the properties of the A-3i material itself, when designing a light-receiving member, the layer structure, chemical composition of each layer, 9 manufacturing method, etc. must be adjusted so that all of the above-mentioned problems can be solved. It needs to be improved.

[Purpose of the invention]

An object of the present invention is to solve the various problems in electrophotographic light-receiving members having conventional light-receiving layers made of silicon-based materials as described above.

That is, the main purpose of the present invention is electrical.

Its optical and photoconductive properties are almost always stable, almost independent of the environment in which it is used, and it has excellent resistance to light fatigue, does not deteriorate even after repeated use, has excellent durability and moisture resistance, and has no residual An object of the present invention is to provide a light-receiving member for electrophotography having a light-receiving layer made of a material based on silicon atoms in which no or almost no potential is observed.

Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support, and between each layer of laminated layers.
It is an object of the present invention to provide a light-receiving member for electrophotography, which has a light-receiving layer made of a silicon-based material that is dense and stable in terms of structural arrangement and has high layer quality.

Still another object of the present invention is that, when applied as a light-receiving member for electrophotography, the present invention has sufficient charge retention ability during charging processing for electrostatic image formation, making ordinary electrophotographic methods extremely effective. It is an object of the present invention to provide a light-receiving member for electrophotography, which has a light-receiving layer made of a material containing silicon atoms as a matrix and exhibits excellent electrophotographic properties that can be applied.

Another object of the present invention is to easily obtain high-quality images with high density, clear halftones, and high resolution without any image defects or blurring during long-term use. An object of the present invention is to provide a light-receiving member for electrophotography having a light-receiving layer made of a material based on.

Still another object of the present invention is to provide a light-receiving member for electrophotography, which has a light-receiving layer made of a silicon-based material, which has high photosensitivity, high signal-to-noise ratio characteristics, and high electrical voltage resistance. It's about doing.

[Structure of the invention]

The electrophotographic light-receiving member of the present invention includes a support, a charge transport layer (hereinafter abbreviated as rCTLJ), a charge generation layer (hereinafter abbreviated as rcGLJ), and a surface layer on the support in this order. and a photoreceptive layer having a layered structure laminated in order from the body side, and the CGL and the CTL have a silicon atom base on the support and contain a small amount (both hydrogen atoms and halogen atoms). (hereinafter abbreviated as rNon-3i (H,X)J), and the CTL contains at least one of carbon atoms, nitrogen atoms, and oxygen atoms, and controls conductivity. It is characterized by having a small portion containing atoms belonging to Group V of the periodic table in a non-uniform distribution state in the thickness direction.

[For production]

The electrophotographic light-receiving member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems and has extremely excellent electrical properties.

Demonstrates optical, photoconductive properties, durability and usage environment characteristics.

In particular, the influence of residual potential on image formation is practically practically non-existent (its electrical characteristics are stable, high sensitivity, high SN
It has light fatigue resistance, repeated use characteristics,
Because it has excellent moisture resistance and electrical pressure resistance, it is possible to stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

Furthermore, the electrophotographic light-receiving member of the present invention has high photosensitivity in the entire visible light range and fast photoresponse. Therefore, in order to be able to repeatedly obtain a large number of high-resolution, high-quality images in a stable state and at high speed, it is possible to repeatedly obtain large numbers of high-resolution, high-quality images in a stable state. CT
By adopting a functionally separated structure using L and CGL, each layer has the important functions of generating photocarriers and transporting the generated photocarriers, which are important functions for electrophotographic light-receiving members. Compared to having both functions in one layer, there is a greater degree of freedom in laying the layers, and products with superior properties can be produced. In addition, since CTL contains a small amount of carbon atoms, nitrogen atoms, and oxygen atoms, the relative permittivity of CTL can be lowered, so the capacitance per layer thickness can be reduced. ,
It is possible to improve charging ability and sensitivity, and it also improves resistance to high voltages and improves durability. In addition, CT
L contains atoms belonging to group V of the periodic table as a substance that controls conductivity in a non-uniform distribution state in the layer thickness direction, so that C has an optimal charge transport ability as desired.
Can design TL.

Furthermore, charge injection properties at the interface between CLT and CGL are improved, resulting in improved charging ability, sensitivity, and residual potential.

Ghosting, sensitivity unevenness, durability, resolution, etc. can be dramatically improved.

In addition, the surface layer provided on the surface dramatically improves mechanical strength and electrical pressure resistance, and effectively prevents charge from being injected from the surface when subjected to charging treatment. , charging capacity, usage environment characteristics.

Durability and electrical durability are improved.

[Detailed description of the invention]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic light-receiving member of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a schematic diagram schematically showing a preferred layer structure of the electrophotographic light-receiving member of the present invention.

The electrophotographic light receiving member 100 shown in FIG.
i (H, CTL103 and Non-3, which have at least a portion that is unevenly distributed in the layer thickness direction
i (H.

The light-receiving layer 102 has a layered structure consisting of a CGL 104 composed of X) and a surface layer 105. surface layer 1
05 has a free surface 106.

Support 101 used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr and stainless steel.

Aj7. Cr, Mo, Au, Nb, Ta,
V, Ti, Pt.

Examples include metals such as pb and alloys thereof.

Polyester is used as the electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass.

Examples include ceramic and paper. It is preferable that at least one surface of these electrically insulating supports is conductively treated, and a light-receiving layer is provided on the conductively treated surface side.

For example, if it is glass, on its surface, N r Cr +
AI, Cr, Mo, Au, Ir, Nb, T
a, V, Ti.

Conductivity is imparted by providing a thin film made of Pt, Pd, InO3, ITO (In203+Sn), etc., or if it is a synthetic resin film such as a polyester film, NiCr, Aj7. Ag, Pb, Zn,
Ni.

Au, Cr, Mo, Ir, Nb,
Ta, V, Tj! , Vacuum evaporation and electron beam evaporation of thin films of metals such as Pt.

The surface is provided with sputtering or the like, or the surface is laminated with the metal to impart conductivity to the surface. The shape of the support can be a plate, an endless belt, or a cylinder with a smooth or uneven surface, and its thickness is determined as appropriate so as to form a desired electrophotographic light-receiving member. When flexibility is required as a light-receiving member for electrophotography, it can be made as thin as possible within a range that allows it to function as a support.

However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

In particular, when recording an image using coherent light such as a laser beam, the surface of the support may be provided with irregularities in order to eliminate image defects caused by so-called interference fringe patterns that appear in visible images.

The unevenness provided on the surface of the support is created by fixing a cutting tool having a 7-shaped cutting edge in a predetermined position on a cutting machine such as a milling machine or a lathe, for example, using a program designed in advance to create a cylindrical support according to desired conditions. By regularly moving the support in a predetermined direction while rotating it according to the rotation angle, the surface of the support is accurately cut to form a desired uneven shape, pitch, and depth. The inverted V-shaped linear protrusion created by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped protrusion may be a double or triple spiral structure, or a crossed spiral structure.

Alternatively, in addition to the spiral structure, a parallel line structure along the central axis may be introduced.

The vertical cross-sectional shape of the uneven convex portions provided on the surface of the support is designed to achieve controlled non-uniformity of the layer thickness within the microcolumns of each layer formed, and between the support and the layer directly provided on the support. In order to ensure good adhesion and desired electrical contact, the inverted V-shape is preferably used (A) and (B) as shown in Figure 2.
), (C), it is desirable that the shape is substantially an isosceles triangle, a right triangle, or a scalene triangle.

Among these shapes, isosceles triangles and right triangles are particularly desirable.

In the present invention, the dimensions of the irregularities provided on the surface of the support in a controlled manner are set in such a way that the object of the present invention can be achieved as a result, taking into account the following points.

That is, the first is Non-3i (H
, Therefore, it is necessary to set the dimensions of the irregularities provided on the surface of the support so as not to cause deterioration in the layer quality of the Non-3i (H,X) photoreceptive layer.

Secondly, if the free surface of the photoreceptive layer has extreme irregularities, it may become impossible to completely clean the image in the cleaning process after image formation.

Further, when cleaning the blade, there is a problem in that the blade may become damaged quickly.

As a result of examining the above-mentioned layer deposition problems, electrophotographic process problems, and conditions for preventing interference fringes, the pitch of the recesses on the surface of the support is preferably 5001 t m or more.
0.3 μm, more preferably 200 μm to 1 μm1
The optimal thickness is preferably 50 μm to 5 μm.

Further, the maximum depth of the recess is preferably 0.1 μm to 5 μm.
m1, preferably 0.3 μm to 3 μm1, optimally 0.3 μm to 3 μm1.
It is desirable that the thickness be 6 μm to 2 μm.

When the pitch and maximum depth of the recesses on the surface of the support are within the above range, the slope of the slope of the recesses (or linear protrusions) is preferably 1 degree to 20 degrees, more preferably 3 degrees to 15 degrees,
The optimum temperature is preferably 4 degrees to 10 degrees.

Furthermore, based on the non-uniformity of the layer thickness of each layer deposited on such a support (the maximum difference in layer thickness is preferably 0.1 μm to 2 μm within the same pitch, more preferably 0.1 p m
~1.5 μm, optimally 0.2 pm to 1 pm
It is desirable that this is done.

Further, as another method for eliminating image defects caused by interference fringe patterns when coherent light such as laser light is used, an uneven shape formed by a plurality of spherical trace depressions may be provided on the surface of the support.

That is, the surface of the support has irregularities smaller than the resolving power required for electrophotographic light-receiving members, and the irregularities are caused by a plurality of spherical trace depressions.

Below, the shape of the surface of the support in the light-receiving member for electrophotography of the present invention and a preferred manufacturing example thereof will be explained with reference to FIGS. 3 and 4. The manufacturing method is not limited to this.

FIG. 3 schematically shows a typical example of the surface shape of the support in the electrophotographic light-receiving member of the present invention, partially enlarging a part of the uneven shape.

In FIG. 3, 301 is a support, 302 is a support surface,
303 indicates a rigid true sphere, and 304 indicates a spherical trace depression.

Furthermore, FIG. 3 also shows one example of a preferred manufacturing method for obtaining the surface shape of the support. In other words, a spherical depression 304 is formed by allowing a rigid true sphere 303 to naturally fall from a position at a predetermined height from the support surface 302 and collide with the support surface 302 . Then, by using a plurality of rigid true spheres 303 having approximately the same diameter R8 and dropping them simultaneously or sequentially from approximately the same height h, the supporting body surface 302 has approximately the same radius of curvature R and Multiple spherical trace depressions 3 having the same width
04 can be formed.

As described above, FIG. 4 shows a typical example of a support having an uneven shape formed by a plurality of spherical trace depressions on its surface.

In FIG. 4, 401 is a support, 402 is a convex position of an uneven portion, 403 is a rigid true sphere, and 404 is a spherical trace depression.

Incidentally, the radius of curvature R and the width of the uneven shape formed by the spherical trace depressions on the surface of the support of the light-receiving member for electrophotography of the present invention serve to prevent the occurrence of interference fringes in the light-receiving member for electrophotography of the present invention. This is an important factor in achieving the effect efficiently. As a result of various experiments, the present inventors have discovered the following points. That is, when the radius of curvature R and the width satisfy the following formula: % formula %, 0.5 or more Newton rings due to shearing interference are present in each trace depression. Furthermore, if the following formula: % formula % is satisfied, one or more Newton rings due to shearing interference will exist in each trace depression.

For this reason, in order to disperse the interference fringes that occur throughout the electrophotographic light receiving member into each trace depression and to prevent the occurrence of interference fringes in the electrophotographic light receiving member, the above-mentioned - 0.035 or more,
Preferably, it is 0.055 or more.

In addition, the width of the unevenness due to the trace depression is at most 500
It is desirable that the thickness be about .mu.m, preferably 200 .mu.m or less, more preferably 100 .mu.m or less.

The example in FIG. 4 shows an example in which a rigid true sphere with approximately the same radius R6 is used, but the support in the present invention is not limited to this, and the purpose of the present invention can be achieved. A plurality of types of rigid true spheres with different radii R8 may be used, with the number and type being managed within the range.

In FIG. 5, C
TL502. CGL503. An example in which a light-receiving layer 500 consisting of a surface layer 504 is formed is shown. Surface layer 504
has a free surface 505.

CGL CGL (104,503) in the present invention is Non
-3i(H,X) and has desired photoconductive properties, particularly charge generation properties.

The CGL in the present invention includes a substance that controls conductivity,
Carbon atom (C), nitrogen atom (N) and oxygen atom (0)
Substantially none of these are contained.

Further, the hydrogen atoms and/or halogen atoms contained in the CGL of the present invention compensate for the dangling bonds of silicon atoms and are effective in improving layer quality, particularly photoconductive properties.

The content of hydrogen atoms, halogen atoms, or the sum of hydrogen atoms and halogen atoms is preferably 1 to 40 at%, more preferably 5 to 30 at%, and optimally 10 to 20 at%. desirable.

In the present invention, the layer thickness of the CGL is determined depending on the light absorption coefficient of the light source used in the electrophotographic image forming apparatus in order to obtain desired electrophotographic characteristics and economical effects, especially to obtain sufficient charge generation ability. The thickness is determined as desired, preferably from 0.01 to 30 μm.

More preferably 0.1 to 20 μm, optimally 1 to 10 μm
It is desirable that this is done.

In the present invention, in order to form a CGL composed of Non-3i (H, ,ECR-C
It can be formed by various thin film deposition methods such as a VD method, a sputtering method, a vacuum evaporation method, an ion blating method, a photo CVD method, and a thermal CVD method.

In addition to these, active species (A) generated by decomposing raw material gas for forming a non-single crystal material;
The active species (B) generated from the film-forming chemical substance that chemically interacts with the active species (B) are separately introduced into the film-forming space for forming the deposited film, and these are caused to chemically react. Method for forming crystalline materials (rHRCVD method)
), a raw material gas for forming a non-single crystal material and a halogen-based oxidant gas having the property of oxidizing the raw material gas are separately introduced into a film forming space for forming a deposited film. Examples include a thin film deposition method such as a method of forming a non-single crystal material by chemically reacting these materials (hereinafter abbreviated as "rFOcVD method"). These thin film deposition methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, equipment capital investment load, manufacturing scale 9, and the desired characteristics of the light-receiving member to be manufactured. The glow discharge method, sputtering method, method, ion blating method, ECR-CVD method, HRCVD method, FOC
The VD method is preferred. In some cases, these methods may be used in combination in the same device system.

For example, Non-3i (H,X
), basically a raw material gas for Si supply that can supply silicon atoms (Si) and a raw material gas for introducing hydrogen atoms (H) or/and halogen atoms (X). A raw material gas for introduction is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber, which is then deposited onto the surface of a predetermined support that has been placed at a predetermined position in advance. N on -S i (
A layer consisting of H, X) may be formed. When forming by sputtering, a target made of Si is used in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
This is accomplished by introducing a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) into a sputtering deposition chamber as needed to form a plasma atmosphere of a desired gas.

In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon is housed in an evaporation board as an evaporation source, and this evaporation source is heated and evaporated by a resistance heating method or an electron beam method (EB method). This can be carried out in the same manner as in the sputtering method, except that the flying evaporated material is passed through a desired gas plasma atmosphere. Non-3i (H,
In order to form a CGL composed of Activated species (A) are generated by generating glow discharge or overheating in the chemical space, and raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (
X) Introduce raw material gas for introduction into another activation space in the same way to generate active species (B), and activate species (A) and active species (B)
were separately introduced into the deposition chamber, and the Non-5
It is sufficient to form a layer consisting of i (H,X).

In order to form a CGL composed of Non-3i (H, (X) A gas is introduced into the deposition chamber at a desired gas pressure separately from the raw material gas, and these gases are caused to chemically react in the deposition chamber, so that the gas is deposited on the surface of a predetermined support that has been placed in a predetermined position in advance. Non-3i
A layer consisting of (H,X) may be formed.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4, Si2H6゜Si3
Silicon hydride (silanes) in a gaseous state or that can be gasified, such as H8, Si 4 HIO, etc., can be used effectively, especially because of its ease of handling during layer fabrication work, good Si supply efficiency, etc. In this respect, SiH4°Si 2 H6 is preferred.

Effective raw material gases for introducing halogen atoms used in the present invention include poly(halogen compounds), such as halogen gases, halogen compounds, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be gasified.

Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, and bromine.

Iodine halogen gas, BrF, CI F, CI
F3.

BrF5. BrF3. IF3. IF7. ICI
, IBr, and other interhalogen compounds.

Specific examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include SiF4, Si2 F6, and 5iC14.

Silicon halides such as SiBr4 are preferred.

When forming the characteristic electrophotographic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas as a raw material gas capable of supplying Si is used. Even if it is not used, CGL consisting of Non-3i (H,X) containing a halogen atom can be formed on a desired support.

CGL containing halogen atoms according to the glow discharge method
Basically, when manufacturing CGL, for example, silicon halide, which is a raw material gas for supplying Si, is introduced into a deposition chamber where CGL is formed at a predetermined gas flow rate, and a glow discharge is generated to process these materials. CGL can be formed on a desired support by forming a plasma atmosphere of these gases, but in order to make it easier to control the ratio of hydrogen atoms introduced, Furthermore, a layer may be formed by mixing hydrogen gas or a silicon compound gas containing hydrogen atoms as desired.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio.

Sputtering method, ion blating method.

In order to introduce halogen atoms into the layer formed by either the HRCV D method or the FOCVD method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a gas plasma atmosphere.

In addition, when introducing hydrogen atoms, a source gas for introducing hydrogen atoms, such as F2 or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gases. Just do it.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl1°HBr, Hl, etc. Hydrogen halide, 5jH2F2, SiH212, SiH2
C12, 5iHCj! 2, SiH2Br2.

Gaseous or gasifiable materials such as halogen-substituted silicon hydrides such as 5iHBr2 may also be mentioned as useful starting materials for CGL formation.

Among these substances, halides containing hydrogen atoms are C
Hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer during GL formation, so it is used as a suitable raw material for halogen introduction in the present invention.

In order to structurally introduce hydrogen atoms into CGL, in addition to the above, F2, SiH4, Si2H6゜S i 3 H
silicon hydride and Si such as
This can also be carried out by coexisting silicon or a silicon compound in the deposition chamber to generate a discharge.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in CGL, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) can be controlled. amount of starting material introduced into the deposition system.

All you have to do is control the discharge power, etc.

CTL The CTL (103,502) in the present invention is composed of a silicon atom, a small number of carbon atoms, a nitrogen atom, and an oxygen atom as constituent elements, and an atom belonging to Group V of the periodic table as a substance that controls conductivity. (M) and N containing
on-3t (H,X) (hereinafter referred to as rNon-3iM (
C,N,0)(H,X)J), and has charge transport properties that satisfy desired electrophotographic properties. Carbon atoms contained in the CTL.

Nitrogen atoms or oxygen atoms may be contained in the CTL in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. It may be included.

Atoms (M) belonging to Group V of the periodic table are contained in a non-uniformly distributed state in the layer thickness direction. In any case, if any of the atoms (M) belonging to Group V of the periodic table, carbon atoms, nitrogen atoms, and oxygen atoms are contained, they are contained in the entire layer region of the CTL.

The atoms (M) are contained in the CTL such that the distribution concentration of atoms (M) belonging to Group V of the periodic table in the layer thickness direction of the CTL is non-uniform in at least some layer regions of the CTL. .

The distribution concentration of carbon atoms, nitrogen atoms, and oxygen atoms in the CTL in the layer thickness direction may be uniform, or the distribution concentration of carbon atoms, nitrogen atoms, and oxygen atoms in the CTL may be uniform, or the distribution concentration in the CTL may be uniform (or some may be The content may be non-uniform in the layer region.

6 to 21 show typical examples of the distribution state of atoms (M) belonging to Group V of the periodic table contained in CTL in the layer thickness direction.

In FIGS. 6 to 21, the horizontal axis represents the contained atoms (M
), the vertical axis shows the layer thickness of CTL, tB shows the position of the end face of CTL on the support side, and tT shows the position of the end face of CTL on the side opposite to the support side. That is, atoms (
The CTL containing M) is layered from the tB side toward the tT side.

FIG. 6 shows a first typical example of the distribution state of atoms (M) contained in the CTL in the layer thickness direction.

In the example shown in FIG. 6, from the interface position tB to the position t+a, the distribution concentration C of atoms (M) takes a constant value of C57, but the atoms (M) are contained in the layer region where they are formed. From position t16, the distributed concentration value Css is gradually and continuously decreased until reaching the interface position tT. At the interface position, the distribution concentration C of atoms (M) is set to a value C59.

In the example shown in FIG. 7, the contained atoms (M)
The distributed density C gradually and continuously decreases from the distributed density value Cso from the position tB to the position tT, forming a distribution state in which the distributed density value Cso becomes the distributed density value C61 at the position tT.

In the case of Fig. 8, the distribution concentration C of atoms (M) from position to to position t17 is a constant value of distribution concentration C62, and gradually and continuously between position t1□ and position tT. At the position tT, the distribution concentration C is substantially zero (substantially zero here means that it is less than the detection limit amount, and the meaning of "substantially zero" hereinafter is also the same). be).

In the case of FIG. 9, the distribution concentration C of atoms (M) is at position t8
The density value C64 is continuously and gradually decreased from the density value C64 until reaching the position tr, and becomes substantially zero at the position 11.

In the example shown in Figure 1O, the distribution concentration C of atoms (M)
is a constant distributed density value C65 between position tB and position t18, and is a constant distributed density value C65 at position tT. Between position t+s and position tT,
The distribution density C is linearly decreased from position t18 to position tT.

In the example shown in FIG. 11, from the position tB to the position tT, the distribution concentration C of atoms (M) decreases linearly from the distribution concentration C66 to substantially zero.

In the example shown in FIG. 12, the contained atoms (M
) distribution density C is 06 from position ts to position tT.
8 gradually and continuously decreases to the value C6 at position tT.
A distribution state of 9 is formed.

In the example shown in FIG. 13, the distribution concentration C of atoms (M) takes a constant value of C70 from position to to position t+9, and from position t19 to position tT, from C7+ to C
The distribution state decreases linearly up to 72.

The examples shown in FIGS. 6 to 13 are all tT
An example was shown in which the distribution concentration C of atoms (M) is higher on the tB side than on the tB side, but if the tT side and tB side are completely reversed, tB
The distribution concentration C of atoms (M) may be greater on the tT side than on the tT side.

For example, in the example shown in FIG. 14, in FIG.
When the side and tB side are reversed, the position t is lower than the interface position tB.
The distribution concentration C of atoms (M) increases gradually and continuously from C75 until reaching 2o, reaches 074 at position t20, and becomes a constant value of C73 from position t2o to interface position tT.

In the example shown in FIG. 15, the distribution concentration C of atoms (M) is from C77 to C76 from position tB to position tT.
A distribution state is formed that gradually and continuously increases up to .

In the example shown in FIG. 16, the distribution concentration C of atoms (M) increases gradually and continuously from position tB to position t21 from substantially zero to C79, and from position t21 to C78. It takes a constant value and forms a distribution state that reaches position tT.

In the example shown in FIG. 17, the distribution concentration C of atoms (M) forms a distribution state in which it gradually and continuously increases from substantially zero to C8o from position tB to position tT. .

In the example shown in FIG. 18, the distribution concentration C of atoms (M) is from C82 to C from position tB to position t2□.
Ca increases linearly up to s+, and from position t22 Ca
It takes a constant value of + and forms a distribution state that reaches position tT.

In the example shown in FIG. 19, the distribution concentration C of atoms (M) forms a distribution state in which it substantially increases linearly from zero to C83 from position tifftB to position tT. .

In the example shown in FIG. 20, the distribution concentration C of atoms (M) is from C85 to C8 from position tB to position D.
A distribution state is formed that gradually and continuously increases up to 4.

In the example shown in FIG. 21, the distribution concentration C of atoms (M) is from Csa to C8 from position tB to position tO.
C8 increases linearly up to 7, and from the position M t 23
It takes a constant value of 6 and forms a distribution state that reaches position tT.

Figures 22 to 31 show the thickness direction of carbon atoms and/or nitrogen atoms and/or oxygen atoms (hereinafter collectively abbreviated as "atoms (Y)") contained in CTL. A typical example of the distribution state is shown.

In FIGS. 22 to 31, the horizontal axis indicates the contained atoms (
Y), the vertical axis shows the layer thickness of CTL, and tB
indicates the position of the end face of the CTL on the support side, and tT indicates the position of the end face of the CTL on the opposite side to the support side.

That is, the CTL containing atoms (Y) is formed in layers from the tB side toward the tT side.

FIG. 22 shows a first typical example of the distribution state of atoms (Y) contained in the CTL in the layer thickness direction.

In the example shown in FIG. 22, from the interface position tB where the support and CTL are in contact to the position t24, the distribution concentration C of atoms (Y) takes a constant value of C89, and the atoms (Y)
) is contained in the formed CTL, and from the position t24, the concentration is gradually and continuously decreased from the concentration C90 to the interface position tT. At the interface position, the distribution concentration C of atoms (Y) is set to a value C91.

In the example shown in FIG. 23, the contained atoms (Y
) forms a distribution state in which the concentration C gradually and continuously decreases from the concentration C92 from the position tB to the position 11r, and reaches the concentration C93 at the position tr.

In the case of Fig. 24, the distribution concentration C of atoms (Y) from position tB to position 125 is a constant value of concentration C94, and gradually and continuously decreases from position C95 between position t25 and position tT. , and the distribution concentration C is substantially zero at the position (here, substantially zero).

is below the detection limit).

In the case of FIG. 25, the distribution concentration C of atoms (Y) is at position t
From B to position tr, the density value C9B is gradually decreased continuously, and becomes substantially zero at position tT.

In the example shown in FIG. 26, the distribution concentration C of atoms (Y)
The density is a constant value of C97 between the position tB and the position +26, and the density is 098 at the position tT. Between position t26 and position tT, the distribution density C is linearly decreased from position ff1t26 to position tT.

In the example shown in FIG. 27, from the position tB to the position tT, the distribution concentration C of atoms (Y) decreases in a linear manner from the concentration C99 to substantially zero.

In the example shown in FIG. 28, the contained atoms (Y
) from position ta to position tr (,
C gradually and continuously decreases from +00 at position tT.
A distribution state like a lot is formed.

In the example shown in FIG. 29, the distribution concentration C of atoms (Y) takes a constant value of ClO2 from position tB to position t27, and from position t27 to position tT, the distribution concentration C of atoms (Y) takes a constant value of ClO2 from position t27 to position tT.
The distribution state decreases linearly up to +04.

In the example shown in FIG. 30, the distribution concentration C of atoms (Y) takes a constant value of ClO3 from position tB to position tT.

The examples shown in FIGS. 22 to 29 are all t
We have shown an example where the distribution concentration C of atoms (Y) is higher on the tB side than on the T side, but if the tT side and tB side are completely reversed, t
The distribution concentration C of atoms (Y) may be higher on the tT side than on the B side. For example, in the example shown in FIG. 31, in FIG. 22, when the tT side and the ta side are reversed, the interface position t
From B to position t2B, the distribution concentration C of atoms (Y) increases gradually and continuously from CXoa until it reaches C+ at position t2B.
07, and the value C1o from position t2a to interface position tT
It becomes a constant value s.

Atoms (M) belonging to group Ⅰ of the periodic table (hereinafter referred to as ``group V'')
"group atoms". ) is an impurity that imparts so-called n-type conductivity in the semiconductor field. Specifically, the Group V atom is P (phosphorus).

As (arsenic), sb (antimony), Bi (bismuth)
etc., with P and As being particularly suitable.

In the present invention, by containing Group V atoms (M) as a conductivity controlling substance in the entire layer region of the CTL, the effect of controlling the conductivity type and/or conductivity and/or the interaction between CGL and CTL is achieved. Although it is possible to obtain the effect of improving the charge injection property during the period, its content is set to be relatively small. The content of atoms (M) is preferably l x 10= ~ I x 103 atoms p p m
, more preferably 5 x 10-'' to 1 x 102 atoms p
It is desirable that p m is optimally between lXl0-'' and 50 atomic ppm.

Further, the entire layer region of the CTL in the present invention contains carbon atoms and/or oxygen atoms and/or nitrogen atoms, and is mainly used to increase dark resistance, control spectral sensitivity, and improve adhesion between the CGL and CTL. You can measure your improvement. The content of carbon atoms, oxygen atoms, or nitrogen atoms, or when at least two of them are contained, the total amount thereof is preferably I X 10-a to 5
×10 atomic %, more preferably 5 X I O-” to 4 ×
It is desirable that the content be 10 atomic %, most preferably I x 10-' to 3×10 atomic %.

Further, the hydrogen atoms and/or halogen atoms contained in the CTL of the present invention can compensate for the dangling bonds of silicon atoms and improve the layer quality.

The content of hydrogen atoms or halogen atoms, or the sum of hydrogen atoms and halogen atoms, contained in CTL is preferably 1 to 70 atom%, more preferably 5 to 50 atom%, and most preferably 10 to 3o It is preferable to express it in atomic percent.

In the present invention, the CTL layer thickness is preferably 5 to 50 μm, more preferably 10 to 40 μm, and most preferably 2 μm from the viewpoint of obtaining desired electrophotographic properties and economical effects.
It is desirable that the thickness be 0 to 30μ.

In the present invention, atoms (Y) can be introduced into the CTL by using them together with the starting materials for forming the CTL, and by controlling the amount of the atoms (Y) in the formed layer.

Glow discharge method, HRCVD method, FOCVD method
In order to form the TL, as a starting material for introducing nitrogen atoms, a small number of gaseous substances having nitrogen atoms as a constituent atom or gasified substances that can be gasified can be used.

For example, a source gas containing silicon atoms (Si), a source gas containing nitrogen atoms (N), and hydrogen atoms (H) and/or halogen atoms (X) as necessary. or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are nitrogen raw materials (N) and hydrogen atoms (H). gas, also at a desired mixing ratio, or silicon atoms (S
i) as a constituent atom and a silicon atom (Si
), nitrogen atoms (N), and hydrogen atoms (H) can be mixed and used.

Alternatively, a raw material gas containing nitrogen atoms (N) may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (H).

Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) include nitrogen (N2), which has N as a constituent atom, or has N and H as constituent atoms,
Ammonia (NH3), hydrazine (N2NNH2
), hydrogen azide (HNa), ammonium azide (N)
Gaseous or gasifiable nitrogen such as (4N3), nitrogen compounds such as nitrides and azides can be mentioned. In addition to this, halogenated nitrogen compounds such as nitrogen trifluoride (F3N) and nitrogen tetrafluoride (F4N2) can be used because they can introduce halogen atoms (X) in addition to nitrogen atoms (N). can be mentioned.

C by glow discharge method, HRCVD method, FOCVD method
In order to form TL, as a starting material for introducing carbon atoms, a small number of gaseous substances having carbon atoms as constituent atoms or gasified substances that can be gasified can be used.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing carbon atoms (C) as constituent atoms, and hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms as necessary. or a raw material gas containing silicon atoms (Si) and a raw material gas containing carbon atoms (C) and hydrogen atoms (H). are also mixed at a desired mixing ratio, or a source gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), carbon atoms (C), and hydrogen atoms (H) are mixed. It can be used in combination with a raw material gas having constituent atoms.

Alternatively, a raw material gas containing carbon atoms (C) as constituent atoms may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms ()() as constituent atoms.

Starting materials that can be effectively used as raw material gases for introducing carbon atoms (C) include saturated hydrocarbons containing C and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, and saturated hydrocarbons having 2 to 4 carbon atoms.
Examples include ethylene hydrocarbons, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C2H6), propane (C3H8).

n-butane (n C4HIO), pentane (05HI
2).

Ethylene hydrocarbons include ethylene (C2H4)1
Propylene (ca Ha), butene-1 (C4H8).

Butene-2(C4H8)lisobutylene(C4H1l)
.

Pentene (CsH+o), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3
H4), butyne (C4H6), and the like.

As a raw material gas containing Si, C, and H as constituent atoms, S
Examples include alkyl silicides such as i (CH3)4 and Si (02H,)4.

In addition to this, CF4゜CCl4
．． Examples include halogenated carbon gases such as CH3CF.

C by glow discharge method, HRCVD method, FOCVD method
As the starting material for introducing oxygen atoms when forming the TL, most gaseous substances or gasified substances having at least oxygen atoms as a constituent atom can be used.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (0) as constituent atoms, and hydrogen atoms ()() or/and halogen atoms (X) as necessary. or a raw material gas containing silicon atoms (Si) and oxygen atoms (0) and hydrogen atoms (H) as constituent atoms. Either mix with the raw material gas at a desired mixing ratio, or mix silicon atoms (
A raw material gas whose constituent atoms are silicon atoms (Si) and silicon atoms (S
t), a raw material gas having three constituent atoms: an oxygen atom (0) and a hydrogen atom (H) can be used in combination.

Alternatively, a raw material gas containing oxygen atoms (0) as constituent atoms may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms.

Starting materials that can be effectively used as raw material gases for introducing oxygen atoms (0) include, for example, oxygen (0□), ozone (03), -nitrogen oxide (NO), and nitrogen dioxide (NO).
2), -nitrogen dioxide (N2 o), nitrogen sesquioxide (N2 o)
03), trinitrogen tetraoxide (N204), nitrogen sesquioxide (N
20s), nitrogen oxide (NO□), silicon atom (Si)
For example, disiloxane (H3SiO3i') (3) with an oxygen atom (0) and a hydrogen atom (H) as constituent atoms.

Examples include lower siloxanes such as trisiloxane ()13SiO3iH20SiH3).

To form CTL by sputtering method, r″
L
wafer and/or SiO2 wafer containing a mixture of Si (!l: Si
This can be carried out by sputtering a wafer containing a mixture of O3 and/or a SiC wafer, or a wafer containing a mixture of Si and SiC in various gas atmospheres.

For example, if a Si wafer is used as a target to contain nitrogen atoms, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms or/and halogen atoms may be diluted with a diluent gas as necessary. These gases may be introduced into a deposition chamber for sputtering to form a gas plasma of these gases to sputter the Si wafer.

Alternatively, by using Si and Si3N4 as separate targets or a single mixed target of Si and Si3N4, in an atmosphere of diluent gas as a sputtering gas, or at least hydrogen atoms (
This is accomplished by sputtering in a gas atmosphere containing H) or/and halogen atoms (X) as constituent atoms.

As the raw material gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms, the raw material gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms in the raw material gas shown in the example of the glow discharge method mentioned above can also be used when sputtering is used. Can be used as an effective gas.

In the present invention, when forming a CTL, the distribution concentration c (y) of atoms (Y) contained in the layer is changed in the layer thickness direction to obtain a desired distribution state in the layer thickness direction (depth pr
In order to form a layer having a distribution concentration C of
This is accomplished by introducing a gas as a starting material for introducing atoms (Y) to change (Y) into the deposition chamber while appropriately changing the gas flow rate according to a desired rate of change curve.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be appropriately changed by any commonly used method such as manually or using an externally driven motor.

When forming by the sputtering method, the desired distribution state (depth) of atoms (Y) in the layer thickness direction is achieved by changing the distribution concentration c (y) of atoms (Y) in the layer thickness direction.
First, as in the case of the glow discharge method, the starting material for introducing atoms (Y) is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is determined. This can be done by appropriately changing as desired.

Second, the target for sputtering is, for example, S
If a target containing a mixture of Si and Si3N4 is used, this can be done by changing the mixing ratio of Si and Si3N4 in advance in the layer thickness direction of the target.

, SiC or 5i02 may be used in the same manner as for Si3 N4.

To structurally introduce group V atoms into the CTL, the starting material for group V introduction is introduced in a gaseous state into the deposition chamber together with other starting materials for forming the CTL during layer formation. Just do it.

As the starting material for introducing Group V atoms, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

In the present invention, effective starting materials for introducing Group V atoms include PH3,
Next to hydrogen ratio such as P2H4, PH4I.

PF3. PF5. PCI! 3. PCj'5. P
Br3. Examples include halogen ratios such as PBr3°PI3. In addition, AsH3, AsF3. AsCf3. A
sBr3. AsF6°SbH3, SbF3. SbF5,
5bCI! 3,5bC15゜BiI3, B1C1!
3, B1Br3, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

CTL and CGL having characteristics that achieve the object of the present invention
A-3i containing a hydrogen atom or/and a halogen atom (hereinafter referred to as rA-3
i (H,X)J) is selected and configured by
It is necessary to appropriately set the temperature and gas pressure of the support as desired.

The support temperature (Ts) is appropriately selected in an optimal range according to the layer design, but it is usually 50°C to 400°C, preferably 100 to 300°C.

Similarly, the optimum range for the gas pressure in the deposition chamber is selected according to the layer design, but usually I x 10-' to 10
Torr, preferably I x 10-” to 3 Torr,
Optimally, it is desirable to set it to l x 10'' to I Torr.

In the present invention, the above-mentioned ranges are mentioned as preferable numerical ranges for the support temperature and gas pressure for producing each layer, but these layer production factors are usually not determined independently and separately. In order to form each layer with desired properties, it is desirable to determine the optimal value of each layer fabrication factor based on mutual and organic relationships.

Polycrystalline silicon containing hydrogen atoms and/or halogen atoms (rpoly-8i (H,
It will be called J. ), there are various methods for forming the layer, including the following methods.

One method is to increase the support temperature to a high temperature, specifically 40°C.
In this method, the temperature is set at 0 to 600° C., and a film is deposited on the support by plasma CVD.

Another method is to first form an amorphous film on the surface of a support, that is, to form a film on the support at a temperature of about 250° C. by plasma CVD, and then annealing the amorphous film. By processing po
This is a method of converting it into ly.

The annealing treatment involves heating the support at 400-600'C.
This is done by heating for about 5 to 30 minutes or by irradiating with laser light for about 5 to 30 minutes.

[Li] The surface layer 105, 504 in the present invention is a non-containing material containing as constituent elements a silicon atom, at least one of a carbon atom, a nitrogen atom, and an oxygen atom, and at least one of a hydrogen atom and a halogen atom. -3i
Consists of (C, N, O) (H, X). The surface layer contains no or substantially no substance that controls conductivity.

The carbon atoms, nitrogen atoms, or oxygen atoms contained in the layer may be uniformly distributed in the layer, or they may be uniformly distributed in the layer thickness direction, but may be non-uniformly distributed. There may be a portion containing it in a distributed state.

However, in any case, it is necessary that the content be uniformly distributed in the in-plane direction parallel to the surface of the support in order to make the properties uniform in the in-plane direction.

Figures 32 to 41 show the thickness direction of carbon atoms and/or nitrogen atoms and/or oxygen atoms (hereinafter collectively referred to as "atoms (Y)") contained in the surface layer. A typical example of the distribution state is shown.

In FIGS. 32 to 41, the horizontal axis indicates the contained atoms (
Y), the vertical axis shows the surface layer thickness, and tB
indicates the position of the end surface of the surface layer on the side opposite to the support side, and tT indicates the position of the end surface of the surface layer on the side opposite to the support side. That is, the surface layer containing atoms (Y) is closer to tT than the tB side.
Layering occurs laterally.

FIG. 32 shows a first typical example of the distribution state of atoms (Y) contained in the surface layer in the layer thickness direction.

In the example shown in FIG. 32, the distribution concentration C of atoms (Y) increases gradually and continuously from position tB to position t29 from c,l l to C1□0, and from position t29 to Cl09 A distribution state is formed in which a constant value of is reached and the position tr is reached.

In the example shown in FIG. 33, the distribution concentration C of atoms (Y) forms a distribution state in which it gradually and continuously increases from CI+3 to C112 from position tB to position fillT.

In the example shown in FIG. 34, the distribution concentration C of atoms (Y) gradually and continuously increases from substantially zero to C1,5 from position ta to position t30, and from position t3° A distribution state is formed in which C1 and C4 take constant values and reach position tT.

In the example shown in FIG. 35, the distribution concentration C of atoms (Y) forms a distribution state in which it gradually and continuously increases from substantially zero to 01,6 from position MtB to position tT. ing.

In the example shown in FIG. 36, the distribution concentration C of atoms (Y) increases linearly from C818 to C1,7 from position tB to position t31, and remains constant at C11□ from position ta+. A distribution state is formed in which the values are taken and reach the position tT.

In the example shown in FIG. 37, the distribution concentration C of atoms (Y) is substantially from zero to 011.0 from position tB to position tT. A distribution state is formed in which the number increases exponentially until -.

In the example shown in FIG. 38, the distribution concentration C of atoms (Y) forms a distribution state in which it gradually and continuously increases from C1□5゛ to CI2゛ from position tB to position tT. There is.

In the example shown in FIG. 39, the distribution concentration C of atoms (Y) increases linearly from CI24 to CI23 from position tB to position t, and from position t3□, C
A distribution state is formed in which a constant value of I22 is reached at position tT.

In the example shown in FIG. 40, the distribution concentration C of atoms (Y) takes a constant value of C1.5 from position tB to position tT.

In the example shown in FIG. 41, the distribution concentration C of atoms (Y) takes a constant value of CI28 from position tB to position t33, and Cl28 from position 133 to position t33.
From position t34, Cl26 takes a constant value and reaches position tT.

The carbon atoms and/or nitrogen atoms and/or oxygen atoms contained in the entire layer region of the surface layer in the present invention mainly have effects such as increasing dark resistance and increasing hardness. The content of atoms (Y) contained in the surface layer is preferably I
O-" ~ 90 atomic %, more preferably I x 10" ~
It is desirable that the content be 85 atomic %, most preferably 10 to 80 atomic %.

Further, the hydrogen atoms and/or halogen atoms contained in the surface layer in the present invention are Non-3i (C, N, O)
It compensates for the dangling bonds present in (H,X) and is effective in improving film quality.

The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the surface layer is preferably 1 to 70 at%.
, more preferably 5 to 50 atom %, optimally 1O to 30 atom %.

In the present invention, the thickness of the surface layer is preferably 0.003 to 30μ, more preferably 0.01 to 20μ, from the viewpoint of obtaining desired electrophotographic properties and economical effects.
, the optimum value is preferably 0.1 to lOμ.

In the present invention, Non-3i (C, N, O) (H,
In order to form the surface layer composed of X), the above-mentioned CTL
A vacuum deposition method similar to that used to form the film is used.

In the case of forming a surface layer that achieves the object of the present invention and has a stable property, the temperature and gas pressure of the support 101 are important factors that influence the properties of each layer.

The temperature of the support is appropriately selected in an optimal range, preferably 50°C to 400'C, more preferably 100 to 300°C.
It is desirable to do so.

The gas pressure in the deposition chamber is also appropriately selected in an optimal range, preferably I x lo = ~10 Torr, more preferably I x 10-3 ~ 3 Torr, most preferably I x 1
It is desirable to set it to 0-'' to 1 Torr.

In the present invention, the above-mentioned ranges are mentioned as preferable numerical ranges for the support temperature and gas pressure for producing the surface layer, but these layer production factors are usually not determined independently and separately. , to form a surface layer with desired properties (it is desirable to determine the optimal value of each layer fabrication factor based on mutual and organic relationships).

The surface layer is Non-3i (C, N, O) (H, X)
Among them, polycrystalline Si (C,N,O) (H,X) (r pol
y-3i (C.

There are various methods for forming a layer composed of N, 0) (referred to as H, X), including the following methods.

One method is to raise the substrate temperature to a high temperature, specifically 400℃.
In this method, the temperature is set at ~600° C., and a film is deposited on the substrate by plasma CVD.

Another method is to first form an amorphous film on the surface of the substrate, that is, form the film by plasma CVD on the substrate at a temperature of about 250'C, and then annealing the amorphous film to convert it into poly. This is the way to do it. The annealing treatment heats the substrate to 400~
This is carried out by heating at 600° C. for about 5 to 30 minutes or by irradiating with laser light for about 5 to 30 minutes.

Next, a method for manufacturing the electrophotographic light-receiving member of the present invention, which is formed by a high frequency (hereinafter abbreviated as RF) glow discharge decomposition method, will be described.

FIG. 42 shows an apparatus for manufacturing an electrophotographic light-receiving member using the RF glow discharge decomposition method.

1011, 1012, 1013, 10114゜l in the diagram
・The gas cylinders 015 and 1016 are sealed with raw material gases for forming the respective layers of the present invention.
9.999%) cylinder, 1012 is I (2 gas (purity 99.999%) cylinder, 1013 is PH3 gas (purity 99.999%, hereafter PH3 gas diluted with I4° gas)
/H2) cylinder, 1014 is No gas (purity 99
．． 5%) cylinder, 1015 is NH3 gas (purity 99,
999%) cylinder, 1016 is CH4 gas (purity 99.
999%) cylinder.

A method for producing an electrophotographic light-receiving member having the layer structure of the present invention on a base cylinder will be described based on a specific example.

That is, SiH4 gas is used as the CGL forming gas.

SiH4 gas as H2 gas and CTL forming gas.

The case where CH4 gas and PI-13/H2 gas are used as surface layer forming gases and SiH4 gas and CH4 gas will be discussed.

In order to flow these gases into the reaction chamber 1001, valves 1051 to 1056 of gas cylinders toll to 1016 are used.
After confirming that the leak valve 1003 of the reaction chamber 1011 is closed and that the inflow valves 1031 to 1036, outflow valves 1041 to 1046, and auxiliary valve 1070 are open, first open the main valve 1002. The reaction chamber 1001 and the gas piping are evacuated.

Next, when the reading of the vacuum gauge 1004 becomes approximately 5X10'Torr, the auxiliary valve 1070, the outflow valve 1041~
Close 1046.

After that, SiH4 gas from gas cylinder 1011, H2 gas from gas cylinder 1012, and P from gas cylinder 1013.
H3/H2 gas, N from gas cylinder 1014.

Gas, NH3 gas from gas cylinder 1015, CH4 gas from gas cylinder 1016, valves 1051 to 1056
The gas pressure is adjusted to 2 kg/crrr using pressure regulators 1061 to 1066.

Next, the inflow valves 1031 to 1036 are gradually opened to supply each of the above gases to the mass flow controllers 1021 to 1021.
26.

In addition, the base cylinder 1 installed in the reaction chamber 1001
The temperature of 007 is set to 50 to 35 by heating heater 1008.
Heat to desired temperature between 0°C.

After the preparation for film formation is completed as described above, the CTL, CGL, and surface layers are formed on the base cylinder 1007.

To form the CTL, gradually open the outflow valves 1041, 1043, 1046 and the auxiliary valve 1070 to
iH4 gas, PH3/H2 gas, CH4 gas in the reaction chamber.
1001. At this time, the SiH4 gas flow rate.

The outflow valve 1041. 1043. 1046
and the opening of the main valve 1002 while watching the vacuum gauge 1004 so that the pressure inside the reaction chamber reaches the desired value. Thereafter, the power supply 1010 is set to the desired power to create an RF glow discharge within the reaction chamber and initiate the formation of CTLs on the substrate cylinder.

After the desired film thickness has been formed, the RF glow discharge is stopped and the outflow valve 1041. 1043. 1045 is closed to stop the flow of gas into the reaction chamber, and the formation of CTL is completed.

A CGL is formed on the CTL formed as described above.

To form the CGL, outflow valve 1041. 104
2 and the auxiliary valve 1070 gradually to open the SiH4
Gas+H2 gas is allowed to flow into the reaction chamber tool.

At this time, the outflow valve 1041. 104
2 and the opening of the main valve 1002 while watching the vacuum gauge 1004 so that the pressure inside the reaction chamber reaches the desired value. Thereafter, the power supply 1010 is set to the desired power to create an RF glow discharge within the reaction chamber to begin forming the CGL on the substrate cylinder. After the desired film thickness has been formed, the RF glow discharge is stopped and the outflow valve 1041. 1042 is closed to stop the flow of gas into the reaction chamber, and the formation of CGL is completed.

A surface layer is formed on the CGL formed as described above. To form the surface layer, an outflow valve 1041, 1
046 and the auxiliary valve 1070 gradually open to
H4 gas and CH4 gas are allowed to flow into the reaction chamber 1001. At this time, adjust the outflow valves 1041 and 1046 so that the SiH4 gas flow rate and CH4 gas flow rate become the desired values, and also adjust the main valve 1002 while watching the vacuum gauge 1004 so that the pressure inside the reaction chamber becomes the desired value. Adjust the aperture. Power source 1010 is then set to the desired power to create an RF glow discharge within the reaction chamber to begin forming a surface layer on the substrate cylinder. After the desired film thickness has been formed, the RF glow discharge is stopped and the outflow valve 1041.1
046 is closed to stop the flow of gas into the reaction chamber, and the formation of the surface layer is completed.

Needless to say, when forming each layer, all outflow valves except for necessary gases are closed (in addition, each gas is in the reaction chamber 1001 and outflow valves 1041-104).
In order to avoid remaining in the piping from 6 to the reaction chamber tool, the outflow valves 1041 to 1046 are closed, the auxiliary valve 1070 is opened, and the main valve 1002 is fully opened to temporarily evacuate the system to a high vacuum. Perform operations as necessary.

Further, during layer formation, the base cylinder 1007 is rotated at a desired speed by a motor 1009 in order to ensure uniform layer formation.

Needless to say, the above-mentioned gas types and valve operations may be changed according to the manufacturing conditions of each layer.

Next, a method for manufacturing an electrophotographic light-receiving member formed by a microwave (hereinafter abbreviated as μW) glow discharge decomposition method will be described.

FIG. 43 shows an apparatus for manufacturing a light receiving member for electrophotography using the μW glow discharge decomposition method.

2011.2012.2013.2014 in the diagram. 2
The raw material gas for forming each layer of the present invention is sealed in the gas cylinders of 2015 and 2016. For example, in 2011, SiH4 gas (purity 99.99
9%) cylinder, 2012 has H2 gas (purity 99,99
9%) cylinder, PH diluted with H2 gas in 2013
3 gas (purity 99.999%, hereinafter r PH3/H2
J) cylinder, 2014 is NO gas (purity 99.5
%) cylinder, 2015 is NH3 gas (purity 99,999
%) cylinder, 2016 is CH4 gas (purity 99.999
%) It is a cylinder.

Examples of gases used when forming an electrophotographic light-receiving member with the apparatus shown in FIG. H2 gas,
SiH4 gas is used as surface layer forming gas.

Let us take up the case of using CH4 gas.

Gas cylinders 2011 to 201617) valves 2051 to 205 are used to flow these gases into the reaction chamber 2001.
6. Confirm that the leak valve 20o3 of the reaction chamber 2011 is closed, and also close the inflow valves 2031 to 2o36.
, outflow valves 2041-2046, auxiliary valve 2070
Make sure that the main valve 200 is open, and then open the main valve 200.
2 to exhaust the reaction chamber 2001 and gas piping.

Next, when the reading of the vacuum gauge 2004 becomes approximately 5XlO=Torr, the auxiliary valve 2070, the outflow valve 2041~
Close 2046.

After that, S i H4 gas from gas cylinder 2011, H2 gas from gas cylinder 2012, PH3/H2 gas from gas cylinder 2o13, and N from gas cylinder 2014.

Gas, NH3 gas from gas cylinder 2015, CH4 gas from gas cylinder 2016, valves 2051 to 205
6 is opened and introduced, and the pressure of each gas is adjusted to 2 Kg/Cd by pressure regulators 2061 to 2066.

Next, gradually open the inflow valves 2031 to 2036 to supply each of the above gases to the mass flow controllers 2021 to 2020.
26.

In addition, the base cylinder 2 installed in the reaction chamber 2001
The temperature of 006 is set to 50 to 35 by heating heater 2005.
Heat to desired temperature between 0°C.

After the preparation for film formation is completed as described above, each layer of the CTL and CGL1 surface layers is formed on the base cylinder 1007.

To form the CTL, the outflow valve 2041.2043
Gradually open ゜2045 and auxiliary valve 2070 and
iH4 gas, P H3/H2 gas, and NH3 gas are flowed into the reaction chamber 2001. At this time, the SiH4 gas flow rate.

PI-13/H□ Gas flow fi, CH4 gas flow rate to the desired value
46 and the main valve 2002 while watching the vacuum gauge 2004 so that the pressure inside the reaction chamber reaches the desired value.
Adjust the aperture. After that, the microwave power source 2008 is set to the desired power, and the waveguide 2009 and dielectric window 2 are
010 to generate a μW glow discharge in the reaction chamber,
Initiate CTL formation on the substrate cylinder. After the desired film thickness has been formed, the μW glow discharge is stopped, the outflow valves 2041, 2043, and 2046 are closed to stop the gas from flowing into the reaction chamber, and the CTL formation is completed.

A CGL is formed on the CTL formed as described above.

To form the CGL, gradually open the outflow valves 2041, 2042 and the auxiliary valve 2070 to release SiH4 gas,
H2 gas is allowed to flow into the reaction chamber 2001.

At this time, adjust the outflow valves 2041 and 2042 so that the SiH4 gas flow rate and H2 gas flow rate become the desired values,
Also, use the vacuum gauge 20 to make sure that the pressure inside the reaction chamber reaches the desired value.
04, adjust the opening of the main valve 2002. Thereafter, the microwave power source 2008 is set to a desired power, and a μW glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 201O to start forming a CGL on the base cylinder. After the desired film thickness is formed, the μW glow discharge is stopped and the outflow valve 2041
．． 2042 to stop the gas from flowing into the reaction chamber, and
Finish forming GL.

A surface layer is formed on the CGL formed as described above. Outflow valve 2041.204 to form the surface layer
6 and the auxiliary valve 2070 are gradually opened to allow SiH4 gas and CH4 gas to flow into the reaction chamber 2001.

At this time, adjust the outflow valves 2041 and 2046 so that the S i H4 gas flow rate and CH4 gas flow rate are at the desired values, and while watching the vacuum gauge 2004 so that the pressure inside the reaction chamber is at the desired value. Adjust the opening of valve 2002.

After that, set the micro power supply 2008 to the desired power,
A μW glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 201O to start forming a surface layer on the base cylinder. After the desired film thickness has been formed, the μW glow discharge is stopped and the outflow valve 2041.20
46 to stop the flow of gas into the reaction chamber, and the formation of the surface layer is completed.

Needless to say, all the outflow valves for gases other than those required for forming each layer are closed, and each gas is in the reaction chamber 2001 and the outflow valves 2041 to 2046.
In order to avoid remaining in the piping leading from the to the reaction chamber 2001, the outflow valves 2041 to 2046 are closed, the auxiliary valve 2070 is opened, and the main valve 2002 is fully opened to temporarily evacuate the system to a high vacuum. Do this as necessary.

Further, during layer formation, the base cylinder 2006 is rotated at a desired speed by a motor 2007 in order to ensure uniform layer formation.

Needless to say, the above-mentioned gas types and valve operations may be changed according to the manufacturing conditions of each layer.

Next, a method for manufacturing an electrophotographic light-receiving member formed by the RCVD method will be described.

FIG. 44 shows an apparatus for manufacturing an electrophotographic light-receiving member using the HRCVD method.

In FIG. 44, 3001 is a film forming chamber, 3002 is an activation chamber (A), 3003. 3018 is a microwave plasma generator, 3004 is a raw material gas introduction pipe for active species (A), 3005 is an active species (A) introduction pipe, 3006 is a motor, 3007 is a heater that heats a cylindrical base,
3008 and 3009 are blowout pipes, 301O is a cylindrical base, and 3011 is a main exhaust valve. Further, 3012 to 3016 are cylinders for supplying raw material gas, 3017 is an activation chamber (B), 3019 is a raw material gas introduction pipe, and 3020 is an active species introduction pipe generated from the activation chamber (B). A method for producing an electrophotographic light-receiving member having a layer structure according to the present invention on a cylindrical substrate using this apparatus will be specifically described.

- For example, Af is used as the cylindrical substrate, SiH4°112 is used as the CGL forming gas, C
As the TL forming gas, SiH4, SiF4°CH4,
H2+ PH37H2 was used.

First, an Al cylindrical substrate 3010 is suspended in a film forming chamber 3001, and a heating heater 3007 is installed inside it so that it can be rotated by a motor 3006.
It was evacuated to 10 Torr.

To form a CTL, H2 gas is introduced from a cylinder 3012 through an introduction pipe 3004 to an activation chamber (A), and activated by a microwave plasma generator 3003.
Active hydrogen is passed through the introduction pipe 3005 to the blowoff pipe 3008
It was then guided to the film forming chamber 3001. On the other hand, SiH4 gas from cylinder 3013, PH3/H2 gas from cylinder 3014, 3
SiF 4 gas from 015 and CH 4 gas from 3016 are introduced into the activation chamber (B) 3017 through the introduction pipe 3019, and after being activated by the microwave plasma generator 3018, they are passed through the introduction pipe 3020 into the blowout pipe 300.
9 to the film forming chamber 3001. At this time, the gas flow rate, internal pressure, and microwave power are set to desired values.

The Af cylindrical substrate 3010 was heated and maintained at a desired temperature by a heater 3007, and the exhaust gas was exhausted by appropriately adjusting the opening of the main exhaust valve 3011. CTLs were formed in this way. F2 gas from cylinder 3012 and SiH from 3013 were placed on top of the above CTL in the same manner.
4 Gas is supplied and the CGL is placed on top of the CGL in the cylinder 301.
A surface layer was sequentially formed by supplying F2 gas from No. 2, S i H4 gas from cylinder 3013, and CH4 gas from cylinder 3016 to form a light-receiving member for electrophotography.

Next, a method for manufacturing an electrophotographic light-receiving member formed by the FOCVD method will be described.

FIG. 45 shows an apparatus for manufacturing an electrophotographic light-receiving member using the FOCVD method.

4011.4012.4013.4014.40 in the diagram
The raw material gas for forming each layer of the present invention is sealed in the 15°4016 gas cylinder.For example, 4011 contains SiH4 gas (purity 99.99).
9%) cylinder, 4012 contains F2 gas (purity 99.99)
9%) cylinder, 4013 is PH3 gas diluted with H2 (purity 99.999% or less, abbreviated as rPH3/H2j)
Cylinder, 4014 is NO gas (purity 99.5%) cylinder, 4015 is ct-t4# gas (purity 99.99%) cylinder, 4016 is F2 gas (10% He dilution, purity 99.
99%).

SiH4 gas + F2 gas as CGL forming gas.

F2 gas and SiH4 gas as CTL forming gas.

A case where C144 gas, PH3/H2 gas + F2 gas is used, and SiH4 gas, CH4 gas + F2 gas is used as the surface layer forming gas will be discussed.

The raw material gases filled in the cylinders 4011 to 4015 are supplied to the respective valves 4031 to 4035 and 4053 to 4.
It passes through a mass flow controller 057 and is introduced into a vacuum chamber 4020 to 4001.

The F2 gas filled in the cylinder 4016 is introduced into the vacuum chamber 4001 through 4021 in the same manner as described above.

The vacuum chamber 4001 is evacuated via a main vacuum valve 4002 by a vacuum evacuation device (not shown).

4061 heats the base cylinder 4060 to an appropriate temperature during film formation, or heats the base cylinder 4060 before film formation.
This is a heater for heating the substrate for preheating the film 60 or for annealing the film after film formation.

Electric power is supplied to the substrate heater from a power source (not shown) via a conductive wire (not shown).

Further, the base cylinder 4060 is rotated by a rotation mechanism 4062 in order to form a uniform film.

To introduce gases 4011 to 4016 into 4001,
When the inside of the chamber of 4001 reaches approximately 5×1 Torr, it is necessary to slowly introduce it by operating various valves.

Further, the temperature of the base cylinder 4060 installed in the chamber 4001 is controlled by the heater 4061 to 50°C.
What is necessary is just to heat to the desired temperature between -350 degreeC.

After the preparation for film formation is completed as described above, films are formed on the base cylinder 4060 in the order of CTL, CGL, and surface layer.

To form CTL, valves 4046, 4048°4
Open 050, outflow valve 4031, 4033° 403
5 and the auxiliary valve 4060 to supply SiH4 gas, PH3/H2 gas, and CH4 gas to the reaction chamber 4001.
Let it flow inside. At this time, SiH4 gas flow rate, PH3/
Outflow valve 4031 so that H2 gas flow rate and CH4 gas flow rate become desired values.

4033 and 4035, and the main valve 4 while watching the vacuum gauge (not shown) until the pressure inside the reaction chamber reaches the desired value.
Adjust the aperture of 002.

Next, open valve 4051, and while watching the mass flow meter 4058, gradually open the valve 4036 until the desired flow rate is reached.After the flow rate has been set and the CTL has been formed to the desired thickness, the CTL Finish forming.

A CGL and a surface layer are formed on the CTL prepared as described above by the same operation as above.

For each layer, flow the necessary gas,
Just operate the valve in the same way as the CTL.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

<Example 1> Using the manufacturing apparatus shown in Fig. 42, the first
An electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the manufacturing conditions shown in Tables 2, 3, and 4.

The produced electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and subjected to initial charging under various conditions. Check the electrophotographic characteristics such as performance, sensitivity, residual potential, ghost, etc.
Charging ability decrease after accelerated endurance running test equivalent to 00,000 sheets 2
Surface scraped.

We investigated the increase in image defects.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above comprehensive evaluation results are shown in Table 5.

As shown in Table 5, good results were obtained for all items. In particular, remarkable superiority was recognized in terms of initial charging ability and durability.

<Example 2> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables 2, 6, and 7, and the same evaluations were performed.

The results are shown in Table 8.

As shown in Table 8, good results were obtained for all items.

<Example 3> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables 2, 9, and 10, and the same evaluations were performed.

The results are shown in Table 11.

As seen in Table 11, good results were obtained for all items.

<Example 4> Using the manufacturing apparatus shown in FIG.
Example 1 under the manufacturing conditions shown in Tables 2, 12, and 13.
A drum was prepared in the same manner as above, and the same evaluation was performed.

The results are shown in Table 14.

As seen in Table 14, good results were obtained for all items.

<Example 5> Using the manufacturing apparatus shown in FIG.
Example 1 under the manufacturing conditions shown in Tables 2, 15, and 16.
A drum was prepared in the same manner as above, and the same evaluation was performed.

The results are shown in Table 17.

As seen in Table 17, good results were obtained for all items.

<Example 6> Using the manufacturing apparatus shown in FIG.
Example 1 under the manufacturing conditions shown in Table 2, Table 18, and Table 19.
A drum was prepared in the same manner as above, and the same evaluation was performed.

The results are shown in Table 20.

As seen in Table 20, good results were obtained for all items.

<Example 7> Using the manufacturing apparatus shown in Fig. 43, electrophotography was performed on an aluminum cylinder that was mirror-finished using the microwave CVD method according to the manufacturing conditions shown in Tables 21, 22, 23, and 24. A light receiving member for use was formed.

The produced electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and subjected to initial charging under various conditions. Check the electrophotographic characteristics such as performance, sensitivity, residual potential, ghost, etc.
Decrease in charging ability after accelerated endurance running test equivalent to 00,000 sheets 9
Surface scraped.

We investigated the increase in image defects.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above comprehensive evaluation results are shown in Table 25.

As shown in Table 25, good results were obtained for all items. In particular, remarkable superiority was recognized in terms of initial charging ability and durability.

<Example 8> Using the manufacturing apparatus shown in Fig. 44, the 26th to
An electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the manufacturing conditions shown in Table 29. The produced electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial chargeability was measured under various conditions. , checking the electrophotographic characteristics such as sensitivity, residual potential, and ghosting, and also checking the chargeability decrease 9 surface scraping 1 after an accelerated durability running test equivalent to 2 million sheets.
We investigated the increase in image defects.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, the scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above comprehensive evaluation results are shown in Table 30.

As seen in Table 30, good results were obtained for all items. In particular, remarkable superiority was recognized in terms of initial charging ability and durability.

<Example 9> Using the manufacturing apparatus shown in Fig. 45, the 31st
An electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the manufacturing conditions shown in Tables 1 to 34.

The prepared electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial chargeability, The electrophotographic characteristics such as sensitivity, residual potential, and ghost were checked, and also the decrease in charging ability, surface scraping, increase in image defects, etc. after an accelerated durability running test equivalent to 2 million sheets were investigated.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above comprehensive evaluation results are shown in Table 35.

As shown in Table 35, good results were obtained for all items. In particular, remarkable superiority was recognized in terms of initial charging ability and durability.

<Example 10> The mirror-finished cylinders were further subjected to lathe processing using a sword bit with various angles to produce cylinders with cross-sectional shapes as shown in Figure 50 and various cross-sectional patterns as shown in Table 37. I prepared several books. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 42 and subjected to drum manufacturing under the manufacturing conditions shown in Table 36. The produced drums were subjected to various evaluations using an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 38 were obtained.

<Example 11> The surface of the mirror-finished cylinder was then subjected to a so-called surface dimple treatment, in which numerous dents were created on the cylinder surface by exposing it to a large number of falling rough bearing balls. A plurality of cylinders having a cross-sectional shape as shown in FIG. 51 and various cross-sectional patterns as shown in Table 40 were prepared. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 42 and subjected to drum manufacturing under the manufacturing conditions shown in Table 39. The produced drums were subjected to various evaluations using an electrophotographic device using a halogen lamp as a light source and an electrophotographic device with a digital exposure function using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 41 were obtained.

<Example 12> Using the manufacturing apparatus shown in FIG. 42, Tables 43 and 44.

A drum was manufactured in the same manner as in Example 1 under the manufacturing conditions shown in Table 45, and the same evaluation was performed.

The results are shown in Table 46.

As shown in Table 46, good results were obtained for all items.

Table 1 Table 2 CGL film formation conditions Table 3 CTL film formation conditions Table 4 Table 5 Continuation of Table 5 ◎ = Very good O: Good △・No practical problem ×・Practical problem Continuation of Table 5 ◎: Very good O: Good Δ: No practical problem ×, No practical problem
6 Table 7 Table 8 △・Okawae Unsatisfied ×: Practically problematic Continuation of Table 8 ◎: Very good O Good Good △, Practically unacceptable × Practically problematic Table 8 Continued ◎・Very good ○: Good Good △: No problem in practical use ×: Problem in practical use
9 Table 10 Table 11 Continuation of Table 11 ◎・Very good ○: Good △: No practical problem ×: Practical problem Continuation of Table 11 ◎: Very good O: Good △ ：No practical problem ×：Practical problem No.
Table 12 Table 13 Table 14 Continuation of Table 14 ◎: Very good ○: Good Δ = No practical problem ×: Practical problem Continuation of Table 14 ◎: Very good ○: Good Δ , Not a problem in practical use Continuation of the table ◎: Very good ○: Good Δ: No practical problem ×・Practical problem
Table 18 Table 19 Table 20 Continuation of Table 20 ◎: Very good 0: Good △: No practical problem ×: Practical problem Continuation of Table 20 ◎: Very good ○: Good △ , There is no practical problem. ×・There is a practical problem.
21 Table 22 Table 23 CGL film forming conditions Table 24 CTL film forming conditions Table 25 Δ, practically no problem × Practically problematic Continuation of Table 25 ◎: Very good 0: Good Δ・No practical problem X - Practical problem Continuation of Table 25 ◎: Very good O: Good Δ: No practical problem Conditions Table 29 CTL Film Forming Conditions Table 30 ◎・Very good ○: Good Δ No practical problem × Practical problem Continuation of Table 30 ◎, Very good ○: Good Δ, No practical problem Not applicable Table CTL film formation conditions No. 35 Table 35 Continued from Table 35 ◎: Very good O: Good Δ・No practical problem ×・Practically problematic Continuation from Table 35 ◎・Very good Q: Good Δ : Not a problem in practical terms × : There is a problem in practical terms Table 36 Table 37 Table 38 Table ◎□ Good for non-wealthy O □ Good Δ□ Not a problem in practice × □ Practical number 4 towns ■ Yes Table 39 Table 40 Table 41 Table ◎□ Impossibly good O □ Good △□ Practically unacceptable × □ Practical No. 4J with Zhao Table 42 Table 43 Table 44 CGL film formation conditions Table 45 CTL film formation conditions Table 46 Continuation of ◎: Very good ○: Good Good △: No practical problem ×: Practical problem Continuation of Table 46 ◎: Very good ○: Good Δ: No practical problem ×: Practical problem Yes [Summary of the Effects of the Invention] By making the electrophotographic light receiving member of the present invention have the specific layer structure as described above, all the problems in the conventional electrophotographic light receiving member composed of A-3i can be solved. In particular, it has extremely excellent initial charging ability, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, and durability. In addition, its electrical properties are stable, and the images obtained using it are of excellent quality, with high density and clear halftones.

In particular, in the present invention, a functionally separated structure using CTL and CGL is used, and atoms (M) belonging to group V of the periodic table are added to the CTL as a substance that controls conductivity, unevenly or partially in the layer thickness direction. In addition, carbon atoms and nitrogen atoms are contained in a non-uniformly distributed state.

By containing at least one type of oxygen atom, it is possible to design freely according to the characteristics of each layer, and the generation of charge and the injection and transport from CGL to CTL occur quickly, resulting in particularly excellent charging ability. , high sensitivity, low residual potential and ghosts, and high resolution images (and high quality images can be obtained stably and repeatedly).

[Brief explanation of the drawing]

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 5 show the uneven shape of the surface of the support and the method for producing the uneven shape, respectively. Figures 6 to 21 are schematic diagrams for explaining the atoms (M) belonging to group V of the periodic table that constitute CTL, and Figures 22 to 31 are schematic diagrams for explaining the carbon atom group, respectively. 32 to 41 are explanatory diagrams for explaining the distribution state of oxygen atoms and/or nitrogen atoms, respectively. An explanatory diagram explaining the state, FIG. 42 is an example of an apparatus for forming a light-receiving layer of the electrophotographic light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method using RF, FIG. 43 is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method using microwaves. FIG. 45 is an example of an apparatus for forming the light-receiving layer of the electrophotographic light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using the HRCVD method. FIG. 46 is a schematic explanatory diagram of a manufacturing device using the FOCVD method, which is an example of a device for forming the CTL of the electrophotographic light-receiving member of the present invention.
Figure 47 shows the flow rate changes of impurity gas and doping gas during film formation when F glow discharge is used. Figure 48 shows the flow rate changes of impurity gas and doping gas during film formation.
, a diagram showing the flow rate changes of impurity gas and doping gas during film formation when formed using the R0CVD method.
, O, A diagram showing the flow rate changes of impurity gas and doping gas during film formation when forming using the CVD method. FIG. 51 is an enlarged view of the cylinder cross section when the cross-sectional shape is V-shaped. FIG. 52 are diagrams showing changes in the flow rates of impurity gas and doping gas during film formation in an embodiment in which the CTL of the electrophotographic light-receiving member of the present invention is formed using RF glow discharge. Regarding FIG. 1, 101... Support 102... CTL 103... CGL 104... Surface layer 105... Free surface Regarding FIGS. 3 and 4, 301, 401... Support 302, 402...Support surface 303.403...Rigid true sphere 304.404...Spherical trace depression Regarding Fig. 5, 500...Light receiving layer 501...Support 502...CTL 503...CGL 504...Surface layer 505...Free surface In Fig. 42, 1001...Reaction chamber 1002...Main exhaust valve 1003...Reaction chamber leak valve 1004...Vacuum gauge 1007... Cylinder base too... Heater for heating the base 1009... Motor 1010 for rotating the cylinder base
... R, F power supply 1011-1017 ... Raw material gas cylinder 1021 ~
1027...Mass flow controller 1031
~1037...Gas inflow valve 1041~1047・
...Gas outflow valves 1051-1057...Valves 1061-1067 of raw material gas cylinder...Pressure regulator Regarding Fig. 43, 2001...Reaction chamber 2002...Main exhaust valve 20 (33... Reaction chamber leak valve 2004...
Vacuum gauge 2005... Substrate heating heater 2006... Cylindrical substrate 2007... Substrate rotation motor 2008... Microwave power supply 2009... Waveguide 2010... Dielectric window 2011-2017.・・Raw material gas cylinder 2021~
2027...Mass flow controller 2031
~2037...Gas inflow valve 2041~2047・
... Gas outflow valves 2051 to 2057 ... Raw material gas cylinder valves 2061N1267 ... Pressure regulator Regarding Fig. 44, 3001 ... Film forming chamber 3002 ... Activation chamber (A) 3003, 3018 ... ...Microwave plasma generator 3004, 3019...Material gas introduction pipe 3005, 3
020...Active species introduction pipe 3006...Motor 3007...Cylinder base heating heater 3008
, 3009... Blowout pipe 301O... Cylindrical base 3011... Main exhaust valves 3012-3016... Raw material gas cylinder 3017...
...Activation chamber (B) Regarding Fig. 45, 4001...Reaction chamber 4002...Main exhaust valves 4011 to 4017...Material gas cylinders 4020, 4
021... Raw material gas introduction pipes 4031 to 4037...
Outflow valves 4046-4052...Inflow valves 4053-4059...Mass flow controller 4060...Cylindrical substrate 4061...Heater 406 for heating the cylindrical substrate
2... Motor for rotating the cylinder base.

Claims (1)

[Claims] (1) A support, and a photoreceptive layer having a layer structure in which a charge transport layer, a charge generation layer, and a surface layer are laminated in this order from the support side on the support, and the charge transport layer and the charge generation layer are made of a non-single crystal material having silicon atoms as a host and containing at least one of hydrogen atoms and halogen atoms, and the charge transport layer is
A portion containing at least one of carbon atoms, nitrogen atoms, and oxygen atoms and containing atoms belonging to Group V of the periodic table as a substance controlling conductivity in a non-uniform distribution state in the layer thickness direction. What is claimed is: 1. A light-receiving member for electrophotography, comprising: