JPH0785178B2 - Photoreceptive member for electrophotography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention refers to electromagnetic waves such as light (light in a broad sense, which means ultraviolet rays, visible rays, infrared rays, x-rays, γ-rays, etc.). The present invention relates to a photoreceptive member for electrophotography, which is sensitive to.

[Description of conventional technology]

In the field of image formation, as a photoconductive material for forming a light receiving part layer in a light receiving member for electrophotography, it has high sensitivity and SN
High ratio [photocurrent (Ip) / dark current (Id)], absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves that are irradiated, fast photoresponsiveness, and the desired dark resistance value. Be pollution-free to the human body,
Such characteristics are required. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used as an office machine as an office machine, the pollution-free property at the time of use is an important point.

Amorphous assilicon (hereinafter referred to as A-Si) is a photoconductive material that has recently received attention based on such a point. For example, German Laid-Open Publication No. 2746967 and No. 2855718.
The publication describes application as a light receiving member for electrophotography.

However, the conventional photoreceptive member for electrophotography having a photoreceptive layer composed of A-Si has electrical, optical, and photoconductive characteristics such as dark resistance, photosensitivity, and photoresponsiveness, and operating environment characteristics. In terms of the above, and further in terms of stability over time and durability, the characteristics have been individually improved, but there is room for further improvement in the overall improvement of characteristics. Is.

For example, when it is applied to a photoreceptive member for electrophotography, it is often observed that a residual potential remains in the conventional use when attempting to increase photosensitivity and dark resistance at the same time. However, when it is used repeatedly for a long time, fatigue is accumulated due to repeated use, which causes a so-called ghost phenomenon in which an afterimage is generated, which is inconvenient.

When the light-receiving layer is made of an A-Si material, in order to improve its electrical and photoconductive properties, a hydrogen atom or a halogen atom such as a fluorine atom or a chlorine atom, and an electrically conductive type are used. The boron atom, the phosphorus atom, etc. are contained in the photoconductive layer as constituent atoms, respectively, for the purpose of controlling the above, or for improving other characteristics. Depending on how these constituent atoms are contained, In some cases, problems may occur in the electrical or photoconductive characteristics or pressure resistance of the formed layer.

That is, for example, the life of a photo-carrier generated in the formed photoconductive layer by light irradiation in the layer is not sufficient, or commonly referred to as "white blank" in the image transferred to the transfer paper, Image defects that are considered to be caused by a local discharge breakdown phenomenon, and when a blade is used for cleaning, image defects commonly called "white stripes" that are thought to be caused by the rubbing have occurred. Further, when used in a humid atmosphere, or when used immediately after being left in a humid atmosphere for a long time, blurring of a so-called image often occurs.

Therefore, while improving the characteristics of the A-Si material itself, when designing the light-receiving member, the layer structure, the chemical composition of each layer, the preparation method, etc. are set so that all of the above problems can be solved. It needs to be devised.

[Object of the Invention]

An object of the present invention is to solve various problems in the electrophotographic light receiving member having the conventional light receiving layer composed of A-Si as described above.

That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially always stable with little dependence on the operating environment, excellent light resistance, and deterioration phenomenon even after repeated use. To provide a photoreceptive member for electrophotography having a photoreceptive layer composed of A-Si and polycrystalline silicon, which does not cause deterioration, has excellent durability and moisture resistance, and has no or almost no residual potential observed. is there.

Another object of the present invention is to provide excellent adhesion between the layer provided on the support and the support or between the layers of the laminated layer,
A-, which is dense and stable in terms of structural arrangement and has high layer quality
Another object of the present invention is to provide a photoreceptive member for electrophotography having a photoreceptive layer composed of Si and polycrystalline silicon.

Still another object of the present invention is that, when applied as a photoreceptive member for electrophotography, it has a sufficient charge retention ability during charging treatment for electrostatic image formation, and ordinary electrophotography is extremely effective. It is an object of the present invention to provide a photoreceptive member for electrophotography having a photoreceptive layer composed of A-Si and polycrystalline silicon, which exhibits excellent electrophotographic properties that can be applied.

Another object of the present invention is to easily obtain a high-quality image with high density, high density, clear halftone, and no image defects or image blurring in long-term use. Another object of the present invention is to provide a light receiving member having a light receiving layer composed of A-Si and polycrystalline silicon for photography.

Still another object of the present invention is to provide a photoreceptive member for electrophotography having a photoreceptive layer composed of A-Si and polycrystalline silicon, which has high photosensitivity, high SN ratio characteristic and high electrical withstand voltage. To do.

[Structure of Invention]

The electrophotographic light-receiving member of the present invention is composed of a support and a polycrystalline material having a silicon atom as a base material on the support,
A charge injection blocking layer containing an atom (a substance that controls conductivity) belonging to Group III or Group V of the periodic table, a silicon atom as a base, and at least one of a hydrogen atom and a halogen atom as a constituent element. A photoconductive layer which is composed of an amorphous material (hereinafter abbreviated as "A-Si (H, X)") and which exhibits photoconductivity, and a silicon atom, a carbon atom, and a hydrogen atom as constituent elements. A surface layer containing a crystalline material and containing 23 atomic% to 39 atomic% of the hydrogen atoms, and a photoreceptive layer containing the surface layer.

Further, the surface layer may contain a halogen atom, and the charge injection blocking layer is a substance that controls conductivity as a constituent atom in a distributed state in which it is distributed uniformly in the layer thickness direction or in a large amount on the support side. Is contained.

Further, the charge injection blocking layer may contain oxygen atoms and / or nitrogen atoms as constituent atoms in a state where the charge injection blocking layer is uniformly distributed in the layer thickness direction or is distributed in a large amount on the support side. Further, oxygen atoms and / or nitrogen atoms in the charge injection blocking layer may be present on the support side.

Further, the photoconductive layer may contain at least one of carbon atoms, oxygen atoms, nitrogen atoms as a constituent atom, and a substance for controlling conductivity.

Further, a long-wavelength photosensitive layer made of an amorphous material containing silicon atoms and germanium atoms and having sensitivity to long-wavelength light may be provided between the charge injection blocking layer and the support.

Further, at least one of oxygen atoms, nitrogen atoms and a substance for controlling conductivity contained in the charge injection blocking layer and the long wavelength light-sensitive layer and germanium atom contained in the long wavelength light-sensitive layer. May be evenly distributed in the layer thickness direction, or may be non-uniformly distributed.

The electrophotographic light-receiving member of the present invention designed so as to have the above-mentioned layer structure can solve all of the above-mentioned problems and has extremely excellent electrical, optical and photoconductive properties. , Shows pressure resistance and operating environment characteristics.

That is, when applied as a photoreceptive member for electrophotography, it has no influence of residual potential on image formation, has stable electrical characteristics, high sensitivity, and high SN ratio. It is possible to stably and repeatedly obtain a high-quality image having excellent light fatigue resistance, repeated use characteristics, high density, clear halftone, and high resolution.

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 configuration diagram schematically shown for explaining the light receiving member for electrophotography of the present invention.

In the electrophotographic light receiving member shown in FIG. 1, a light receiving layer 100 is provided on a support 101 for the light receiving member, and the light receiving layer 100 is composed of polycrystalline silicon. A charge injection blocking layer 102, A-Si (H, X), and a photoconductive photoconductive layer 103, and a polycrystalline material having silicon atoms, carbon atoms and hydrogen atoms as constituent elements. The surface layer 104 has a free surface 105.

Hereinafter, each layer constituting the light receiving member for electrophotography shown in FIG. 1 will be described.

Support The support used in the present invention may be conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, Al, Cr, Mo, Au, Nb, Ta,
Examples thereof include metals such as V, Ti, Pt, and Pd, or alloys thereof.

As the electrically insulating support, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, or polyamide, glass, ceramic, paper or the like is usually used. . It is desirable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is provided on the surface side subjected to the conductive treatment.

For example, if it is glass, NiCr, Al, Cr,
Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , I
Conductivity is imparted by providing a thin film of TO (In ₂ O ₃ + SnO ₂ ) or the like, or NiCr, Al, Ag, Pb, Zn, N in the case of synthetic resin film such as polyester film.
A thin film of metal such as i, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the surface is laminated with the metal. Then, conductivity is imparted to the surface. The shape of the support may be any shape such as a cylindrical shape, a belt shape, a plate shape, and the shape is determined as desired.
In the case of continuous high speed copying, it is desirable to use an endless belt or a cylinder. The thickness of the support is appropriately determined so that a desired electrophotographic light-receiving member is formed. When flexibility is required as the electrophotographic light-receiving member,
It is made as thin as possible within the range where the function as a support is sufficiently exhibited. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is usually 10 μm or more.

In particular, when image recording is performed using a coherent light such as a laser beam, unevenness may be provided on the surface of the support in order to eliminate an image defect due to a so-called interference fringe pattern that appears in a visible image.

FIG. 15 shows a light receiving member including a light receiving layer 1500 on a support 1501 having an uneven shape and along the inclined surface of the unevenness. At this time, since the degrees of inclination at the interfaces formed in the free surface 1504 and the light receiving layer 1500 are different, the reflection angles of the reflected light at the interfaces formed in the free surface and the light receiving layer 1500 are different.

Therefore, shearing interference corresponding to a so-called Newton's ring phenomenon occurs, and the interference fringes are dispersed in the depression. As a result, even if microscopic interference fringes appear, the images appearing through such a light receiving member are such that they are not visually recognizable. That is, the use of a support having a surface shape that increases, in a light-receiving layer formed by forming a multi-layered light-receiving layer 1500 thereon, the light passing through the light-receiving layer 1500,
The reflected light at the layer interface and the surface of the support and the interference between them effectively prevent the formed image from becoming a striped pattern.

In FIG. 15, 1502-1 is a charge injection blocking layer, 1502-2
Is a photoconductive layer and 1503 is a surface layer.

The unevenness provided on the surface of the support is obtained by fixing a cutting tool having a V-shaped cutting edge to a predetermined position of a cutting machine such as a milling machine or a lathe, and rotating a cylindrical support according to a program designed in advance as desired. However, by regularly moving in a predetermined direction, the surface of the support is precisely cut to form a desired uneven shape, pitch, and depth. The inverted V-shaped linear protrusions created by the irregularities formed by such a cutting method have a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped projection may be a double or triple multiple spiral structure or a cross 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 convex and concave portions provided on the surface of the support is such that the layer thickness is controlled to be nonuniform in the microcolumns of each layer to be formed, and the support and the layer directly provided on the support. In order to secure good adhesion and desired electrical contact between the two, the shape is inverted V, but preferably it is substantially an isosceles triangle, a right triangle or an isosceles triangle as shown in FIG. Is desirable. Among these shapes, an isosceles triangle and a right triangle are preferable.

In the present invention, each dimension of the irregularities provided on the surface of the support in a controlled state is set so that the object of the present invention can be achieved as a result, in consideration of the following points.

That is, the first is the A-Si (H, X) layer constituting the light receiving layer,
It is structurally sensitive to the state of the layered surface, and the layer quality greatly changes depending on the surface state.

Therefore, it is necessary to set the dimension of the unevenness provided on the surface of the support so as not to deteriorate the layer quality of the A-Si (H, X) layer.

Secondly, if the free surface of the light-receiving layer has extreme irregularities, it becomes impossible to completely perform cleaning after image formation.

Further, when the blade cleaning is performed, there is a problem that the damage of the blade becomes faster.

As a result of studying the above-mentioned problems in layer deposition, problems in the process of electrophotography, and conditions for preventing interference fringe patterns, the pitch of recesses on the surface of the support is preferably 500 μm to 0.3 μm.
m, more preferably 200 μm to 1 μm, optimally 50 μm
It is desirable that the thickness is -5 μm.

The maximum depth of the recess is preferably 0.1 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm, optimally 0.6 μm
It is desirable to be set to ˜2 μm. When the pitch and maximum depth of the concave portion on the surface of the support are within the above range, the inclination of the inclined surface of the concave portion (or the linear protrusion) is preferably 1 to 20 degrees,
It is more preferably 3 to 15 degrees, and most preferably 4 to 10 degrees.

Further, the maximum layer thickness difference due to the non-uniform layer pressure of each layer deposited on such a support is preferably 0.1 within the same pitch.
It is desirable that the thickness is from 2 μm to 2 μm, more preferably from 0.1 μm to 1.5 μm, and most preferably from 0.2 μm to 1 μm.

Further, as another method for eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, the surface of the support may be provided with a concavo-convex shape by a plurality of spherical trace dents.

That is, the surface of the support has unevenness smaller than the resolution required for the electrophotographic light-receiving member, and the unevenness is due to a plurality of spherical trace depressions.

Hereinafter, the shape of the surface of the support in the electrophotographic light-receiving member of the present invention and a preferred production example thereof will be described with reference to FIGS. 16 and 17, and the shape of the support in the light-receiving member of the present invention and The manufacturing method is not limited to this.

FIG. 16 schematically shows a typical example of the shape of the surface of the support in the electrophotographic light-receiving member of the present invention by partially enlarging a part of the uneven shape.

In FIG. 16, 1601 is a support, 1602 is a support surface, 1603
Is a rigid spherical body, and 1604 is a spherical dent.

Further, FIG. 16 also shows an example of a preferred manufacturing method for obtaining the surface shape of the support. That is, a rigid spherical body 1603
The spherical depressions by allowing them to naturally fall from a position at a predetermined height above the support surface 1602 and colliding with the support surface 1602.
1604 can be formed. Then, by using a plurality of rigid true spheres 1603 having substantially the same diameter R'and dropping them simultaneously or sequentially from the same height h, the support surface 1602 has substantially the same radius of curvature R and the same width D. A plurality of spherical trace indentations 1604 can be formed having

As described above, FIG. 17 shows a typical example of a support having an uneven shape formed by a plurality of spherical trace depressions on the surface.

In the figure, 1701 indicates a support, 1702 indicates the position of the convex portion of the concave-convex portion, 1703 indicates a rigid spherical body, and 1704 indicates the concave surface.

By the way, the radius of curvature R and the width D of the uneven shape due to the spherical dents on the surface of the support of the light receiving member for electrophotography of the present invention.
Is an important factor for efficiently achieving the effect of preventing the occurrence of interference fringes in the light receiving member of the present invention. The present inventors have made the following discoveries as a result of various experiments. That is, the radius of curvature R and the width D are as follows: If the above condition is satisfied, there are 0.5 or more Newton rings due to shear ring interference in each of the dents. Furthermore, the following formula: If the above condition is satisfied, there will be one or more Newton rings due to shear ring interference in each of the dent depressions.

From these things, to disperse the interference fringes generated in the entire light receiving member in each trace recess, in order to prevent the occurrence of interference fringes in the light receiving member, the D / R is 0.035, preferably 0.055 or more. Is desirable.

In addition, the width D of the unevenness due to the trace depression is at most 500 μm
Degree, preferably less than 200 μm, more preferably 100 μm
The following is preferable.

Charge Injection Blocking Layer The charge injection blocking layer in the present invention is composed of polycrystalline silicon, and is made of such a material that the substance controlling the conductivity is uniformly or preferably distributed in a large amount on the support side in the whole layer region of the layer. Contains in a uniform state. Furthermore, if necessary, oxygen atoms or / and nitrogen atoms are uniformly or preferably contained in a non-uniform state so as to be distributed in large numbers on the support side in the whole layer region or a part of the layer region of the layer, It is possible to improve the adhesion between the layer and the support and to adjust the band gap.

Examples of the substance for controlling the conductivity contained in the charge injection blocking layer include so-called impurities in the field of semiconductors. In the present invention, the substance belongs to Group III of the periodic table which gives p-type conduction characteristics. An atom (hereinafter referred to as “Group III atom”) or an atom belonging to Group V of the periodic table (hereinafter referred to as “Group V atom”) that provides N-type conductivity is used. As the group III atom, specifically, B (boron),
There are Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferable. As the group V atom, specifically, P (phosphorus), As
(Arsenic), Sb (antimony), Bi (bismuth), etc.
P and As are particularly preferable.

2 to 6 show II contained in the charge injection blocking layer.
A typical example of the state of distribution of group I atoms or group V atoms in the layer thickness direction is shown.

In the examples of FIGS. 2 to 6, the horizontal axis represents the distribution concentration C of group III atoms or group V atoms, the vertical axis represents the layer thickness t of the charge injection blocking layer, and t _B is the interface position on the support side. , _{T T} indicates the position of the interface on the side opposite to the support side. That is, the charge injection blocking layer is formed from the t _B side toward the t _T side.

FIG. 2 shows a first typical example in which the group III atoms or the group V atoms contained in the charge injection blocking layer are distributed in the layer thickness direction.

In the example shown in FIG. 2, from the interface position t _B to the position t ₁ , the content concentration C of the group III atom or the group V atom is contained so that it has a constant value C ₁ . _{From 1} , the distribution concentration C is gradually and continuously decreased from C ₂ until reaching the interface position t _T. At the interface position t _T , the distribution concentration C is C ₃ .

In the example shown in FIG. 3, the distribution concentration C of the group III atom or the group V atom contained is gradually and continuously decreased from C ₄ until it reaches the position t _T from the position t _B. C _{5 at T}
The distribution state is such that

In the example shown in FIG. 4, the distribution concentration C of the group III atom or the group V atom has a constant value of C ₆ between the position t _B and the position t ₂ , and C _{7 at the} position t _T. It is said that Between the position t ₂ and the position t _T , the distribution concentration C is linearly reduced from the position t ₂ to the position t _T.

In the example shown in FIG. 5, the distribution concentration C takes a constant value of C ₈ from the position t _B to the position t _3, and a linear function from C ₉ to C ₁₀ from the position t ₃ to the position t _T. It is said that the distribution state is decreasing.

In the example shown in FIG. 6, the distribution density C takes a constant value of C ₁₁ from the position t _B to the position t _T.

In the present invention, the charge injection blocking layer is a group III atom or a group V atom.
When a large number of group atoms are contained on the support side, the maximum distribution concentration value of group III atoms or group V atoms is preferably 50 atom ppm or more, more preferably 80 atom ppm or more.
It is desirable that the layers are formed so that the distribution state may be at least atomic ppm or more, optimally at least 100 atomic ppm.

In the present invention, the content of the group III atom or the group V atom contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably 30 Up to 5 × 10 ⁴ atomic ppm, more preferably 50
~ 1 x 10 ⁴ atom ppm, optimally 1 x 10 ^{2 to} 5 x 10 ³ atom ppm
Is desirable.

As described above, the charge injection blocking layer is improved in adhesiveness between the support and the charge injection blocking layer, and between the charge injection blocking layer and the photoconductive layer, mainly by containing oxygen atoms and / or nitrogen atoms. Is improved or the band gap of the layer is adjusted.

7 to 13 show typical examples of the distribution state of oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer in the layer thickness direction.

In the examples of FIGS. 7 to 13, the horizontal axis represents the distribution concentration C of oxygen atoms and / or nitrogen atoms, the vertical axis represents the layer thickness t of the charge injection blocking layer, t _B represents the interface position on the support side, t _T indicates the position of the interface on the side opposite to the support side. That is, the charge injection blocking layer is formed from the t _B side toward the t _T side.

FIG. 7 shows a first typical example of the distribution state of oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer in the layer thickness direction.

In the example shown in FIG. 7, from the interface position t _B to the position t ₄ , the oxygen atom and / or nitrogen atom content concentration C is a constant value C ₁₂ and is contained and distributed from the position t _4. The concentration C is gradually and continuously reduced from C ₁₃ until reaching the interface position t _T. The distribution concentration C is C _{14 at the} interface position t _T.

In the example shown in FIG. 8, the distribution concentration C of contained oxygen atoms and / or nitrogen atoms gradually decreases continuously from C ₁₅ from position t _B to position t _T , and at position t _T. C
A distribution state of ₁₆ is formed.

In the case of FIG. 9, the distribution concentration C of oxygen atoms and / or nitrogen atoms is constant at C ₁₇ from the position t _B to the position t ₅ .
It gradually decreases continuously between the position t ₅ and the position t _T, and is qualitatively zero at the position t _T.

In the case of FIG. 10, the oxygen atom and / or the nitrogen atom are located
The distribution concentration C is continuously and gradually reduced from C ₁₉ from t _B to the position t _T, and is substantially zero at the position t _T.

In the example shown in FIG. 12, the distribution concentration C of oxygen atoms and / or nitrogen atoms has a constant value of C ₂₂ from position t _B to position t _7, and from C ₂₃ from position t ₇ to position t _T. It is assumed that the distribution state decreases linearly until C ₂₄ .

In the example shown in FIG. 11, the distribution concentration C of oxygen atoms and / or nitrogen atoms is C ₂₀ between the position t _B and the position t _6.
Is a constant value and is C _{21 at the} position t _T. Position t
_{Between 6} and the position t _T , the distribution concentration C is a linear function at the position t.
It is reduced from ₆ to the position t _T.

In the example shown in FIG. 13, the distribution density C takes a constant value of C ₂₅ from the position t _B to the position t _T.

In the present invention, when the charge injection blocking layer contains oxygen atoms and / or nitrogen atoms in a distribution state in which a large number of oxygen atoms are distributed on the support side, the distribution concentration value of oxygen atoms or / and nitrogen atoms or the maximum value of the sum of both atoms is: It is preferably 500 atom ppm or more, more preferably 800 atom ppm or more, most preferably 1000 atom pp.
It is desirable that the layers are formed so that the distribution state of m or more can be obtained.

In the present invention, the content of oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer, or the sum of both, is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably Is preferably 0.001 to 50 atom%, more preferably 0.002 to 40 atom%, and most preferably 0.003 to 30 atom%.

In the present invention, the thickness of the charge injection blocking layer is preferably 0.01 to 10 μm, more preferably 0.05 to 8 μm, most preferably from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable to set it to 0.1 to 5 μ.

Photoconductive Layer The photoconductive layer in the present invention is composed of A-Si (H, X) and has photoconductive characteristics satisfying desired electrophotographic characteristics.

In addition, a substance for controlling conductivity may be contained in the whole layer region of the layer within a range that does not impair the properties required for the layer.

Further, at least one of a carbon atom, an oxygen atom and a nitrogen atom may be contained in the whole layer region of the layer within a range not impairing the properties required for the layer.

As the substance for controlling the conductivity, a group III atom or a group V atom can be used as in the charge injection blocking layer described above.

When the entire region of the photoconductive layer of the present invention contains a group III atom or a group V atom, it mainly exerts the effect of controlling the conductivity type and / or the conductivity, and the group III atom or the group V atom Content is relatively small, preferably 1 x 10
^{-3 to} 3 x 10 ² atom ppm, more preferably 5 x 10 ^-3 to 10 ² atom p
pm, optimally 1 × 10 ^-2 to 50 atomic ppm is desirable.

When the photoconductive layer of the present invention contains oxygen atoms or carbon atoms in the entire layer region, the effect is mainly to increase the dark resistance and improve the adhesion between the charge injection blocking layer and the photoconductive layer. However, it is desirable that the content of oxygen atoms is relatively small so that the photoconductive properties of the layer are not deteriorated.

In the case of a nitrogen atom, in addition to the above points, the photosensitivity can be improved in the coexistence with, for example, a Group III atom, especially B. The content of oxygen atoms or nitrogen atoms contained in the photoconductive layer, or the sum of both is preferably 1 × 10 ⁻³ to 10
³ atomic ppm, more preferably 5 × 10 ^{−2 to} 5 × 10 ² atomic ppm, and most preferably 1 × 10 ⁻¹ to 2 × 10 ² atomic ppm.

In the present invention, in order to effectively achieve the object, the photoconductive layer which is formed on the support and constitutes a part of the light receiving layer has the following semiconductor characteristics and is irradiated with light. It is composed of A-Si (H, X) showing photoconductivity with respect to.

p-type A-Si (H, X) --- containing only the acceptor. Alternatively, a substance containing both a donor and an acceptor and having a high relative concentration of the acceptor.

A p ^- type A-Si (H, X) --- type having a low acceptor concentration (Na) or a low relative acceptor concentration.

n-type A-Si (H, X) --- containing only a donor.
Alternatively, a substance containing both a donor and an acceptor and having a high relative concentration of the donor.

n ^- type A-Si (H, X) --- types having a low donor concentration (Nd) or a low relative donor concentration.

i-type A-Si (H, X) --- NaNdO or N
aNd's.

In the present invention, the halogen atom (X) contained in the charge injection blocking layer and / or the photoconductive layer is preferably F or C.
l, Br, I, especially F, Cl are desirable.

In the present invention, to form the charge injection blocking layer and / or the photoconductive layer, for example, a vacuum deposition method utilizing a discharge phenomenon such as a glow discharge method, a microwave discharge method, a sputtering method, or an ion plating method. Made by
For example, in order to form the charge injection blocking layer and / or the photoconductive layer by the glow discharge method, basically, a raw material gas for supplying Si, which can supply silicon atoms (Si), and a hydrogen atom (H) introduction Or / and a raw material gas for introducing a halogen atom (X) is introduced into a deposition chamber whose inside can be decompressed to cause glow discharge in the deposition chamber, and a predetermined support previously installed at a predetermined position. A-Si (H, X) on the surface
Alternatively, a layer made of polycrystalline silicon may be formed.
Also, when forming by the sputtering method, for example, Ar, H
When sputtering a target composed of Si in an atmosphere of an inert gas such as e or a mixed gas based on these gases, a gas for introducing a hydrogen atom (H) or / and a halogen atom (X) is used. It may be introduced into the deposition injection for spattering.

As the raw material gas for supplying Si used in the present invention, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc. in a gas state or gasifiable silicon hydride (silanes) Can be used effectively, and in particular, the ease of handling layer formation work, Si
SiH ₄ and Si ₂ H ₆ are preferable as they have good supply efficiency.

As a raw material gas for introducing a halogen atom used in the present invention, many halogen compounds can be cited, for example, halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Alternatively, a halogen compound that can be gasified is preferable.

Further, a silicon compound containing halogen atoms, which is composed of silicon atoms and halogen atoms and is in a gas state or can be gasified, can be mentioned in the present invention as being effective.

Specific examples of the halogen compound that can be preferably used in the present invention include halogen gas of fluorine, chlorine, bromine and iodine, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ and IF _7. , ICl, IBr
Interhalogen compounds such as

As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, specifically, for example, Si
Preferable examples are silicon halides such as F ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ .

When forming a characteristic photoconductive member of the present invention by the glow discharge method using a silicon compound containing such a halogen atom, without using a hydrogenated silicon gas as a source gas capable of supplying Si In both cases, a layer made of A-Si: H or polycrystalline silicon containing a halogen atom as a constituent element can be formed on a predetermined support.

When a layer containing halogen atoms is manufactured according to the glow discharge method, basically, a halogen gas, which is a raw material gas for supplying Si, and a gas such as Ar, H ₂ and He, etc., have a predetermined mixing ratio and gas flow rate. A desired layer can be formed on a predetermined support by introducing into a deposition chamber for forming a desired layer as described above, and causing a glow discharge to form a plasma atmosphere of these gases. However, in order to measure the introduction of hydrogen atoms, a predetermined amount of a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer.

Further, each gas may be used not only as a single type but also as a mixture of a plurality of types at a predetermined mixing ratio.

In order to form a layer of A-Si (H, X) or polycrystalline silicon by the reaction sputtering method or the ion plating method, for example, in the case of the sputtering method, a target made of Si is used. In the case of the ion plating method, sputtering is performed in a predetermined gas plasma atmosphere, and in the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a vapor deposition boat as an evaporation source, and the silicon evaporation source is subjected to a resistance heating method or an electron beam method ( It can be performed by heating and evaporating by the EB method, etc. and passing the flying evaporate in a predetermined gas plasma atmosphere.

At this time, in order to introduce a halogen atom into the layer formed by either the sputtering method or the ion plating method, the gas of the halogen compound or the silicon compound containing the halogen atom is introduced into the deposition chamber. What is necessary is just to introduce and form a plasma atmosphere of the gas.

When introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or a gas such as the above-mentioned silanes is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. You can do it.

In the present invention, the halogen compound or the halogen-containing silicon compound described above is used as an effective one as a raw material gas for introducing a halogen atom, but in addition, HF, HCl, HBr, HI, etc. Hydrogen halide, SiH ₂ F ₂ , S
Halogen-substituted silicon hydrides such as iH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr _{3 and the} like, also in the gas state or capable of being gasified, and a halide having a hydrogen atom as one of the constituent elements. It can be mentioned as an effective starting material for forming the charge injection blocking layer and the photoconductive layer.

The halide containing these hydrogen atoms is introduced into the layer formed at the time of layer formation at the same time as the introduction of the halogen atom into which a hydrogen atom extremely effective in controlling the electrical or photoelectric properties is also introduced. In this case, it is used as a preferable raw material for introducing halogen.

To introduce hydrogen atoms structurally into the layer to be formed,
Another of H ₂ above, or _{SiH 4, Si 2 H 6,} Si 3 H 8, Si 4 and the H ₁₀ such as silicon hydride gas coexist in the silicon compound in the deposition chamber for supplying a Si discharge It can also be done by causing.

For example, in the case of the reaction sputtering method, a Si target is used, and a gas for introducing a halogen atom and H ₂ gas are introduced into the deposition chamber together with an inert gas such as He and Ar as needed, and a plasma atmosphere is introduced. And then sputtering the Si target to form A-Si (H, X) on the substrate.
Alternatively, a layer made of polycrystalline silicon is formed.

Furthermore, it is possible to introduce a gas such as B ₂ H _{6 while} also doping impurities.

In the present invention, the amount of hydrogen atom (H) or the amount of halogen atom (X) or the amount of hydrogen atom and halogen atom contained in the charge injection blocking layer and the photoconductive layer of the electrophotographic light-receiving member to be formed. It is desirable that the sum of the amounts is 1 to 40 atomic%, and more preferably 5 to 30 atomic%.

In order to control the amount of hydrogen atoms (H) and / or halogen atoms (X) contained in the formed layer, for example, the temperature of the support or / and the hydrogen atoms (H), or the halogen atoms (X) may be adjusted. It suffices to control the amount of the starting material used for inclusion in the volumetric device system, the discharge power, and the like.

In order to make the charge injection blocking layer or the photoconductive layer contain a group III atom or a group V atom, and a carbon atom, an oxygen atom or a nitrogen atom, the charge injection blocking layer or the light is formed by a glow discharge method or a reaction sputtering method. At the time of forming the conductive layer, a starting material for introducing a group III atom or a group V atom and starting materials for introducing an oxygen atom, a nitrogen, and a carbon are respectively introduced into the charge injection blocking layer and the photoconductive layer. It is made by using it together with a starting material for forming a layer and controlling its amount in the layer to be formed.

As such a starting material for introducing a carbon atom, for introducing an oxygen atom and / or for introducing a nitrogen atom, or a starting material for introducing a group III atom or a group V atom, at least a carbon atom, an oxygen atom and Most of the gasified substances having any of nitrogen atoms or group III atoms or group V atoms as constituent atoms or gasified substances can be used.

For example, if an oxygen atom is contained, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (O) as constituent atoms, and if necessary, hydrogen atoms (H) or halogen atoms. A raw material gas containing (X) as a constituent atom is mixed and used at a desired mixing ratio, or
A raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) as constituent atoms are also mixed at a desired mixing ratio, or
It is possible to use a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing silicon atoms (Si), oxygen atoms (O) and hydrogen atoms (H) as constituent atoms. I can.

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

Specific examples of starting materials for introducing oxygen atoms and for introducing nitrogen atoms include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), Nitrogen dioxide (N ₂ O), Nitrogen trioxide (N ₂ O ₃ ), Nitrogen dioxide (N ₂ O ₄ ), Nitrogen dioxide (N ₂ O ₅ ), Nitric oxide (N
O ₃ ), nitrogen (N ₂ ), ammonia (NH ₃ ), hydrogen azide (H
N ₃ ), hydrazine (NH ₂ NH ₂ ), silicon atom (Si), oxygen atom (O) and hydrogen atom (H) as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane ( H
₃ SiOSiH ₂ OSiH ₃ ) and other lower siloxanes.

Examples of the carbon atom-containing compound as a raw material for introducing carbon atoms include saturated hydrocarbons having 1 to 4 carbon atoms and 2 to 4 carbon atoms.
Ethylene-based hydrocarbons, acetylene-based hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, saturated hydrocarbons include methane (CH ₄ ),
Ethane (C ₂ H _6), propane (C ₃ H _8), n- butane (n-C ₄
H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene-based hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-
1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C
₄ H ₈ ), pentene (C ₅ H ₁₀ ) acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ),
Examples include butyne (C ₄ H ₆ ).

As a source gas containing Si, C and H as constituent atoms, Si (C
Mention may be made of alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

When the glow discharge method is used to form the charge injection blocking layer and the photoconductive layer containing the group III atom or the group V atom, the starting material used as the source gas for forming the layer is A- A starting material for introducing a group III atom or a group V atom into a material appropriately selected from the starting materials for forming the charge injection blocking layer and the photoconductive layer, which are composed of Si (H, X) or polycrystalline silicon. Is added. As a starting material for introducing such a Group III atom or a Group V atom, a substance in a gas state containing a Group III atom or a Group V atom as a constituent atom or a gasified substance capable of being gasified is used. Any of these may be used.

What is effectively used as a starting material for introducing a Group III atom in the present invention is, specifically, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B for introducing a boron atom. ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆
Examples thereof include boron hydrides such as H ₁₄ and boron halides such as BF ₃ , BCl ₃ , BBr _{3 and the} like. In addition to these, AlCl ₃ , GaCl ₃ , In
Cl ₃ , TlCl ₃ etc. can also be mentioned.

In the present invention, what is effectively used as a starting material for introducing a Group V atom is, specifically, for introducing a phosphorus atom,
PH ₃ , P ₂ H ₄ etc. Phosphorus hydride, PH ₄ I, PF ₃ , PF ₅ , PCl ₃ , PC
Examples thereof include phosphorus halides such as l ₅ , PBr ₃ , PBr ₅ , and PI ₃ .
In addition, AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , Sb
_{F 3, SbF 5, SbCl 3} , SbCl 5, BiH 3, BiCl can also be mentioned _3, BiBr _3, etc..

The content of the group III atom or the group V atom introduced into the charge injection blocking layer and the photoconductive layer containing the group III atom or the group V atom depends on the group III atom or the group III atom introduced into the deposition chamber. It can be arbitrarily controlled by controlling the gas flow rate of the starting material for introducing the Group V atom, the gas flow rate, the discharge power, the support temperature, the pressure in the deposition chamber, and the like.

The temperature of the support for effectively achieving the object of the present invention is appropriately selected, but in the case of the charge injection blocking layer composed of polycrystalline silicon, preferably 200 ° C to 700 ° C.
℃, more preferably 250 ℃ ~ 600 ℃ is desirable A-
In the case of a photoconductive layer composed of Si (H, X), preferably 50
C. to 350.degree. C., more preferably 100.degree. C. to 300.degree. C. is desirable.

In the formation of the charge injection blocking layer and the photoconductive layer in the present invention, the delicate control of the composition ratio of the atoms constituting the layer and the control of the layer thickness are easy as compared with other methods. It is desirable to adopt a sputtering method or a sputtering method, but when forming the charge injection blocking layer and the photoconductive layer by these layer forming methods, the discharge power and gas at the time of forming the layer are the same as the above-mentioned support temperature. The pressure is an important factor that influences the characteristics of the charge injection blocking layer and the photoconductive layer created.

In producing the charge injection blocking layer and the photoconductive layer having the characteristics capable of achieving the object of the present invention with high productivity and efficiency, the discharge power condition is that the charge injection blocking layer is made of a polycrystalline material. When forming a layer, preferably 100 to 5
000W, more preferably 200 to 2000W, preferably when forming a photoconductive layer composed of an amorphous material, preferably 10 to 1000W, more preferably 20 to 500W, The gas pressure in the deposition chamber is preferably 10 ^{−3 to} 0.8 Torr, and more preferably 5 × 10 ^{−3 to} 0.5 Torr when the charge injection blocking layer made of a polycrystalline material is formed. When forming a photoconductive layer which is desirably composed of an amorphous material, preferably 0.01 to 1 Torr, more preferably
It is desirable to set it to about 0.1 to 0.5 Torr.

In the present invention, the above-mentioned ranges are mentioned as the desirable numerical ranges of the support temperature and the discharge power for forming the charge injection blocking layer and the photoconductive layer, but these layer forming factors are usually independently separated. However, it is desirable to determine the optimum value of each layer forming factor based on the mutual and organic relationships so as to form the charge injection blocking layer and the photoconductive layer having desired characteristics.

In the present invention, the amount of carbon, oxygen or nitrogen contained in the photoconductive layer to be formed, or the sum of the amounts of two or more of these, greatly enhances the characteristics of the electrophotographic light-receiving member to be formed. It depends on what is desired, and it has to be appropriately determined as desired, but it is preferably 0.0005 to 30 atom%, more preferably 0.001 to 20 atom%, and most preferably 0.002 to 15 atom%.

The layer thickness of the photoconductive layer is appropriately determined as desired so that the photocarriers generated by irradiation with light having desired spectral characteristics are efficiently transported, and preferably 1 to
It is desirable that the thickness is 100 μ, more preferably 2 to 50 μ.

In the present invention, a long-wavelength photosensitive layer made of an amorphous material containing silicon atoms and germanium atoms and having sensitivity to long-wavelength light is provided between the charge injection blocking layer and the support. May be.

Further, the long-wavelength photosensitive layer may contain at least one of oxygen atoms, nitrogen atoms and a substance that controls conductivity in a uniform or non-uniform distribution state in the layer thickness direction.

By providing the layer, the electrophotographic light-receiving member of the present invention has high photosensitivity in the entire visible range, particularly excellent matching with a semiconductor laser, and improved photoresponsiveness.

Further, by containing either one of an oxygen atom and a nitrogen atom in the layer, the adhesion between the layer and the support or / and the layer and the charge injection blocking layer and the band gap of the layer can be adjusted. .

Furthermore, by containing a substance that controls conductivity in the layer, it is possible to prevent charge injection from the support or improve the efficiency of transporting photoexcited charges.

In order to form a long-wavelength photosensitive layer composed of an amorphous material containing silicon atoms and germanium atoms by the glow discharge method, basically, a silicon source gas for supplying silicon atoms (Si) can be supplied. With the germanium atom (Ge)
The source gas for supplying Ge and the source gas for introducing hydrogen atom (H) and / or for introducing halogen atom (X) are introduced into a deposition chamber where the inside can be depressurized. A glow discharge may be generated in the deposition chamber to form a layer on the surface of a predetermined support which is installed at a predetermined position in advance. Further, when formed by the sputtering method, for example, a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases,
Alternatively, it was diluted with a diluting gas such as He or Ar, if necessary, using two sheets of the target composed of the target and Ge or using a target composed of Si and Ge. As a raw material gas for Ge supply, a gas for introducing hydrogen atoms (H) and / or halogen atoms (X) is introduced into a deposition chamber for spattering, if necessary, to form a plasma atmosphere of the desired gas. Made by

As the raw material gas for supplying Si used in the present invention, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc. in a gas state or gasifiable silicon hydride (silanes) Can be used effectively, and in particular, the ease of handling layer formation work, Si
SiH ₄ and Si ₂ H ₆ are preferable as they have good supply efficiency.

Materials that can be used as the source gas for Ge supply include GeH ₄ , Ge
₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge
Germanium hydride in a gas state or gasifiable such as ₈ H ₁₈ and Ge ₉ H ₂₀ can be effectively used. Particularly, it is easy to handle during the layer forming work, and the Ge supply efficiency is good. In this respect, GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ are preferable.

As a raw material gas for introducing a halogen atom used in the present invention, many halogen compounds can be cited, for example, halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Alternatively, a halogen compound that can be gasified is preferable.

Further, in the case of forming a long-wavelength photosensitive layer, a halogen compound or a silicon compound containing halogen is effectively used as a raw material gas for introducing a halogen atom, but in addition, GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂
Cl ₂ , GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂ I
₂ , GeH ₃ I and other hydrogenated germanium halides, and other halides containing hydrogen atoms as one of the constituent elements, GeF ₄ , GeCl
_{4, GeBr 4, GeI 4,} GeF 2, GeCl 2, GeBr 2, given as a starting material GeI ₂ and halogenated germanium, etc. in a gaseous state or substances effective long wavelength light for photosensitive layer formation can be gasified I can do things.

In the present invention, the content of the germanium atom contained in the long-wavelength photosensitive layer is appropriately determined as desired so that the object of the present invention can be effectively achieved, but with respect to the sum with the silicon atom. , Preferably 1 to 10 × 10 ⁵ atom pp
m, preferably 100-9.5 × 10 ⁵ atomic ppm, optimally 500-8
It is desirable that the concentration is × 10 ⁵ atom ppm.

The long-wavelength photosensitive layer may further contain at least one of a conductivity controlling substance, an oxygen atom and a nitrogen atom.

In the present invention, the content of the substance for controlling the conductive properties contained in the long wavelength photosensitive layer is preferably 0.01 to
5 × 10 ⁵ atom ppm, more preferably 0.5 to 1 × 10 ⁴ atom pp
m, optimally 1 to 5 × 10 ³ atomic ppm is desirable.

The amount of nitrogen atoms (N) or the amount of oxygen atoms (O) or the sum of the amounts of nitrogen atoms and oxygen atoms (N + O) contained in the long-wavelength photosensitive layer is preferably 0.01 to 40 atom%, more preferably Is preferably 0.05 to 30 atom%, optimally 0.1 to 25 atom%.

The support temperature for effectively achieving the object of the present invention is appropriately selected from the optimum range, but when forming a long-wavelength photosensitive layer composed of an amorphous material, preferably 50 ° C to 35 ° C.
The temperature is preferably 0 ° C, more preferably 100 ° C to 300 ° C.

In the formation of the long-wavelength photosensitive layer in the present invention, the delicate control of the composition ratio of the atoms constituting the layer and the control of the layer thickness are easy as compared with other methods, so that the glow discharge method or the sputtering method is used. However, when the long-wavelength photosensitive layer is formed by these layer forming methods, the discharge power and gas pressure at the time of forming the layer act on the long-wavelength photosensitive layer in the same manner as the support temperature. It is an important factor that influences the characteristics of the wavelength light-sensitive layer.

In producing the long-wavelength photosensitive layer having the characteristics capable of achieving the object of the present invention with good productivity and efficiency, the discharge power condition is that the long-wavelength photosensitive layer composed of an amorphous material is used. When forming a film, it is preferably 10 to 1000 W, and more preferably 20 to 500 W. Regarding the gas pressure in the deposition chamber, a long wavelength photosensitive layer composed of an amorphous material is formed. In this case, it is preferably 0.01 to 1 Torr, and more preferably 0.1 to 0.5 Torr.

In the present invention, the support temperature for forming the long wavelength light-sensitive layer, the range described above as a desirable numerical value range of the discharge power is mentioned, these layer forming factors,
It is usually not independently determined separately, but it is desirable to determine the optimum value of each layer forming factor based on mutual and organic relations so as to form a long-wavelength photosensitive layer having desired characteristics. .

In the present invention, the layer thickness of the long wavelength photosensitive layer is preferably 30
Å ~ 50μm, more preferably 40Å ~ 40μm, optimally 50
Å ~ 30μm is desirable.

In the electrophotographic light-receiving member of the present invention, the support 101
For the purpose of further improving the adhesion between the light-sensitive layer and the long-wavelength photosensitive layer or the charge injection blocking layer, for example, Si ₃ N ₄ , SiO ₂ , SiC, Si
An adhesion layer made of an amorphous material containing at least one of O hydrogen atom and halogen atom, at least one of nitrogen atom, oxygen atom, and carbon atom, and silicon atom may be provided.

Surface layer The surface layer formed on the photoconductive layer has a free surface, and achieves the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance use environment characteristics, and durability. It is provided for this purpose.

Further, in the present invention, since each of the amorphous materials forming the photoconductive layer and the surface layer forming the light receiving layer has a common constituent element of silicon atom, it is possible to form a layered interface. The chemical stability is sufficiently ensured.

The surface layer is made of a polycrystalline material composed of silicon atoms, carbon atoms and hydrogen atoms.

The surface layer is formed by glow discharge method, spattering method, ion implantation method, ion plating method,
It is made by the electron beam method or the like. These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, a load level of capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be manufactured. It is relatively easy to control the production conditions for producing a photoreceptive member for electrophotography having, and it is easy to introduce it into a surface layer for producing carbon atoms and hydrogen atoms together with silicon atoms, and it is easy to introduce the glow A discharge method or a spattering method is preferably adopted.

Further, in the present invention, the surface layer may be formed by using the glow discharge method and the sputtering method together in the same apparatus system.

To form the surface layer by the glow discharge method, the raw material gas is mixed with a diluting gas at a predetermined mixing ratio if necessary,
It is introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into gas plasma by causing a glow discharge to form a surface on the photoconductive layer already formed on the support 101. The layers may be deposited.

In the present invention, as the raw material gas for forming the surface layer, Si,
Most of the gaseous substances having at least one of C and H as constituent atoms or the gasified substances capable of being gasified can be used.

When a source gas containing Si as a constituent atom is used as one of Si, C, and H, for example, a source gas containing Si as a constituent atom, a source gas containing C as a constituent atom, and a constituent atom of H as a constituent atom. Or a raw material gas having Si as a constituent atom and a raw material gas having C and H as a constituent atom are mixed at a desired mixing ratio. Alternatively, the raw material gas containing Si as a constituent atom and the raw material gas containing Si, C and H as three constituent atoms can be mixed and used.

Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms.

In the present invention, SiH ₄ and Si ₂ H containing Si and H as constituent atoms are effectively used as the source gas for forming the surface layer.
₆ , Si ₃ H ₈ , Si ₄ H _10, etc. Silanes and other hydrogenated silicon gas, C and H as constituent atoms, for example, carbon number 1 ~
4 saturated hydrocarbon, C2-C4 ethylene hydrocarbon, C2-C3 acetylene hydrocarbon, etc. are mentioned.

Specifically, saturated hydrocarbons include methane (CH ₄ ),
Ethane (C ₂ H ₆ ), propane (C ₃ H ₈ , n-butane (n-C ₄ H
₁₀ ), pentane (C ₅ H ₁₂ ), ethylene-based hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-
1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C
₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene-based hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C
₃ H ₄ ), butyne (C ₄ H ₆ ) and the like.

As a source gas containing Si, C and H as constituent atoms, Si (C
Alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ can be mentioned. In addition to these raw material gases, H ₂ is of course also used as an effective raw material gas for introducing H.

To form the surface layer 104 by the sputtering method,
Single crystal or polycrystalline Si wafer or C wafer or
It may be carried out by targeting a wafer containing a mixture of Si and C and sputtering these in various gas atmospheres.

For example, if you use a Si wafer as a target,
The raw material gas for introducing C and H is diluted with a diluting gas, if necessary, and introduced into the deposition chamber for the sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. Good.

Also, separately, Si and C are used as separate targets, or
By using a single target of mixed Si and C, the sputtering is performed in a gas atmosphere containing at least hydrogen atoms.

As the raw material gas for introducing C or H, the raw material gas shown in the example of the glow discharge described above can be used as an effective gas even in the case of sputtering.

In the present invention, a so-called rare gas such as He, Ne, Ar or the like can be preferably used as the diluting gas used when the surface layer is formed by the glow discharge method or the sputtering method.

The surface layer 104 in the present invention is carefully formed to provide its desired properties as desired.

That is, a substance having Si, C, and H as constituent atoms structurally takes a form from crystalline to amorphous depending on its preparation condition, and has electrical properties from conductive to semiconducting to insulating. And a property from a photoconductive property to a non-photoconductive property. Therefore, in the present invention, a surface layer formed of a polycrystalline material having desired properties according to the purpose is formed. As described above, the selection of the production conditions is strictly made according to the desire.

That is, by forming a surface layer composed of a polycrystalline material containing silicon atoms, carbon atoms and hydrogen atoms as constituent elements, the defect concentration in the surface layer is reduced, and the structure is dense and stable. As a result, the ability to prevent charge injection from the free surface is improved, and the residual potential and ghost, etc. due to charge traps due to defects are reduced, and electrophotographic characteristics are improved. Furthermore, the hardness of the surface layer has increased, and the durability has dramatically improved.

When the surface layer is formed on the surface of the photoconductive layer, the temperature of the support during formation of the layer is an important factor that influences the structure and characteristics of the layer formed, and is an object of the present invention. It is desirable that the support temperature during layer formation be strictly controlled so that a surface layer having characteristics can be formed as desired.

As the temperature of the support for forming the surface layer for effectively achieving the object of the present invention, an optimum range is appropriately selected according to the method of forming the surface layer, and the formation of the surface layer is performed. However, preferably 50 ℃ ~ 350 ℃, more preferably 100 ℃
A temperature of ~ 300 ° C is desirable. For the formation of the surface layer, the glow discharge method and the sputtering method are used because it is relatively easy to control the composition ratio of the atoms that form the layer and the layer thickness compared to other methods. Is advantageous, but when the surface layer is formed by these layer forming methods,
Similar to the support temperature, the discharge power and gas pressure during layer formation are one of the important factors that influence the characteristics of the surface layer to be formed.

The discharge power condition for the surface layer having the characteristics for achieving the object of the present invention to be produced effectively with good productivity is preferably 100 to 5000 W, and more preferably 200 W.
~ 2000W is recommended. The gas pressure in the deposition chamber is preferably 10 ^{−3 to} 0.8 Torr, more preferably 5 × 10 ^{−3 to} 0.5 Torr.
It is desirable to set it to about rr.

In the present invention, the support temperature for forming the surface layer,
Although the values in the above-mentioned range are mentioned as the desirable numerical value range of the discharge power, these layer forming factors are not independently determined and a surface layer made of a polycrystalline material having desired characteristics is formed. As described above, it is desirable that the optimum value of each layer forming factor is determined based on the mutual organic relation.

The amount of carbon atoms and hydrogen atoms contained in the surface layer in the electrophotographic light-receiving member of the present invention is the same as the conditions for forming the surface layer, and the surface layer can achieve desired characteristics for achieving the object of the present invention. Is an important factor that is formed.

The amount of carbon atoms contained in the surface layer in the present invention is preferably 1 × 10 6 with respect to the total amount of silicon atoms and carbon atoms.
^{-3 to} 90 atom%, optimally 10 to 80 atom% is desirable. The content of hydrogen atoms is usually 1 × 10 ⁻³ to 70 atom%, preferably 1 × 10 ^{−2 to} 65 atom%, optimally 5 × 10 ⁻² to the total amount of constituent atoms. It is desirable to set the content to 60 atom%, and the light-receiving member formed when the hydrogen content is in such a range is practically far superior to the conventional one and can be sufficiently applied. is there.

That is, defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer composed of a polycrystalline material containing silicon atoms, carbon atoms and hydrogen atoms have a characteristic as a photoreceptive member for electrophotography. It is known to have an adverse effect, for example, deterioration of charging characteristics due to injection of electric charges from a free surface, fluctuation of charging characteristics due to change of surface structure under use environment, for example, high humidity, and further during corona charging or light exposure. Charge retention is injected into the surface layer from the photoconductive layer at the time of irradiation and trapped by defects in the surface layer, which may be an afterimage phenomenon upon repeated use.

However, by using a polycrystalline material containing silicon atoms, carbon atoms, and hydrogen atoms for the surface layer, the defects in the surface layer are greatly reduced, and as a result, all of the above problems are eliminated, and in particular, the conventional It is possible to make a dramatic improvement in electrical characteristics and high-speed continuous usability.

Hydrogen content in the surface layer, H2 gas flow rate, support temperature,
It can be controlled by discharge power, gas pressure and the like.

Further, a halogen atom may be contained in the surface layer. As a method of containing a halogen atom in the surface layer,
For example, if the source gas is SiF ₄ , SiFH ₃ , Si ₂ F ₆ , SiF ₃ SiH ₃ , SiCl
Mixing a halogenated silicon gas such as ₄ or
It may be formed by mixing a halogenated carbon gas such as CF ₄ , CCl ₄ , or CH ₃ CF ₃ with the glow discharge decomposition method or the sputtering method.

The numerical range of the layer thickness in the present invention is one of the important factors for effectively achieving the object of the present invention.

The numerical range of the layer thickness of the surface layer in the present invention is appropriately determined according to the intended purpose in order to effectively achieve the object of the present invention.

Also, the layer thickness of the surface layer, in relation to the layer thickness of the photoconductive layer, must be appropriately determined as desired under the organic relationship according to the characteristics required for each layer region. There is. In addition, it is desirable to consider in terms of economical efficiency in consideration of productivity and mass productivity.

The thickness of the surface layer in the present invention is preferably 0.003
~ 30μ, more preferably 0.004-20μ, optimally 0.005-10
It is desirable that it be μ.

The layer thickness of the light-receiving layer of the light-receiving member for electrophotography according to the present invention is appropriately determined according to the purpose according to the purpose.

In the present invention, as the layer thickness of the light receiving layer, the characteristics imparted to the photoconductive layer and the surface layer constituting the light receiving layer are effectively utilized, respectively, and the object of the present invention is effectively achieved. The layer thickness of the photoconductive layer and the surface layer is appropriately determined according to the desire, and preferably the layer thickness of the photoconductive layer is several hundred to several thousand times the layer thickness of the surface layer. The above is preferable.

The specific value is preferably 3 to 100 μ, more preferably 5 to 70 μ, and most preferably 5 to 50 μ.

Next, the outline of the method for producing a photoconductive member of the present invention will be described.

FIG. 18 shows an example of an apparatus for manufacturing a light receiving member for electrophotography.

In the gas cylinders 1102 to 1106 in the figure, raw material gases for forming the respective layers of the present invention are sealed. For example, 1102 is SiH ₄ (purity 99.999%) cylinder,
1103 is B ₂ H ₆ gas diluted with H ₂ (purity 99.999%, hereinafter B ₂
Abbreviated as H ₆ / H ₂ . ), 1104 is H ₂ gas (purity 99.99999%) cylinder, 1105 is NO gas (purity 99.999%) cylinder, 1106 is CH ₄
It is a gas (purity 99.99%) cylinder.

A gas cylinder is required to allow these gases to flow into the reaction chamber 1101.
Check that valves 1122 to 1126 and leak valves 1135 of 1102 to 1106 are closed, and check that the inflow valves 1112 to 111 are closed.
6. After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are opened, the main valve 1134 is opened first to exhaust the reaction chamber 1101 and the gas pipe. Next vacuum gauge 1136
When the reading of about 5 × 10 ^-6 torr is reached, the auxiliary valve 113
2, 1133 and the outflow valves 1117 to 1121 are closed.

Next, an example of forming the electrophotographic light-receiving member having the layer structure shown in FIG. 1 on the cylindrical substrate 1137 will be described.
SiH ₄ gas from gas cylinder 1102, H ₂ gas from gas cylinder 1104, B ₂ H ₆ / H ₂ gas from gas cylinder 1103, gas cylinder 11
From NO, open the valves 1122 to 1125 from NO gas respectively to adjust the pressure of the outlet pressure gauges 1127 to 1130 to 1 kg / cm ² , respectively, and gradually open the inflow valves 1112 to 1115 respectively, and in the mass flow controllers 1107 to 1110. Inflow respectively. Subsequently, the outflow valves 1117 to 1120 auxiliary valves 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. SiH ₄ gas flow rate at this time
The outflow valves 1117 to 1120 are adjusted so that the ratio of the B ₂ H ₆ / H ₂ gas flow rate and the NO gas flow rate becomes a desired value, and the vacuum gauge 1136 is adjusted so that the pressure in the reaction chamber becomes a desired value. Adjust the opening of the main valve 1134 while watching the reading. Then, after confirming that the temperature of the base cylinder 1137 is set to a desired temperature by the heater 1138, the power source 1140 is set to a desired electric power to cause glow discharge in the reaction chamber 1101, and at the same time, in advance. B ₂ according to the designed rate of change curve
The flow rate of H ₆ / H ₂ gas and / or NO gas can be adjusted manually or by a method such as an externally driven motor.
Is gradually changed to control the distribution concentration of boron atoms and / or oxygen atoms contained in the layer formed in the layer thickness direction.

As described above, when the charge injection blocking layer made of polycrystalline silicon containing boron atoms and oxygen atoms is formed to the desired layer thickness, the outflow valves 1120 and 1118 are closed and the reaction chamber 11 is closed.
Block the inflow of B ₂ H ₆ / H ₂ gas and NO gas into 01 and adjust outflow valves 1117 and 1119 at the same time to adjust SiH ₄ gas and H ₂ gas.
By controlling the gas flow rate and continuing layer formation, a photoconductive layer containing no oxygen atoms and boron atoms is formed on the charge injection blocking layer to a desired layer thickness.

When forming a photoconductive layer containing oxygen atoms and / or boron atoms, the flow rate may be adjusted to a desired value instead of closing the outflow valve 1118 or / and 1120.

When halogen atoms are contained in the charge injection blocking layer and the photoconductive layer, SiF ₄ gas, for example, is further added to the above gas and fed into the reaction chamber 1101.

When forming each layer, the layer formation rate can be further increased depending on the selection of gas species. For example, instead of SiH ₄ gas
If a layer is formed using Si ₂ H ₆ gas, it can be increased several times, and productivity is improved.

To form a surface layer on the photoconductive layer formed as described above, for example, SiH ₄ gas, CH ₄ gas and, if necessary, H Diluted gas such as _{2 is} caused to flow into the reaction chamber 1101 at a desired flow rate ratio to cause glow discharge according to desired conditions.

The amount of carbon atoms contained in the surface layer can be controlled as desired, for example, by arbitrarily changing the flow rate ratio of SiH ₄ gas and CH ₄ gas introduced into the reaction chamber 1101 as desired. I can.

The amount of hydrogen atoms contained in the surface layer can be controlled as desired by, for example, arbitrarily changing the flow rate of the H ₂ gas introduced into the reaction chamber 1101.

It goes without saying that all the outflow valves other than the gas necessary for forming each layer are closed, and when forming each layer, the gas used for forming the previous layer is the same as the outflow valve 1117 in the reaction chamber 1101. ~ 1121 to avoid remaining in the piping from the inside of the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valve 1132 is opened, the main valve 1134 is fully opened, and the system is temporarily evacuated to a high vacuum. Do as needed.

Further, during the layer formation, in order to make the layer formation uniform, the base cylinder 1137 is rotated at a constant speed by the motor 1139.

Example 1 Using the manufacturing apparatus shown in FIG. 18, an electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the manufacturing conditions shown in Table 1. Further, using a device of the same type as in FIG. 18, a sample having only the surface layer formed on a cylinder having the same specifications and a sample having only the charge injection blocking layer formed thereon were separately prepared as analysis samples. The light receiving member (hereinafter referred to as a drum) is set in an electrophotographic apparatus to check the electrophotographic characteristics such as initial charging ability, residual potential and ghost under various conditions. We investigated the deterioration of charging ability, deterioration of sensitivity, and the increase of image defects after the endurance of 10,000 sheets. Furthermore, 35
The image deletion of the drum in a high temperature and high humidity atmosphere of 85 ° C was also evaluated. And the evaluated drum is
The upper, middle and lower parts of the image area were cut out and subjected to quantitative analysis of hydrogen contained in the surface layer using SIMS.
Also, for the sample with only the surface layer and the charge injection blocking layer,
After cutting out the upper, middle, and lower parts of the sample in the generatrix direction, an X-ray diffractometer was used to cut Si (111) around a diffraction angle of 27 °.
The diffraction pattern corresponding to was obtained and the presence or absence of crystallinity was examined. Based on the above evaluation results, the hydrogen content in the surface layer, and the presence or absence of crystallinity of the surface layer and the charge injection blocking layer,
Shown in the table. As can be seen from Table 2, a remarkable superiority was recognized especially in the items of initial charging ability, image deletion, residual potential, ghost, and increase in image defects.

<Comparative Example 1> A drum and a sample were prepared by the same apparatus and method as in Example 1 except that the manufacturing conditions were changed as shown in Table 3, and the same evaluation and analysis were performed. The results are shown in Table 4.

As shown in Table 4, it was confirmed that various items were inferior to those of Example 1.

Example 2 Using the manufacturing apparatus of FIG. 18, an electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the manufacturing conditions of Table 5. In addition, a sample in which only a surface layer was formed on a cylinder having the same specifications and a device in which only a charge injection blocking layer were formed using the same device as in FIG. 18 were separately prepared as analysis samples. The light receiving member (hereinafter referred to as a drum) is set in an electrophotographic apparatus to check the electrophotographic characteristics such as initial charging ability, residual potential and ghost under various conditions. We investigated the deterioration of charging ability, deterioration of sensitivity, and the increase of image defects after the endurance of 10,000 sheets. Furthermore, the image deletion of the drum in an atmosphere of high temperature and high humidity of 35 ° C and 85% was also evaluated. Then, for the drum that has been evaluated, cut out the parts corresponding to the upper, middle, and lower parts of the image part and use SIMS for quantitative analysis of the hydrogen contained in the surface layer, and also in the charge injection blocking layer. The component profiles of boron (B) and oxygen (O) in the layer thickness direction were examined. On the other hand, for the samples with only the charge injection element layer and only the surface layer, after cutting out the parts corresponding to the upper, middle, and lower directions of the sample in the generatrix direction, use an X-ray diffractometer to measure Si at a diffraction angle of about 27 °. (11
The diffraction pattern corresponding to 1) was obtained and the presence or absence of crystallinity was investigated. Table 6 shows the above evaluation results, the hydrogen content in the surface layer, and the presence or absence of crystallinity of the surface layer and the charge injection blocking layer. Further, FIG. 21 shows the component profile of the element in the charge injection blocking layer. As can be seen from Table 6, remarkable advantages were observed particularly in the items of initial chargeability, residual potential, ghost, image deletion, image defects, and increase in image defects.

<Example 3 (Comparative Example 2)> A plurality of drums and surface layers were formed under the same conditions as in Example 1 except that the preparation conditions of the surface layer were changed to several conditions shown in Table 7. A sample for analysis was prepared. These drums and samples were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 8 were obtained.

<Example 4> The production conditions of the photoconductive layer were changed to several conditions shown in Table 9,
Other than that, a plurality of drums were prepared under the same conditions as in Example 1. As a result of subjecting these drums to the same evaluation as in Example 1, the results shown in Table 10 were obtained.

Example 5 The conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 11, and only the plurality of drums and the charge injection blocking layer were formed under the same conditions as in Example 1 except for the above. Samples were prepared separately. These drums and samples were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 12 were obtained.

Example 6 A plurality of drums and a charge injection blocking layer were formed under the same conditions as in Example 1 except that the conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 13. Samples were prepared separately. These drums and samples were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 14 were obtained.

Example 7 A plurality of drums were prepared under the same conditions as in Example 1 except that the conditions for producing the long wavelength photosensitive layer were changed to several conditions shown in Table 15. These drums were subjected to the same evaluations as in Example 1, and the results shown in Table 16 were obtained.

<Example 8> A plurality of drums were prepared under the same conditions as in Example 1 except that the conditions for producing the long-wavelength photosensitive layer were changed to several conditions shown in Table 17. These drums were subjected to the same evaluations as in Example 1, and the results shown in Table 18 were obtained. And the No. 802 drum, which has been evaluated, is above / middle of the image section.
The lower part was cut out and the component profile of germanium (Ge) in the layer thickness direction in the long wavelength photosensitive layer was investigated using SIMS. The result is shown in FIG.

Example 9 An adhesion layer was formed on a base cylinder under several kinds of manufacturing conditions shown in Table 19, and a light receiving member was further formed thereon under the same manufacturing conditions as in Example 1. Formed. These light-receiving members were subjected to the same evaluations as in Example 1, and the results shown in Table 20 were obtained.

<Example 10> Mirror-processed cylinders were further subjected to lathe processing with a sword bite having various angles, and a plurality of cylinders having a cross-sectional shape as shown in FIG. 19 and various cross-sectional patterns as shown in Table 21 were prepared. I prepared a book. The cylinders were sequentially set in the production apparatus shown in FIG. 18 and subjected to the drum production under the same production conditions as in Example 1. The prepared drum was evaluated variously by an electrophotographic apparatus having a digital exposure function using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 22 were obtained.

<Embodiment 11> The surface of a cylinder that has been mirror-finished is continuously exposed to the dropping base of a large number of bearing balls to produce countless dents on the cylinder surface, so-called surface dimple processing is performed, and FIG. A plurality of cylinders having a cross-sectional shape like this and various cross-sectional patterns as shown in Table 23 were prepared. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 18 and subjected to the drum manufacturing under the same manufacturing conditions as in Example 1. The drum thus prepared was subjected to various evaluations with an electrophotographic apparatus having a digital exposure function using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 24 were obtained.

<Comparative Example 3> A drum and a sample were produced by the same apparatus and method as in Example 1 except that the production conditions were changed as shown in Table 25, and subjected to the same evaluation and analysis. The results are shown in Table 26.

As shown in Table 26, it was recognized that various items were inferior to those of Example 1.

[Summary of Effects of the Invention] The light-receiving member of the present invention has the same layer structure as that of the above-described specific layer structure of the light-receiving member for electrophotography having a photoconductive layer composed of A-Si (H, X). As a result, A-Si (H, X)
Capable of solving all the problems of the conventional electrophotographic light-receiving member composed of, and having particularly excellent moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc. Is. In addition, there is no effect of residual potential, and its electrical characteristics are stable, and the image obtained by using it has high density and clear halftone, and is very excellent. .

In particular, in the electrophotographic light-receiving member of the present invention, by using a charge injection blocking layer made of polycrystalline silicon, a relatively low resistance photoconductive layer having sensitivity to light in a relatively wide range of wavelengths is used. Became possible. Moreover, because of the specific layer structure as described above, a large number of charges that have been irradiated with light and thermally excited are swept sufficiently fast not only in the photoconductive layer but also in the charge injection blocking layer and the surface layer. Even under the exposure condition, no residual potential or ghost is generated at all, and a high-quality image with high resolution can be stably and repeatedly obtained.

Also, by forming a surface layer composed of a polycrystalline material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent elements, the defect concentration in the surface layer is reduced, and the structure is dense and stable. Therefore, the ability to prevent the injection of electric charges from the free surface is improved, and the residual potential and ghost due to the trap of electric charges due to defects are reduced, and the electrophotographic characteristics are improved. Furthermore, the hardness of the surface layer has increased, and the durability has dramatically improved.

[Brief description of drawings]

FIG. 1 is a schematic layer structure diagram for explaining a layer structure of a light-receiving member for electrophotography of the present invention, and FIGS. 2 to 6 are respectively II which constitute a charge injection blocking layer.
FIGS. 7 to 13 are explanatory views for explaining a distribution state of group I atoms or group V atoms, and FIGS. 7 to 13 are diagrams for explaining distribution states of oxygen atoms and / or nitrogen atoms constituting the charge injection blocking layer, respectively. Explanatory drawing, FIG. 14, FIG. 16 and FIG. 17 are schematic views for explaining the uneven shape of the support surface and a method for producing the uneven shape, and FIG. 15 is the photoreceptor for electrophotography of the present invention. FIG. 18 is a schematic view showing another example of the member, and FIG. 18 is a schematic explanatory view of a manufacturing device by a glow discharge method as an example of a device for forming a light receiving layer of the light receiving member for electrophotography of the present invention. 19 and 20 are schematic diagrams showing the shape of the support, FIG. 21 is a distribution diagram showing the distribution of boron and oxygen in the layer, and FIG. 22 is a distribution diagram showing the distribution of germanium in the layer. . About Figure 1 100 ... Photoreceptive layer, 101 ... Support, 102 ... Charge injection blocking layer, 103 ... Photoconductive layer, 104 ... Surface layer, 105 ... Free surface, About Figure 1500 ... Photoreceptive layer, 1501 support, 1502-1 charge injection blocking layer, 1502-2 photoconductive layer, 1503 surface layer,
1504 …… Free surface, about Figures 16 and 17 1601, 1701 …… Support, 1602, 1702 …… Support surface, 160
3,1703 …… Rigid spherical body, 1604,1704 …… Spherical trace depression About Figure 18 1101 …… Reaction chamber, 1102-1106 …… Gas cylinder, 1107-11
11 …… mass flow controller, 1112 ～ 1116 …… inflow valve, 1117 ～ 1121 …… outflow valve, 1122 ～ 1126 …… valve, 1127 ～ 1131 …… pressure regulator, 1132,1133 …… auxiliary valve, 1134 …… Main valve, 1135 ... Leak valve,
1136 ... Vacuum gauge, 1137 ... Base cylinder, 1138 ... Heater, 1139 ... Motor, 1140 ... High frequency power source.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minor Kato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasushi Fujioka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Co., Ltd. (56) References JP-A-59-119360 (JP, A)

Claims (7)

[Claims] 1. A support, a charge injection blocking layer which is composed of a polycrystalline material having a silicon atom as a base, and which contains an atom belonging to Group III or V of the periodic table on the support, and silicon. Atomic matrix, composed of an amorphous material containing at least one of a hydrogen atom and a halogen atom as a constituent element, a photoconductive layer exhibiting photoconductivity, and a constituent element of a silicon atom, a carbon atom, and a hydrogen atom. And a photoreceptive layer having a surface layer containing the hydrogen atom of 23 atom% to 39 atom%, and a photoreceptive member for electrophotography. 2. The electrophotographic light-receiving member according to claim 1, wherein the surface layer contains a halogen atom. 3. The photoreceptive member for electrophotography according to claim 1, wherein the photoconductive layer contains at least one kind of carbon atom, oxygen atom and nitrogen atom. 4. The photoreceptive member for electrophotography according to claim 1, wherein the charge injection blocking layer contains oxygen atoms and / or nitrogen atoms. 5. The electron according to claim 1, wherein the charge injection blocking layer contains atoms belonging to Group III or Group V of the periodic table in a distributed state in which a large amount is distributed on the support side. Photoreceptive member for photography. 6. The photoreceptive member for electrophotography according to claim 4, wherein the charge injection blocking layer contains the oxygen atoms and / or nitrogen atoms in a distributed state in which a large amount is distributed on the support side. 7. The photoreceptive member for electrophotography according to claim 4, wherein oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer are internally present on the support side.