JPH0797232B2 - Photoreceptive member for electrophotography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to light (light in a broad sense, which means ultraviolet rays, visible rays, ultraviolet rays, x-rays, γ-rays, etc.). The present invention relates to an electrophotographic light-receiving member that is sensitive to electromagnetic waves.

[Description of Prior Art]

In the field of image formation, as a photoconductive material that constitutes the light-receiving layer in the light-receiving member for electrophotography, it has high sensitivity and a high SN ratio [photocurrent (Ip) / dark current (Id)], and It is required to have characteristics such as having absorption spectrum characteristics adapted to the spectrum characteristics, having fast photoresponsiveness and having a desired dark resistance value, and being harmless to a human body during use. 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.
Japanese Patent Laid-Open Publications and the like describe 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 properties such as dark resistance value, photosensitivity and photoresponsiveness, and operating environment properties. In terms of the above, and further in terms of stability over time and durability, the characteristics have been individually improved, but in the actual situation there is room for further improvement in measuring the overall characteristics. is there.

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, there are many inconveniences such as accumulation of fatigue due to repeated use, which causes a so-called ghost phenomenon which causes an afterimage.

When the light-receiving layer is made of an A-Si material, in order to improve its electrical and photoconductive properties, a hydrogen atom (H) or a halogen atom (X) such as a fluorine atom or a chlorine atom is used. , And a boron atom, a phosphorus atom, or the like for controlling the electric conductivity type, or other atom for improving other characteristics as a constituent atom in the photoconductive layer.
Depending on how these constituent atoms are contained, problems may occur in the electrical or photoconductive properties or the electrical withstand voltage of the formed layer.

That is, for example, the photoconductive layer formed by photoirradiation does not have a sufficient life in that layer, or the image transferred to the transfer paper is commonly referred to as "white blank". When a blade is used for the cleaning means, an image defect that is considered to be caused by a general electric discharge breakdown phenomenon, and an image defect commonly referred to as "white streak" that is considered to be caused by the rubbing are generated. Further, when used in a humid atmosphere, or when used immediately after being left in a humid atmosphere for a long period of time, it is not uncommon for blurry images to occur.

Therefore, while improving the characteristics of the A-Si material itself, when designing the light receiving member, the layer constitution, the scientific 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] It is an object of the present invention to solve various problems in a light-receiving member for electrophotography having a conventional light-receiving layer composed of a material having a silicon atom as a base as described above. .

That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially stable regardless of the operating environment, are excellent in light fatigue resistance, and deteriorate even after repeated use. An object of the present invention is to provide a photoreceptive member for electrophotography, which has a photoreceptive layer composed of a material having a silicon atom as a base material, in which durability is high, moisture resistance is high, and residual potential is not or hardly observed. .

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,
It is an object of the present invention to provide a photoreceptive member for electrophotography having a photoreceptive layer which is dense and stable in terms of structural arrangement and has a high layer quality and which is composed of a material having a silicon atom as a base.

Still another object of the present invention is that, when applied as a photoreceptive member for electrophotography, it has 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, which has a photoreceptive layer composed of a material containing a silicon atom as a base material and which exhibits excellent electrophotographic properties that can be applied.

Another object of the present invention is to obtain a high-quality image with high resolution, high density, high density, halftone without any image defects or image blurring during long-term use. Another object of the present invention is to provide a light-receiving member for electrophotography, which has a light-receiving layer composed of a material having atoms as a base.

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

[Structure of Invention]

The electrophotographic light-receiving member of the present invention has a layer structure in which a support and a charge injection blocking layer, a charge generation layer, a charge transport layer and a surface layer are laminated in this order from the support side. And a photoreceptive layer having, wherein the surface layer contains a silicon atom, at least one of a carbon atom, a nitrogen atom and an oxygen atom, and at least one of a hydrogen atom and a halogen atom. Composed of materials,
The charge injection blocking layer, the charge generation layer (hereinafter abbreviated as “CGL”), and the charge transport layer (hereinafter abbreviated as “CTL”) have a silicon atom as a base, and at least hydrogen atoms and halogen atoms are included. An atom that is composed of a non-single-crystal material containing either one of them (hereinafter abbreviated as “Non-Si (H, X)”) and in which the charge injection blocking layer belongs to Group III or Group V of the periodic table. And the charge transport layer contains at least one of a carbon atom, a nitrogen atom and an oxygen atom, and the concentration of the atom belonging to Group III or V of the periodic table is increased in the layer thickness direction. It has at least a portion containing in a non-uniform distribution state having a portion increasing or decreasing from the support side, and the layer thickness of the charge generation layer is thinner than the layer thickness of the charge transport layer.

[Action]

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 is extremely excellent in electrical, optical and photoconductive properties. The characteristics, durability and operating environment characteristics are shown.

Further, since a charge injection blocking layer is provided between the support and CGL, it is possible to effectively prevent the charge in the CGL from being injected from the support side when subjected to a charging treatment. The charging ability is dramatically improved.

In particular, the effect of residual potential on image formation is practically practically stable, its electrical characteristics are stable, it has high sensitivity and high SN, and it has light resistance, repeated use characteristics, and moisture resistance. Since it has excellent properties and electrical withstand voltage, it is possible to stably repeat high-quality images with high density, clear halftone, and high resolution.

Further, the electrophotographic light-receiving member of the present invention has high photosensitivity and fast photoresponse in the entire visible light range. Therefore, it is suitable for forming an image based on a digital signal so that a large number of high-resolution and high-quality images can be repeatedly obtained in a stable state at high speed. In addition, as a light receiving layer
By having a function separation type configuration using CTL and CGL,
By providing separate layers with the important functions of the photoreceptive member for electrophotography, that is, the generation of electric charges (photocarriers) and the transport of the generated electric charges, one layer has both functions. It has a high degree of freedom and has excellent characteristics. Further, since the CTL contains at least one kind of carbon atom, nitrogen atom and oxygen atom, the relative permittivity of the CTL can be reduced, so that the capacity per layer thickness can be reduced and the electrostatic charge can be reduced. The performance and sensitivity can be improved, the withstand voltage against high voltage is improved, and the durability is also improved. In addition, by containing a substance that controls conductivity in the CTL in a non-uniform distribution state in the layer thickness direction, it is possible to design a CTL having an optimum charge transporting ability as desired.

Furthermore, since the charge injection property at the interface between CTL and CGL is also improved, charging ability, sensitivity, residual potential, ghost, sensitivity unevenness, durability, resolution, etc. can be dramatically improved.

In addition, since the surface layer is provided on the surface, mechanical strength and electrical strength are dramatically improved, and it is effective to inject charges from the surface into the layer when subjected to a charging treatment. It is possible to prevent, and the charging ability, use environment characteristics, durability and electrical durability are dramatically improved.

[Specific Description of the Invention]

Hereinafter, the light-receiving member for electrophotography of the present invention will be described in detail with reference to the drawings with reference to specific examples.

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

The electrophotographic light-receiving member 100 shown in FIG. 1 has a light-receiving layer 102 on a support 101 for an electrophotographic light-receiving member, and the light-receiving layer 102 is a substance that controls conductivity ( Non-Si (H, X) containing M ₀ ) uniformly or non-uniformly in all layers
(Hereinafter, abbreviated as “Non-SiMo (H, X)”) charge injection blocking layer 103 composed of CGL104 composed of Non-Si (H, X)
And composed of Non-Si (H, X) and containing at least one of carbon atom, nitrogen atom and oxygen atom,
CTL1 having at least a portion containing a substance (M) that controls conductivity in an uneven distribution in the layer thickness direction
05 and the surface layer 106. Surface layer 106
Has a free surface 107.

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, V, Ti, Pt, Pb
And the like, or alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, ceramics, paper and the like. It is preferable that at least one surface of these electrically insulating supports is subjected to a conductive treatment and a light receiving layer is provided on the surface side subjected to the conductive treatment.

For example, in the case of glass, NiCr, Al, Cr, Mo,
Conductivity is provided by providing a thin film made of Au, Ir, Nb, Ta, V, Ti, Pt, Pb, InO ₃ , ITO (In ₂ O ₃ + Sn), etc., or with a synthetic resin film such as polyester film. If available, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Tl, Pt
A thin film of a metal such as is provided on the surface by vacuum deposition, electron beam deposition, sputtering, or the like, or the surface is laminated with the metal to impart conductivity to the surface.
The shape of the support may be a plate-like endless belt having a smooth surface or an uneven surface, a cylindrical shape, or the like, and its thickness is
It is appropriately determined so as to form a desired electrophotographic light-receiving member, but in the case where flexibility as an electrophotographic light-receiving member is required, a range in which the function as a support is sufficiently exhibited. It can be made as thin as possible. However, it is usually 10 μm or more in terms of mechanical strength and the like in manufacturing and handling the support.

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

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 accurately cut to form a desired uneven shape, pitch, and depth. The inverted V-shaped linear protrusion formed by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped projection may be a double or triple multiple spiral structure or a cross spiral structure.

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

The vertical cross-sectional shape of the convex and concave portions provided on the surface of the support is between the controlled nonuniformity of the layer thickness in the minute column of each layer to be formed and the support and the layer directly provided on the support. In order to ensure good adhesiveness and desired electrical contactability, it is formed into an inverted V shape, but it is preferable to use (A),
As shown in (B) and (C), it is desirable that the shape is substantially an isosceles triangle, a right triangle, or an isosceles triangle. Among these shapes, isosceles triangles and right triangles are preferable.

In the present invention, each dimension of the unevenness 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 that the non-Si (H, X) layer that constitutes the charge injection blocking layer, the charge generation layer, and the charge transport layer is structurally sensitive to the state of the surface on which the layer is formed, and Layer quality varies greatly. Therefore, it is necessary to set the dimension of the unevenness provided on the surface of the support so as not to deteriorate the quality of the non-Si (H, X) layer.

Second, if the free surface of the light-receiving layer has extreme irregularities, the cleaning cannot be completely performed in the cleaning for 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 examining the above-mentioned problems in layer deposition, process problems in electrophotography, and conditions for preventing interference fringe patterns,
The pitch of the recesses on the surface of the support is preferably 500 μm to 0.3.
μm, more preferably 200 μm to 1 μm, optimally 50 μm
It is preferably 5 μm.

The maximum depth of the recess is preferably 0.1 μm to 5 μm,
More preferably 0.3 μm to 3 μm, optimally 0.6 μm to 2 μm
It is desirable to be m. 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 linear projection) is preferably 1 to 20 degrees, more preferably 3 to 15 degrees, Optimally, it is desirable that the angle is 4 to 10 degrees.

Further, the maximum layer thickness difference based on the non-uniformity of the layer thickness of each layer deposited on such a support is preferably within the same pitch.
0.1 μm to 2 μm, more preferably 0.1 μm to 1.5 μm, most preferably 0.2 μm to 1 μm.

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

That is, the surface of the support has unevenness smaller than the resolution required for the electrophotographic light-receiving member, and the unevenness is
This is due to the multiple spherical dents.

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 below with reference to FIGS. 3 and 4, but the shape of the support in the light-receiving member of the present invention will be described. And the manufacturing method thereof is not limited thereto.

FIG. 3 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 the uneven shape.

In FIG. 3, 301 is a support, 302 is the surface of the support, 303 is a rigid spherical body, and 304 is a spherical dent.

Further, FIG. 3 also shows an example of a preferable manufacturing method for obtaining the surface shape of the support. That is, it is shown that the spherical hollow 304 can be formed by allowing the rigid true sphere 303 to naturally fall from a position of a predetermined height above the support surface 302 and colliding with the support surface 302. Then, by using a plurality of rigid true spheres 303 having substantially the same diameter R ₀ and dropping them at substantially the same height h at the same time or in a timely manner, the support surface 302 has substantially the same radius of curvature R. And a plurality of spherical imprints 304 having the same width D can be formed.

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

In FIG. 4, 401 is a support, 402 is the position of the convex portion of the uneven portion,
403 is a rigid spherical body, and 404 is a spherical dent.

By the way, the radius of curvature R and the width D of the uneven shape due to the spherical trace depressions 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 electrophotographic 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 is 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.

Therefore, in order to prevent the occurrence of interference fringes in the electrophotographic light-receiving member by dispersing the interference fringes generated in the entire electrophotographic light-receiving member in the respective trace depressions, the D / R Is 0.035, preferably 0.055 or more.

In addition, the width D of the unevenness due to the trace depression is 500 μ at the maximum.
m, preferably less than 200 μm, more preferably 100 μm
It is desirable that the thickness is m or less.

In the example of FIG. 4, an example in which a rigid true sphere having substantially the same radius R ₀ is used is shown, but the support in the present invention is not limited to this, and the object of the present invention is With the number and types managed within the range to be achieved, the radius
A plurality of kinds of rigid true spheres having different R ₀ may be used.

FIG. 5 shows an example in which a light-receiving layer 500 composed of a charge injection blocking layer 502, CGL503, CTL504, and a surface layer 505 is formed on a support 501 prepared by the above method. The surface layer 505 is a free surface
Has 506.

Charge Injection Blocking Layer The charge injection blocking layer is composed of Non-SiMo (H, X) as described above. The charge injection blocking layer in the present invention has a function of blocking the injection of charges into CGL from the support side when the surface of the photoreceptor layer is subjected to a charging treatment of one polarity and the other polarity. It has a so-called rectifying property, which does not exhibit such a function when subjected to a charging process. In order to impart such a function, the charge injection blocking layer contains a relatively large amount of a substance (M ₀ ) which controls one conductivity type and which controls conductivity.

The substance (M ₀ ) for controlling the conductivity is uniformly contained in the layer interface direction of the charge injection blocking layer, but its distribution concentration C (M ₀ ) is uniform in the layer thickness direction. Or it may be non-uniform. However, in any case, it is contained in the entire region of the charge injection blocking layer.

When the distribution concentration C (M ₀ ) is non-uniform, it is preferable that the distribution concentration C (M ₀ ) is contained so as to be distributed more on the support side.

The conductivity controlling substance (M ₀ ) contained in the charge injection blocking layer may have the same polarity as the conductivity controlling substance (M) contained in the CTL described later, and They may have different polarities, and may be the same substance or different substances.

However, the CT from the free surface side when subjected to charging treatment
In order to make the injection of charges into CGL into L and from the support side more effective, the conductivity controlling substances contained in the charge injection blocking layer and CTL have at least polarities different from each other. Is preferred.

These are appropriately determined in consideration of the purpose when the layer of the light-receiving layer is designed. Specific examples of the substance (M ₀ ) contained in the charge injection blocking layer that controls conductivity are the same as the substance (M) described below that controls conductivity.

6 to 10 show typical distribution states in the layer thickness direction of the substance (M ₀ ) controlling the conductivity when the charge injection blocking layer contains a non-uniform concentration in the layer thickness direction. An example is shown.

In the examples of FIGS. 6 to 10, the horizontal axis represents the distribution concentration C (M ₀ ) of the substance (M ₀ ), and the vertical axis represents the layer thickness t of the charge injection blocking layer, t
_B indicates the interface position on the support side, and t _T indicates the interface position on the side opposite to the support side. That is, the charge injection blocking layer is t _T from the t _B side.
Layer formation is performed toward the side.

FIG. 6 shows a first typical example of the state of distribution of the substance (M ₀ ) contained in the charge injection blocking layer in the layer thickness direction.

In the example shown in FIG. 6, from the interface position t _B side to the position of t ₄ , the distribution concentration C (M ₀ ) of the substance (M ₀ ) is contained while taking a constant value C ₁₂ from the position t ₄ The distribution concentration C (M ₀ ) is the interface position t
_It gradually decreases continuously from C ₁₃ until reaching _T. The distribution concentration C is C _{14 at the} interface position t _T.

In the example shown in FIG. 7, the substance contained (M ₀ ).
The distribution concentration C (M ₀ ) of C forms a distribution state in which it gradually decreases continuously from C ₁₅ from position t _B to position t _T and becomes C _{16 at} t _T.

In the example shown in FIG. 8, the distribution concentration C of the substance (M ₀ ).
(M ₀ ) has a constant value of C ₁₇ between the position t _B and the position t ₅ , and is C _{18 at the} position t _T. Between the position t ₅ and the position t _T , the distribution concentration C (M ₀ ) is linearly reduced from the position t ₅ to the position t _T.

In the example shown in FIG. 9, the distribution concentration C (M ₀ ) is at the position t
_{From B} to position t _6, the constant value of C ₁₉ is taken, and from position t ₆ to position
Up to t _T, the distribution is a linear function that decreases from C ₂₀ to C ₂₁ .

In the example shown in FIG. 10, the distribution concentration C (M ₀ ) is at the position t
The constant value of C ₂₂ is taken from _B to the position t _B.

In the present invention, when the charge injection blocking layer contains the substance (M ₀ ) controlling conductivity, in a distribution state in which a large amount is distributed on the support side, the maximum value of the distribution concentration C (M ₀ ) of the substance (M ₀ ) is preferable. Is preferably 50 atomic ppm or more, more preferably 80 atomic ppm or more, and optimally 100 atomic ppm or more so that a layered state can be formed.

In the present invention, the content of the substance (M ₀ ) 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
To 5 × 10 ⁴ atom ppm, more preferably 50 to 1 × 10 ⁴ atom ppm,
Optimally, 1 × 10 ^{2 to} 5 × 10 ³ atomic ppm is desirable.

The charge injection blocking layer, by containing carbon atoms and / or nitrogen atoms and / or oxygen atoms, mainly improves the adhesion between the support and the charge injection blocking layer and between the charge injection blocking layer and CGL. Adhesion is improved.

12 to 17 show the distribution of carbon atoms and / or oxygen atoms and / or nitrogen atoms (collectively referred to as “atoms (Z)”) contained in the charge injection blocking layer in the layer thickness direction. A typical example of a condition is shown.

In the examples of FIGS. 12 to 17, the horizontal axis represents the distribution concentration C _Z of atoms (Z), the vertical axis represents the layer thickness t of the charge injection blocking layer, t _B represents the interface position on the support side, and t _T Indicates the position of the interface on the side opposite to the support side. That is, the charge injection blocking layer is t _T from the t _B side.
Layer formation is performed toward.

FIG. 11 shows a first typical example of the distribution state of atoms (Z) contained in the charge injection blocking layer in the layer thickness direction.

11 is distributed concentration C from the position t ₇ the distribution concentration C _Z is contained while taking a constant value that is C ₂₃ position to the atom of t ₇ from the interface position t _B (Z) in the example shown in FIG interface The position is gradually and continuously reduced from C ₂₄ until reaching t _T. The distribution concentration C is C _{25 at the} interface position t _T.

In the example shown in FIG. 12, the contained atom (Z)
The distribution concentration C _Z of C forms a distribution state in which it gradually decreases continuously from C ₂₆ from position t _B to position t _T and becomes C _{27 at} position t _T.

In the case of FIG. 13, from the position t _B to the position t ₈ is an atom (Z).
The distribution concentration C _Z of C has a constant value of C ₂₈ , is gradually and continuously reduced between the positions t ₈ and t _T, and is substantially zero at the position t _T.

In the case of FIG. 14, the distribution concentration C _Z of the atom (Z) is gradually decreased from C ₃₀ continuously from the position t _B to the position t _T.
It is substantially zero at the position t _T.

In the example shown in FIG. 15, the distribution concentration of atoms (Z)
C _Z has a constant value of C ₃₁ between the position t _B and the position t ₉ , and is C _{32 at the} position t _T. Between the position t ₉ and the position t _T , the distribution concentration C _Z is a linear function from the position t ₉ to the position t _T.
Has been reduced to.

In the example shown in FIG. 16, the distribution concentration of atoms (Z)
C _Z takes a constant value of C ₃₃ from position T _B to position t ₁₀ ,
From t ₁₀ to the position t _T , the distribution state is linearly decreasing from C ₃₄ to C ₃₅ .

In the example shown in FIG. 17, the distribution concentration of atoms (Z)
C _Z has a constant value of C ₃₆ from position t _B to position t _T.

In the present invention, when the charge injection blocking layer contains atoms (Z) in a distribution state in which a large number of atoms (Z) are distributed on the support side, the maximum value of the distribution concentration C _Z of atoms (Z) is preferably 500 atomic ppm or more, and more preferably 800 atom ppm or more, optimally 1000 atom pp
It is desirable that the layers are formed so that a distribution state of m or more can be obtained.

In the present invention, the content of the atom (Z) 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 0.
The content is preferably 001 to 50 atomic%, more preferably 0.002 to 40 atomic%, and most preferably 0.003 to 30 atomic%.

Hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer in the present invention can compensate for dangling bonds existing in Non-SiMo (H, X) and improve the layer quality.

The content of hydrogen atom or halogen atom or the sum of hydrogen atom and halogen atom is preferably 1 to 50 atom%, more preferably 5 to 40 atom%, and most preferably 10 to 30 atom%.

In the present invention, the thickness of the charge injection blocking layer is preferably 0.01 to 10 .mu., More preferably 0.05 to 8 .mu., Most preferably 0.1 to 5 .mu., From the viewpoint of obtaining desired electrophotographic characteristics and economical effects. It is desirable to be done.

The charge injection blocking layer is formed by a vacuum deposition film forming method similar to CGL and CTL described later, by appropriately setting numerical conditions of film forming parameters so that desired characteristics can be obtained.

CGL The CGL in the present invention is composed of Non-Si (H, X) and has desired photoconductive characteristics, particularly charge generation characteristics.

In the CGL in the present invention, as in the case of CTL described later, any of the substance (M), the carbon atom (C), the nitrogen atom (N), and the oxygen atom (O) that control conductivity are substantially contained. Not contained in.

Further, the hydrogen atom and / or halogen atom contained in CGL in the present invention compensates for dangling bonds of silicon atom and is effective in improving the layer quality, particularly in improving the photoconductive property.

The content of hydrogen atom or halogen atom or the sum of hydrogen atom and halogen atom in CGL is preferably 1 to 40 atom%,
It is more preferably 5 to 30 atom%, and most preferably 10 to 20 atom%.

In the present invention, the layer thickness of CGL is that the desired electrophotographic characteristics can be obtained, and the economical effect, especially the absorption coefficient of light of the light source used in the electrophotographic image forming apparatus so as to obtain sufficient charge generation ability. It is appropriately determined according to the desire, and is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm, and most preferably 1 to 10 μm.

In the present invention, to form a CGL composed of Non-Si (H, X), for example, a glow discharge method (low frequency CVD, high frequency CVD
AC discharge CVD such as microwave CVD, or DC discharge CVD), ECR-CVD method, sputtering method, vacuum deposition method, ion plating method, optical CVD method, thermal CVD method, and various other thin film deposition methods. can do.

In addition to these, the active species (A) generated by decomposing the raw material gas for forming the non-single crystal material and the active species (A)
And the active species (B) generated from the film-forming chemical substance that chemically interacts with each other are separately introduced into the film formation space for forming the deposited film and chemically reacted with each other. A method for forming a crystalline material (hereinafter abbreviated as “HRCVD method”), a source gas for forming a non-single-crystal material, and a halogen-based oxidant gas having a property of oxidizing the source gas are separately deposited. Examples thereof include a thin film deposition method such as a method of introducing a non-single crystal material into a film formation space for forming a film and chemically reacting these materials (hereinafter, abbreviated as “FOCVD method”). These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level of capital investment, manufacturing scale, and desired characteristics of the light receiving member to be produced. Since it is relatively easy to control the conditions for manufacturing a photoreceptive member for photography and it is possible to easily introduce halogen atoms and hydrogen atoms together with silicon atoms, the glow discharge method, the sputtering method, etc. Method, ion plating method, ECR-CVD method, HRCVD method, FOCVD method are suitable. In some cases, these methods may be used together in the same device system. For example, non-Si by glow discharge method
In order to form a CGL composed of (H, X), basically, a raw material gas for supplying silicon atoms (Si) and a raw material gas for introducing hydrogen atoms (H) or / and a halogen are available. A raw material gas for introducing atoms (X) is introduced into a deposition chamber in which the inside pressure can be reduced under a desired gas pressure state to cause glow discharge in the deposition chamber, and a predetermined support installed in a predetermined position in advance. A layer made of Non-Si (H, X) may be formed on the body surface. Further, when forming by the sputtering method, for example, using 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, if necessary. , Hydrogen atom (H)
Alternatively, and / or a gas for introducing a halogen atom (X) is introduced into a deposition chamber for sputtering and a plasma atmosphere of a desired gas is formed.

In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon is housed in an evaporation board as an evaporation source, and this evaporation source is heated and evaporated by a resistance heating method, an electron beam method (EB method), or the like to fly. Other than passing the evaporate through the desired gas plasma atmosphere,
It can be carried out in the same manner as in the case of the sputtering method. CGL composed of Non-Si (H, X) by HRCVD method
In order to form the gas, for example, a raw material gas for supplying Si is introduced into the activation space provided in the preceding stage in the deposition chamber where the inside pressure can be reduced under a desired gas pressure state, and a glow discharge is generated in the activation space. The active species (A) is generated by heating or overheating, and the raw material gas for introducing the hydrogen atom (H) and / or the raw material gas for introducing the halogen atom (X) is similarly activated in another activation space. To generate active species (B), and the active species (A) and the active species (B) are separately introduced into the deposition chamber, and on the surface of a predetermined support previously installed at a predetermined position. A layer made of Non-Si (H, X) may be formed on. CG composed of Non-Si (H, X) by FOCVD method
In order to form L, for example, a source gas for supplying Si is introduced into a deposition chamber in which the inside pressure can be reduced under a desired gas pressure state, and a halogen (X) gas is supplied into the deposition chamber separately from the source gas. It is sufficient to introduce under pressure and chemically react these gases in the deposition chamber to form a layer made of Non-Si (H, X) on the surface of a predetermined support which is installed in a predetermined position in advance.

Examples of the substance that can be used as the raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H _{10 in} a gas state or a gasifiable silicon hydride (silane). Are used effectively, and in particular, SiH ₄ , Si ₂ H in terms of ease of handling during layer formation work, good Si supply efficiency, etc.
₆ is mentioned as a preferable one.

As a raw material gas for introducing a halogen atom used in the present invention, many halogen compounds can be mentioned, for example, halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives and the like in gas state or gas. Preferred examples thereof include halogen compounds that can be converted.

Further, a silicon hydride compound containing a halogen atom capable of gasification or gasification, which has silicon atoms and halogen atoms as constituent elements, can be mentioned as an effective one in the present invention.

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 , IF ₇ and 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,
Silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ can be mentioned as preferable ones.

In the case of forming the characteristic electrophotographic light-receiving member of the present invention by the glow discharge method using a silicon compound containing such a halogen atom, a hydrogenated silicon gas as a source gas capable of supplying Si is used. It is possible to form a CGL composed of Non-Si (H, X) containing a halogen atom on a desired support without using it.

According to the glow discharge method, when producing CGL containing a halogen atom, basically, for example, in a deposition chamber for forming CGL by adjusting the silicon halide, which is the raw material gas for Si supply, to a predetermined gas flow rate. Introduced, by generating a glow discharge to form a plasma atmosphere of these gases, it is possible to form CGL on the desired support,
In order to make it easier to control the introduction ratio of hydrogen atoms, hydrogen gas or a gas of a silicon compound containing hydrogen atoms may be mixed in a desired amount with these gases to form a layer.

Further, each of the soots may be used not only as a single kind but also as a mixture of plural kinds at a predetermined mixing ratio.

Sputtering method, Ion plating method, HRCVD method, F
In any case of the OCVD method, in order to introduce a halogen atom into the layer to be formed, a gas of the above halogen compound or a silicon compound containing the above halogen atom is introduced into the deposition chamber, and It is only necessary to form a plasma atmosphere.

Further, in the case of introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or the gases of the above-mentioned silanes may be introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gases. Good.

In the present invention, the halogen compound described above as a raw material gas for introducing a halogen atom, or a silicon compound containing a halogen is used as an effective one, in addition, HF, HCl, HBr, such as HI Hydrogen halide, SiH
₂ F ₂ , SiH ₂ l ₂ , SIH ₂ Cl ₂ , SiHCl ₂ , SiH ₂ Br ₂ , SiHBr _{2 and} other halogen-substituted silicon hydrides, etc. Gas state or gasifiable substances are also effective starting points for CGL formation It can be mentioned as a substance. Among these substances, the halides containing hydrogen atoms are introduced because, at the same time as the introduction of halogen atoms into the layer during the formation of CGL, hydrogen atoms that are extremely effective in controlling the electrical or photoelectric properties are also introduced. In the invention, it is used as a preferable raw material for introducing halogen.

In order to introduce a hydrogen atom structurally into CGL, in addition to the above, H
₂ or by causing silicon hydrides such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ and silicon or a silicon compound for supplying Si to coexist in the deposition chamber to cause discharge. It can be carried out.

To control the amount of hydrogen atoms (H) or / and halogen atoms (X) contained in CGL, for example, to include the support temperature or / and hydrogen atoms (H), or halogen atoms (X). It suffices to control the amount of the starting material used for the above to be introduced into the deposition apparatus system, the discharge power, and the like.

CTL The CTL 105 of the present invention contains, as constituent elements, at least one of a silicon atom, a carbon atom, a nitrogen atom and an oxygen atom, and a substance (M) that controls conductivity.
It is composed of n-Si (H, X) (hereinafter abbreviated as “Non-SiM (C, N, O) (H, X)”) and has charge transport characteristics satisfying the required electrophotographic characteristics. The carbon atoms, nitrogen atoms or oxygen atoms contained in the CTL105 may be contained in the CTL105 in a uniformly distributed state, or may be contained in an unevenly distributed state in the layer thickness direction. It may be contained so that there may be a part. Material that controls conductivity (M)
Is contained in a state of being distributed nonuniformly in the layer thickness direction. That is, the substance (M) is contained in a non-uniform distribution state in which the concentration of the substance (M) increases or decreases from the support side in the layer thickness direction. In any case, when the substance (M) for controlling conductivity, carbon atom, nitrogen atom and oxygen atom is contained, it is contained in the entire layer region of CTL103.
The substance (M) is contained in the CTL 105 such that the concentration of the substance (M) that controls the conductivity in the layer thickness direction of the CTL 105 becomes non-uniform in at least a part of the layer region of the CTL 105.

The distribution concentration of carbon atoms, nitrogen atoms and oxygen atoms in the CTL 105 in the layer thickness direction may be uniform, or is non-uniform in at least a part of the layer region of the CTL 105 like the substance (M) that controls conductivity. May be contained so that

18 to 33 show typical examples of the distribution state of the substance (M) contained in CTL in the layer thickness direction for controlling the conductivity. In the following description, the substance (M),
Carbon atom (C), nitrogen atom (N) and oxygen atom (O)
Are collectively referred to as “atom (Y)”.

In Figures 18 to 33, the horizontal axis represents the contained atom (Y).
Distribution concentration C, the vertical axis represents the layer thickness of the CTL, t _B is the position of the end surface of the CTL on the support side, and t _T is the CTL on the side opposite to the support side.
The position of the end face of is shown. That is, the layer of CGL containing atoms (Y) is formed from the t _B side toward the t _T side.

FIG. 18 shows a first typical example of the distribution state of atoms (Y) contained in CTL in the layer thickness direction.

In the example shown in FIG. 18, from the interface position t _B to the position t ₁₆ , a layer region where atoms (Y) are formed while the distribution concentration C of atoms (Y) has a constant value C _57. It is contained in (Y) and gradually and continuously decreases from the distribution concentration value C ₅₈ from the position t ₁₆ to the interface position t _T. At the interface position t _T , the distribution concentration C of atoms (Y) has a value C ₅₉ .

In the example shown in FIG. 19, the contained atom (Y)
Distribution density C of the distribution density value from position t _B to position t _T
A distribution state is formed in which the distribution concentration value C ₆₁ gradually decreases continuously from C ₆₀ and reaches the distribution concentration value C ₆₁ at the position t _T.

In the case of FIG. 20, from the position t _B to the position t ₁₇ , the distribution concentration C of the atom (Y) is a constant value with the distribution concentration value C ₆₂ ,
The distribution concentration C is gradually and continuously reduced between the position t ₁₇ and the position t _T, and the distribution concentration C is substantially zero at the position t _T (where substantially zero is less than the detection limit amount). The same applies to the meaning of "substantially zero".

In the case of FIG. 21, the distribution concentration C of the atoms (Y) is reduced continuously and gradually from the density value C ₆₄ up to the position t _T to the position t _B, is substantially zero at the position t _T ing.

In the example shown in FIG. 22, the distribution concentration C of atoms (Y)
Is a constant value with the distribution density value C ₆₅ between the position t _B and the position t ₁₈ , and is a distribution density value C _{66 at} the position t _T.
Between the position t ₁₈ and the position t _T , the distribution concentration C is linearly reduced from the position t ₁₈ to the position t _T.

In the example shown in FIG. 23, the distribution concentration C of atoms (Y) decreases linearly from the position t _B to the position t _{T so} that the distribution concentration value C ₄₇ becomes substantially zero. There is.

In the example shown in FIG. 24, the contained atom (Y)
Distribution concentration C forms a gradual continuous decrease in distribution, such as a value C ₆₉ in the position t _T from the value C ₆₈ up to the position t _T to the position t _B.

In the example shown in FIG. 25, the distribution concentration C of the atom (Y) takes a constant value C ₇₀ from the position t _B to the position t _19, and the value C ₇₁ from the position t ₁₉ to the position t _T. It is assumed that the distribution state decreases linearly up to the value C ₇₂ .

In the example shown in FIG. 26, the distribution concentration C of the atom (Y) gradually and continuously increases from the position t _B to the position t ₂₀ from the value C ₇₅ to C ₇₄ , and from the position t ₂₀ to the position C _73. Takes a constant value of
The distribution state is formed so as to reach the position t _T.

In the example shown in FIG. 27, the distribution concentration C of the atoms (Y) forms a distribution state such that gradually increases continuously from a value C ₇₇ up to the position t _T to the position t _B to C ₇₆ ing.

In the example shown in FIG. 28, the distribution concentration C of the atoms (Y) gradually increases continuously from substantially zero up to the position t ₂₁ from the position t _B to C _79, from the position t ₂₁ is A distribution state is formed in which a constant value of C ₇₈ is taken and the position reaches t _T.

In the example shown in FIG. 29, the distribution concentration C of the atom (Y) forms a distribution state in which the distribution concentration C gradually increases continuously from zero to C ₈₀ from the position t _B to the position t _T. is doing.

In the example shown in FIG. 30, the distribution concentration C of atoms (Y) increases linearly from C ₈₂ to C ₈₁ from position t _B to position t _22, and from position t ₁₇ to position C _81. Has a constant value and reaches a position t _T to form a distribution state.

In the example shown in FIG. 31, the distribution concentration C of the atom (Y) forms a distribution state in which the distribution concentration C increases linearly from zero to C ₈₃ from the position t _B to the position t _T. ing.

In the example shown in FIG. 32, the distribution concentration C of atoms (Y) forms a distribution state in which it gradually increases continuously from C ₈₅ to C ₈₄ from the position t _B to the position t _T. There is.

In the example shown in FIG. 33, atomic distribution concentration C (Y) is increased from C ₈₈ up to the position t ₂₃ from the position t _B C ₈₇ to a linear function manner, the C ₈₆ is the position t ₂₃ It takes a constant value and forms a distribution state that reaches the position t _T.

34 to 43, the layer thickness direction of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in CTL (hereinafter collectively referred to as "atoms (Y)") A typical example of the distribution of is shown.

In Figures 34 to 43, the horizontal axis represents the contained atom (Y).
Distribution concentration C, the vertical axis represents the layer thickness of the CTL, t _B is the position of the end surface of the CTL on the support side, and t _T is the CTL on the side opposite to the support side.
The position of the end face of is shown. That is, the CTL containing the atom (Y) is layered from the t _B side toward the t _T side.

FIG. 34 shows a first typical example of the distribution state of atoms (Y) contained in CTL in the layer thickness direction.

In the example shown in FIG. 34, the interface position where CGL and CTL contact
From t _B to the position of t ₂₄ , the distribution concentration C of the atom (Y) is C _89.
The atom (Y) is contained in the CTL to form a constant value, and is gradually and continuously reduced from the concentration value C ₉₀ from the position t ₂₄ to the interface position t _T. At the interface position t _T , the distribution concentration C of atoms (Y) has a value C ₉₁ .

In the example shown in FIG. 35, the contained atom (Y)
Distribution concentration C of the distribution concentration C from position t _B to position t _T
A distribution state is formed in which the distribution concentration value C ₉₃ gradually decreases continuously from ₉₂ and becomes the distribution concentration value C ₉₃ at the position t _T.

In the case of FIG. 36, from the position t _B to the position t ₂₅ , the distribution concentration C of the atom (Y) has a constant value of the concentration C _94, and the position t ₂₅
And between the position t _T, gradually reduced continuously from C _95, at the position t _T, the distribution concentration C is substantially zero (where substantially less than the detection limit amount is zero Is the case).

In the case of Figure 37, the distribution concentration C of the atoms (Y) is up to the position t _T to the position t _B, it is reduced continuously and gradually from the concentration C _96, is substantially zero at the position t _T ing.

In the example shown in FIG. 38, the distribution concentration C of atoms (Y) is
Is a constant value with the concentration C ₉₇ between the position t _B and the position t ₂₆ , and is a concentration C _{98 at the} position t _T. Between the position t ₂₆ and the position t _T , the distribution density C is linearly reduced from the position t ₂₆ to the position t _T.

In the example shown in FIG. 39, from the position t _B to the position t _T , the distribution concentration C of the atom (Y) is linearly decreased from the concentration C ₉₉ to substantially zero.

In the example shown in FIG. 40, the contained atom (Y)
The distribution density C of C gradually decreases continuously from C ₁₀₀ from the position t _B to the position t _T , and forms a distribution state of C ₁₀₁ at the position t _T.

In the example shown in FIG. 41, the distribution concentration C of the atom (Y) takes a constant value of C ₁₀₂ from the position t _B to the position t _27, and from the C ₁₀₃ to C ₁₀₄ from the position t ₂₇ to the position t _T. It is assumed that the distribution state decreases linearly until.

In the example shown in FIG. 42, the distribution concentration C of atoms (Y) has a constant value of C ₁₀₅ from the position t _B to the position t.

34 example shown in FIG. To FIG. 41 are all but towards the t _B side of the t _T side is an example distribution concentration C is large atomic (Y) to reverse the t _T side and t _B side at all The distribution concentration C of atoms (Y) may be higher on the t _T side than on the t _B side.
In the example shown in FIG. 43, in FIG. 44, when the t _T side and the t _B side are reversed, the distribution concentration C of atoms (Y) gradually increases from C ₁₀₈ from the interface position t _B to the position t _28. Continuously increases to C ₁₀₇ at position t ₂₈ and C from position t ₂₈ to interface position t _{T.
It is} a constant value of ₁₀₆ .

Examples of the above-mentioned substance (M) that controls conductivity include so-called impurities in the field of semiconductors, and in the present invention, an atom belonging to Group III of the periodic table that gives p-type conductivity (hereinafter referred to as “group Group III atom ") or n
An atom belonging to Group V of the periodic table (hereinafter, referred to as “Group V atom”) that gives the type conduction characteristic is used. Specific examples of the group III atom include B (boron), Al (aluminum), and Ga.
There are (gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferable. Specific examples of the Group V atom include P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), and the like, with P and As being particularly preferable.

In the present invention, the effect of mainly controlling the conductivity type and / or the conductivity by containing a group III atom or a group V atom as the substance (M) for controlling conductivity in the entire layer region of CTL105, and / or Alternatively, the effect of improving the charge injection property between CGL and CTL can be obtained, but the content thereof is set to a relatively small amount. The content of the substance (M) is preferably 1 × 10 ⁻³ to 1 × 10 ³ atom ppm, more preferably 5 × 10 ⁻³ to 1 × 10 ² atom ppm, most preferably 1 × 10 ^−2. It is desirable to set the concentration to 50 atom ppm.

Further, the whole layer region of the CTL of the present invention contains carbon atoms and / or oxygen atoms and / or nitrogen atoms, and is mainly used for high dark resistance and control of spectral sensitivity, and for CGL and CTL.
It is possible to improve the adhesion between and. Carbon atom,
The content of oxygen atoms or nitrogen atoms, or when at least two of them are contained, the total content thereof is preferably 1 × 10 ^{−3 to} 5 × 10 atom%, more preferably Is 5 × 10 ^-2 to 4 × 10 atomic%, optimally 1 × 10 ^-1 to
It is desirable that the content be 3 × 10 atomic%.

Further, the hydrogen atom contained in the CTL of the present invention or /
And the halogen atom can compensate the dangling bond of the silicon atom and improve the layer quality.

The content of hydrogen atom or halogen atom or the sum of hydrogen atom and halogen atom contained in CTL is preferably 1 to 70 atom%, more preferably 5 to 50 atom%, most preferably 10 atom%.
It is desirable to set it to -30 atom%.

In the present invention, the layer thickness of CTL is preferably 5 to 50 μ, more preferably 10 to 40 μ, and most preferably 20 to 30 from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable that it be μ.

In the present invention, the layer thickness of CGL is preferably thinner than the layer thickness of CTL.

In the present invention, in order to introduce an atom (Y) into CTL, C
It may be used together with the starting material for forming TL, and the amount thereof may be controlled and contained in the formed layer.

To form a CTL by the glow discharge method, HRCVD method, or FOCVD method, the starting material for introducing nitrogen atoms must be at least a gaseous substance containing nitrogen atoms as constituent atoms or a gasified substance that can be gasified. Most of the can be used.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing nitrogen atoms (N) as constituent atoms, and optionally hydrogen atoms (H) or halogen atoms (X) as constituent atoms. A raw material gas 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 nitrogen atoms (N) and hydrogen atoms (H) as constituent atoms. Is also mixed at a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms and three atoms of silicon atoms (Si), nitrogen atoms (N) and hydrogen atoms (H) are mixed. It is possible to mix and use a raw material gas that is a constituent atom.

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 nitrogen atoms (N) as constituent atoms.

A starting material effectively used as a raw material gas for introducing a nitrogen atom (N) includes N as a constituent atom, or N and H as a constituent atom, for example, nitrogen (N ₂ ),
Gaseous or gasifiable nitrogen such as ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen such as nitrides and azides A compound can be mentioned. In addition to this, in addition to the introduction of nitrogen atoms (N), the introduction of halogen atoms (X) is also possible, so nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F)
₄ N ₂ ) and other halogenated nitrogen compounds.

In order to form CTL by glow discharge method, HRCVD method, FOCVD method, as a starting material for introducing carbon atoms, a gaseous substance containing at least carbon atoms as constituent atoms or a gasified substance which can be gasified is used. Most of the can be used.

For example, a source gas containing silicon atoms (Si) as constituent atoms, a source gas containing nitrogen atoms (C) as constituent atoms, and, if necessary, hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. Or a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing carbon atoms (C) and hydrogen atoms (H). Is also mixed at a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms, and three atoms of silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H). It is possible to mix and use a raw material gas that is a constituent atom.

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 carbon atom (C) as constituent atoms.

Starting materials that are effectively used as raw material gases for introducing carbon atoms (C) include C and H as constituent atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms and 2 to 2 carbon atoms.
4, 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 such as acetylene (C ₂ H ₂ ), methylacetylene (C
₃ H ₄ ), butyne (C ₄ H ₆ ) and the like. As the source gas containing Si, C and H as constituent atoms, Si (CH ₃ ) ₄ and Si (C ₂ H
₅ ) There may be mentioned alkylsilicides such as ₄ .

In addition to this, CF ₄ , CCl ₄ , CH ₃ CF can be introduced in addition to the introduction of halogen atoms (X) in addition to the introduction of carbon atoms (C).
Examples thereof include halogenated carbon gas such as ₃ .

In the case of forming a CTL by glow discharge method, HRCVD method, FOCVD method, as a starting material for introducing oxygen atoms, at least a gaseous substance containing oxygen atoms as constituent atoms or a gasified substance capable of being gasified is selected. Most can be used.

For example, a source gas containing silicon atoms (Si) as constituent atoms, a source gas containing oxygen atoms (O) as constituent atoms, and optionally hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. 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 mixed with each other at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) as constituent atoms, and three gases of silicon atoms (Si), oxygen atoms (O) and hydrogen atoms (H). It is possible to mix and use a raw material gas that is a constituent atom.

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

Starting materials that are effectively used as raw material gases for introducing oxygen atoms (O) include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), and nitrogen dioxide (NO ₂ ). , Nitric oxide (N ₂ O), Nitric oxide (N ₂ O ₃ ), Nitric oxide (N ₂ O ₄ ), Nitric oxide (N ₂ O ₅ ), Nitric oxide (NO
₂ ), silicon atoms (Si), oxygen atoms (O), hydrogen atoms (H) and constituent atoms, such as disiloxane (H ₃ SiOS
Examples thereof include lower siloxanes such as iH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ).

To form a CTL by the sputtering method, a monocrystalline or polycrystalline Si wafer or a Si ₃ N ₄ wafer or a wafer containing Si and Si ₃ N ₄ mixed and / or SiO is formed at the time of forming the CTL. ₂ wafers or Si
And / or SiO ₂ mixed and contained
Alternatively, a SiC wafer or a wafer containing a mixture of Si and SiC as a target may be used as a target and sputtered in various gas atmospheres.

For example, in order to contain nitrogen atoms, if a Si wafer is used as a target, the raw material gas for introducing nitrogen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluting gas as necessary. The Si wafer may be sputtered by introducing it into a deposition chamber for sputtering and forming a gas plasma of these gases.

Separately, Si and Si ₃ N ₄ are separate targets,
Alternatively, by using a single target in which Si and Si ₃ N ₄ are mixed, at least a hydrogen atom (H) or / and a halogen atom (X) are constituted in the atmosphere of a diluting gas as a gas for sputtering. Is sputtered in a gas atmosphere containing as.

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

In the present invention, when the CTL is formed, the distribution concentration C (Y) of atoms (Y) contained in the layer is changed in the layer thickness direction to obtain a desired distribution state (depth profile) in the layer thickness direction. In order to form the layer having the above, in the case of the glow discharge method, the HRCVD method, and the FDCVD method, the starting material gas for introducing the atom (Y) whose distribution concentration C (Y) should be changed, and the gas flow rate thereof are desired. It is made by introducing it into the deposition chamber while appropriately changing it according to the change rate curve of.

For example, the operation of appropriately changing the opening of a predetermined needle valve provided in the middle of the gas flow path system may be performed by some commonly used method such as manual operation or an external drive motor.

When forming by the sputtering method, the distribution concentration C (Y) of the atom (Y) in the layer thickness direction is changed in the layer thickness direction,
Desired distribution of atoms (Y) in the layer thickness direction (depth profile
To form e), first, as in the case of the glow discharge method, the starting material for introducing the atom (Y) is used in a gas state, and the gas for introducing the gas into the deposition chamber is used. This is done by appropriately changing the flow rate as desired.

Second, a target for sputtering, such as Si
If you are using the mixed Tagetsuto the top of the Si ₃ N ₄ and a mixing ratio of Si and Si ₃ N _4, in the layer thickness direction of Tagetsuto, made by allowed to advance changed.

When SiC or SiO ₂ is used, it may be performed in the same manner as Si ₃ N ₄ .

In CTL, a substance (M) that controls conduction characteristics, for example, I-th
To introduce a group II atom or a group V atom structurally,
At the time of layer formation, a starting material for introducing a group III atom or a starting material for introducing a group V may be introduced in a gaseous state together with another starting material for forming CGL into the deposition chamber. As a starting material for introducing such a Group III atom, it is desirable to employ a gaseous material at room temperature and atmospheric pressure or a material that can be easily gasified under at least the layer forming conditions. As a starting material for introducing such a group III atom, specifically, for introducing a boron atom, B ₂ H ₆ , B ₄ H
Examples thereof include boron hydrides such as ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ and B ₆ H ₁₄ , and boron halides such as BF ₃ , BCl ₂ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₂ , TlCl _{3 and the} like can be mentioned.

As a starting material for introducing a group V atom, PH ₃ , P ₂ H is effectively used in the present invention for introducing a phosphorus atom.
Phosphorus hydride such as ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , P
Examples include phosphorus halides such as Br ₅ and PI ₃ . Besides this, As
_{H 3, AsF 3, AsCl 3} , AsBr 3, AsF 5, SbH 3, SbF 3, SbF 5, Sb
Cl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group V atom.

Non-S CGL, CTL having characteristics that can achieve the object of the present invention
A-Si containing a hydrogen atom and / or a halogen atom as i (H, X) (hereinafter referred to as "A-Si (H, X)")
In order to select and configure the above, it is necessary to appropriately set the temperature and gas pressure of the support as desired.

The support temperature (Ts) is appropriately selected in accordance with the layer design, but is usually 50 ° C to 400 ° C, preferably 100 ° C to 400 ° C.
A temperature of 300 ° C is desirable.

Similarly, the gas pressure in the deposition chamber is also appropriately selected in accordance with the layer design, but in the normal case, it is 1 × 10 ^{−4 to} 10 Torr, preferably 1 × 10 ^{−3 to 3} Torr, optimally 1 × 10 ^−2. ~ 1 Torr is desirable.

In the present invention, the above-mentioned ranges are mentioned as the desirable numerical ranges of the substrate temperature and the gas pressure for producing and printing the respective layers, but these layer producing factors are not usually independently determined separately. In order to form each layer having a desired characteristic, it is desirable to determine the optimum value of each layer forming factor based on mutual and organic relation.

Polycrystalline silicon containing hydrogen atoms and / or halogen atoms (hereinafter referred to as “poly-Si (H, X)”) is selected as Non-Si (H, X) constituting CGL, CTL. In the case of constituting, there are various methods for forming the layer, and for example, the following method can be mentioned.

One method is to raise the support temperature to a high temperature, specifically 400
This is a method in which the temperature is set to ˜600 ° C. and a film is deposited on the support by plasma CVD.

Another method is to first form an alumophore-like film on the surface of the support, that is, form a film by plasma CVD on the support having a support temperature of about 250 ° C., and subject the amorphous-like film to an annealing treatment. This is a method of making poly. The annealing treatment was carried out with the support at 400-6
It is carried out by heating to 00 ° C. for about 5 to 30 minutes, or by irradiating with laser light for about 5 to 30 minutes.

Surface Layer The surface layer in the present invention is a non-Si (C containing at least one of a silicon atom, a carbon atom, a nitrogen atom and an oxygen atom, and at least one of a hydrogen atom and a halogen atom as constituent elements. , N, O) (H, X). The surface layer contains no or substantially no substance (M) that controls conductivity as contained in CTL.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be uniformly distributed in the layer, or they may be uniformly distributed in the layer thickness direction but are nonuniform. There may be a portion that is contained in a distributed state.

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

FIGS. 44 to 53 show the carbon atoms and / or nitrogen atoms and / or oxygen atoms (hereinafter collectively referred to as “atoms (Y)”) contained in the surface layer in the layer thickness direction. A typical example of distribution is shown.

In Figures 44 to 53, the horizontal axis represents the contained atom (Y).
Of the distribution concentration C, the vertical axis represents the layer thickness of the surface layer, t _B represents the position of the end surface of the surface layer on the support side, and t _T represents the position of the end surface of the surface layer on the side opposite to the support side. That is, the surface layer containing atoms (Y) is formed from the t _B side toward the t _T side.

FIG. 44 shows a first typical example of the distribution state of atoms (Y) contained in the surface layer in the layer thickness direction.

In the example shown in FIG. 44, the distribution concentration C of atoms (Y) gradually and continuously increases from C ₁₁₁ to C ₁₁₀ from the position t _B to the position t _29, and from the position t ₂₉ to C _109. A distribution state is formed such that a constant value of is taken to reach the position t _T.

In the example shown in FIG. 45, the distribution concentration C of the atom (Y) forms a distribution state in which it gradually increases continuously from C ₁₁₃ to C ₁₁₂ from the position t _B to the position t _T. There is.

In the example shown in FIG. 46, the distribution concentration C of the atom (Y) gradually increases substantially continuously from zero to C ₁₁₅ from the position t _B to t _30, and the distribution concentration C of C from the position t ₃₀ A distribution state is formed such that a constant value of ₁₁₄ is taken and the position reaches the position t _T.

In the example shown in FIG. 47, the distribution concentration C of atoms (Y) forms a distribution state in which the distribution concentration C of the atom (Y) gradually increases substantially continuously from zero to C ₁₁₆ from the position t _B to the position t _T. is doing.

In the example shown in FIG. 48, the distribution concentration C of the atom (Y) increases linearly from C ₁₁₈ to C ₁₁₇ from position t _B to position t _T, and from the position t ₃₁ to C ₁₁₇ . The distribution is formed such that it takes a constant value and reaches the position t _T.

In the example shown in FIG. 49, the distribution concentration C of the atom (Y) forms a distribution state in which it increases linearly from zero to C ₁₁₉ from the position t _B to the position t _T. ing.

In the example shown in FIG. 50, the distribution concentration C of atoms (Y) forms a distribution state in which it gradually increases continuously from C ₁₂₅ to C ₁₂₀ from position t _B to position t _T. There is.

In the example shown in FIG. 51, the distribution concentration C of atoms (Y)
Increases linearly from C ₁₂₄ to C ₁₂₃ from the position t _B to the position t ₃₂ , and takes a constant value of C ₁₂₂ from the position t ₃₂ and takes the position t.
_It has a distribution that reaches _T.

In the example shown in FIG. 52, the distribution concentration C of atoms (Y) takes a constant value of C ₁₂₅ from the position t _B to the position t _T.

In the example shown in FIG. 53, the distribution concentration C of atoms (Y) takes a constant value of C ₁₂₈ from the position t _B to t _33, and a constant value of C ₁₂₇ from the position t ₃₃ to t _34. Take position t ₃₄
Rather, a distribution state is formed in which a constant value of C ₁₂₆ is taken and the position reaches t _T.

The carbon atoms and / or nitrogen or / and oxygen atoms contained in the entire surface layer region of the present invention mainly exert effects such as high dark resistance and high hardness. The content of atoms (Y) contained in the surface layer is preferably 1 × 10 ^{−3 to} 90 atom%, more preferably 1 × 10 ^{−1 to} 85 atom%, and most preferably 10 to
It is preferably set to 80 atom%.

In addition, the hydrogen atom and / or the halogen atom contained in the surface layer in the present invention compensates the dangling bonds present in the Non-Si (C, N, O) (H, X) and improves the film quality. Play.

The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the surface layer is preferably 1 to 70 atom%, more preferably 5 to 50 atom%, most preferably 10 to 30 atom%.
Is.

In the present invention, the thickness of the surface layer is preferably from the viewpoint of obtaining desired electrophotographic characteristics, and economical effects.
0.003 to 30μ, more preferably 0.01 to 20μ, optimally 0.1
It is desirable to be set to ~ 10μ.

In the present invention, in order to form the surface layer composed of Non-Si (C, N, O) (H, X), a vacuum deposition method similar to the above-mentioned method of forming CGL is adopted.

When forming a surface layer having properties capable of achieving the object of the present invention, the temperature and gas pressure of the support 101 are important factors that influence the properties of each of the layers.

The support temperature is appropriately selected as an optimum range, but preferably
The temperature is preferably 50 to 400 ° C, and more preferably 100 to 300 ° C.

The gas pressure in the deposition chamber is also selected as appropriate, but is preferably 1 × 10 ^{-4 to} 10 Torr, more preferably 1 × 10 ^{-3 to 3} Torr.
rr, optimally 1 × 10 ^{-2 to} 1 Torr.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the substrate temperature and the gas pressure for forming the surface layer, but these layer forming factors are not usually independently determined separately. It is desirable to determine the optimum value for each layer-forming factor on the basis of mutual and organic relationships to form a surface layer having desired characteristics.

The surface layer is composed of a material whose main body is Non-Si (C, N, O) (H, X). Among them, polycrystalline Si (C, N, O) (H, X) is used.
There are various methods for forming a layer composed of (hereinafter referred to as “poly-Si (C, N, O) (H, X)”), and for example, the following method can be given.

One of the methods is to raise the substrate temperature to a high temperature, specifically 400 to 6
This is a method in which the temperature is set to 00 ° C. and a film is deposited on the substrate by a plasma CVD method.

In another method, an amorphous film is first formed on the surface of the substrate, that is, a film is formed by plasma CVD on the substrate whose substrate temperature is, for example, about 250 ° C., and the amorphous film is annealed. It is a method of converting. In the annealing treatment, the substrate is heated at 400 to 600 ° C. for about 5 to 30 minutes, or laser light is applied for about 5 to 30 minutes.
It is performed by irradiating for a minute.

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

FIG. 54 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the RF glow discharge decomposition method.

In the gas cylinders 1011, 1012, 1013, 1014, 1015, 1016, 1017 in the figure, raw material gas for forming each layer of the present invention is sealed, for example 1011 Si
H ₄ gas (purity 99.999%) cylinder, H ₁₂ gas for 1012 (purity
99.999%) cylinder, 1013 B ₂ H ₆ gas diluted with H ₂ gas (purity 99.999%, hereinafter abbreviated as “B ₂ H ₆ / H ₂ ”) cylinder,
1014 is an NO gas (purity 99.5%) cylinder, 1015 is a PH ₃ gas diluted with H ₂ gas (purity 99.999%, hereinafter abbreviated as “PH ₃ / H ₂ ”) cylinder, and 1016 is an NH ₃ gas (purity 99.999). %) Cylinder, 1017 is a CH ₄ gas (purity 99.999%) cylinder.

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

That is, as an example of forming a photoreceptive member for electrophotography, SiH ₄ gas, H ₂ gas, B ₂ H ₆ / H ₂ gas, and NO gas are used as the CGL forming gas as the charge injection blocking layer forming gas. SiH ₄
Gas, H ₂ gas, SiH ₄ gas, NH ₃ gas, B ₂ H ₆ gas as CTL forming gas, SiH ₄ gas, CH as surface layer forming gas
_Take up the case of using ₄ gases.

To allow these gases to flow into the reaction chamber 1001, check that the valves 1051 to 1057 of the gas cylinders 1011-1017, the leak valve 1003 of the reaction chamber 1001 are closed, and the inflow valves 1031 to 1037 and the outflow valve. 1041-1047, auxiliary valve
Make sure the 1070 is open, then first open the main valve.
1002 is opened to evacuate the reaction chamber 1001 and the gas pipe.

Next, when the reading of the vacuum gauge 1004 reaches about 5 × 10 ⁻⁶ Torr, the auxiliary valve 1070 and the outflow valves 1041 to 1047 are closed.

After that, SiH ₄ gas from the gas cylinder 1011, gas cylinder 1012
H ₂ gas, gas cylinder 1013 to B ₂ H ₆ / H ₂ gas, gas cylinder 1014 to NO gas, gas cylinder 1016 to NH ₃ gas, gas cylinder 1017 to CH ₄ gas, valves 1051 to 1054,1056,1
Open 957 to introduce pressure regulator 1061-1064,1066,1067
Each gas pressure is adjusted to ² Kg / cm ² by.

Next, gradually open the inflow valves 1031-1034, 1036, 1037,
Mass flow controller 1021 ~ 1024,1
It will be introduced in 026 and 1027.

The temperature of the base cylinder 1007 installed in the reaction chamber 1001 is heated to a desired temperature between 50 and 350 ° C. by the heater 1008.

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

To form the charge injection blocking layer, the outflow valves 1041, 1042,
1043, 1044 and the auxiliary valve 1070 are gradually opened to allow SiH ₄ gas, H ₂ gas, B ₂ H ₆ / H ₂ gas and NO gas to flow into the reaction chamber 1001. At this time, SiH ₄ gas flow rate, H ₂ gas flow rate, B ₂ H ₆ /
Adjust the outflow valves 1041, 1042, 1043, and 1044 so that the H ₂ gas flow rate and NO gas flow rate reach the desired values, and also check the vacuum gauge 1004 so that the pressure inside the reaction chamber reaches the desired values. Adjust the opening of valve 1002. After that, the power source 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber 1001, and the formation of the charge injection blocking layer on the base cylinder is started. After the desired film thickness is formed, the RF glow discharge is stopped, and the outflow valves 1041, 1042, 1043, 1044 are closed to stop the outflow of gas into the reaction chamber, and the formation of the charge injection blocking layer is completed. .

A CTL is formed on the charge injection blocking layer formed as described above.

To form CGL, the outflow valves 1041 and 1042 and the auxiliary valve 1070 are gradually opened to supply SiH ₄ gas and H ₂ gas to the reaction chamber 10.
Inflow into 01. At this time, the outflow valves 1041 and 1042 are adjusted so that the SiH ₄ gas flow rate and the H ₂ gas flow rate reach desired values, and the main pressure is adjusted while observing the vacuum gauge 1004 so that the pressure inside the reaction chamber reaches a desired value. Adjust the opening of valve 1002.
After that, set the power supply 1010 to the desired power and set RF in the reaction chamber.
A glow discharge is initiated to initiate the formation of CGL on the substrate cylinder. After the desired film thickness is formed, the RF glow discharge is stopped, and the outflow valves 1041 and 1042 are closed to stop the inflow of gas into the reaction chamber to complete the formation of CGL.

CTLs are formed on CGLs formed as above. CT
To form L, the outflow valves 1041, 1043, 1045 and the auxiliary valve 1070 are gradually opened, and SiH ₄ gas, B ₂ H ₆ gas, NH
₃ Gas is allowed to flow into the reaction chamber 1001. At this time, the outflow valves 1041, 1043, and 1045 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ gas flow rate, and the NH ₃ gas flow rate reach the desired values, and the pressure inside the reaction chamber reaches the desired value. Adjust the opening of the main valve 1002 while watching the vacuum gauge 1004. Then power 1010
Is set to a desired power to generate an RF glow discharge in the reaction chamber and start forming CTLs on the substrate cylinder. After the desired film thickness is formed, the RF glow discharge is stopped, the outflow valves 1041, 1043, 1045 are closed to stop the gas flow into the reaction chamber, and the CTL formation is completed.

A surface layer is formed on the CTL formed as described above. To form the surface layer, the outflow valves 1041 and 1047 and the auxiliary valve 1070 are gradually opened to allow SiH ₄ gas and CH ₄ gas to flow into the reaction chamber 1001. At this time, SiH ₄ gas flow rate,
CH ₄ effluent such that the gas flow rate becomes a desired value the valve 1041,10
47 is adjusted, and the opening of the main valve 1002 is adjusted while observing the vacuum gauge 1004 so that the pressure in the reaction chamber becomes a desired value. After that, the power source 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber, and the formation of the surface layer on the substrate cylinder is started. After the desired film thickness is formed, the RF glow discharge is stopped, the outflow valves 1041 and 1047 are closed to stop the inflow of gas into the reaction chamber, and the formation of the surface layer is completed.

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and each gas is in the reaction chamber 1001 and the outflow valve 1041 to
In order to avoid remaining in the pipe from 1047 to the reaction chamber 1001, the outflow valves 1041 to 1047 are closed and the auxiliary valve 10
70 is opened, the main valve 1002 is fully opened, and the system is once evacuated to a high vacuum, if necessary.

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

It goes without saying that the above-mentioned gas species and valve operation may be changed according to the production conditions of each layer.

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

FIG. 55 shows a method for producing a light receiving member for electrophotography by the μW glow discharge decomposition method.

In the gas cylinders 2011, 2012, 2013, 2014, 2015, 2016, 2017 in the figure, the raw material gas for forming each layer of the present invention is sealed, for example, in 2011
SiH ₄ gas (purity 99.999%) cylinder, H ₂ gas (purity 99.999%) cylinder in 2012, B ₂ H ₆ diluted with H ₂ gas in 2013
Gas (purity 99.999%, hereinafter abbreviated as “B ₂ H ₆ / H ₂ ”) cylinder, 2014 is NO gas (purity 99.5%) cylinder, and 2015 is PH ₃ gas diluted with H ₂ gas (purity 99.999%, Below “PH ₃ /
H ₂ ") cylinder, 2016 is NH ₃ gas (purity 99.999%)
Cylinder 2017 is a CH ₄ gas (purity 99.999%) cylinder.

As an example of the gas used to form the photoreceptive member for electrophotography in the apparatus shown in FIG. 55, SiH ₄ gas, B ₂ H ₆ / H ₂ gas, and NO gas are used as the charge injection blocking layer forming gas. SiH ₄ gas and H ₂ gas as forming gas, and SiH ₄ gas as CTL forming gas
Gas, NH ₃ gas, B ₂ H ₆ gas as the surface layer forming gas
Let us consider the case of using iH ₄ gas and CH ₄ gas.

A gas cylinder is required to allow these gases to flow into the reaction chamber 2001.
Make sure that valves 2051 to 2057 of 2011-2017, leak valve 2003 of reaction chamber 2001 are closed, and also inflow valves 2031 to 2037, outflow valves 2041 to 2047, and auxiliary valve 20.
Make sure 70 is open, then first open main valve 20
Open 02 to evacuate the reaction chamber 2001 and the gas pipe.

Next, when the reading of the vacuum gauge 2004 reaches about 5 × 10 ⁻⁶ Torr, the auxiliary valve 2070 and the outflow valves 2041 to 2047 are closed.

After that, from gas cylinder 2011 SiH ₄ gas, gas cylinder 2012
From H ₂ gas, gas cylinder 2013 From B ₂ H ₆ / H ₂ gas, gas cylinder 2014 From NO gas, gas cylinder 2015 From PH ₃ / M ₂ gas, gas cylinder 2016 From NH ₃ gas, gas cylinder 2017 From C
H ₄ gas is introduced by opening valves 2051 to 2057, and pressure regulator
Adjust each gas pressure to 2Kg / cm ² by 2061 to 2067.

Next, the inflow valves 2031 to 2037 are gradually opened to introduce the above gases into the mass flow controllers 2021 to 2027.

Further, the temperature of the base cylinder 2006 installed in the reaction chamber 2001 is heated to a desired temperature between 50 and 350 ° C. by the heater 2005.

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

To form the charge injection blocking layer, the outflow valves 2041, 2042,
2043, 2044 and the auxiliary valve 2070 are gradually opened to allow SiH ₄ gas, H ₂ gas, B ₂ H ₆ / H ₂ gas, and NO gas to flow into the reaction chamber 2001. At this time, SiH ₄ gas flow rate, H ₂ gas flow rate, B ₂ H ₆ /
Adjust the outflow valves 2041,2042,2043,2044 so that the H ₂ gas flow rate and NO gas flow rate are at the desired values, and also while watching the vacuum gauge 2004 so that the pressure in the reaction chamber is at the desired value. Adjust the opening of valve 2002. After that, the microwave power source 2008 is set to a desired power, a μW glow discharge is generated in the reaction chamber 2001 through the waveguide 2009 and the dielectric window 2010, and the formation of the charge injection blocking layer on the substrate cylinder is started. After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valves 2041, 2042, 2043, 2044 are closed to stop the outflow of gas into the reaction chamber 2001 to form a charge injection blocking layer. To finish.

A CTL is formed on the charge injection blocking layer formed as described above.

To form CGL, the outflow valves 2041 and 2042 and the auxiliary valve 2070 are gradually opened to allow SiH ₄ gas and H ₂ gas to flow into the reaction chamber 2001. At this time, the outflow valves 2041 and 2042 are adjusted so that the SiH ₄ gas flow rate and the H ₂ gas flow rate are at desired values, and the vacuum gauge 2004 is set so that the pressure in the reaction chamber is at a desired value.
Adjust the opening of the main valve 2002 while watching. Then, set the microwave power supply 2008 to the desired power and
A μW glow discharge is generated in the reaction chamber through 2009 and the dielectric window 2010 to initiate the formation of CGL on the substrate cylinder. After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valves 2041 and 2042 are closed to stop the inflow of gas into the reaction chamber to complete the formation of CGL.

CTLs are formed on CGLs formed as above. CT
To form L, the outflow valves 2041, 2043, 2045 and the auxiliary valve 2070 are gradually opened, and SiH ₄ gas, B ₂ H ₆ gas, NH ₃
Gas is introduced into the reaction chamber 2001. At this time, the outflow valves 2041, 2043, 2045 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ gas flow rate, and the NH ₃ gas flow rate reach the desired values, and the pressure in the reaction chamber reaches the desired value. Adjust the opening of the main valve 2002 while watching the vacuum gauge 2004. After that, the microwave power source 2008 is set to a desired power, a μW glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 2010, and CTL formation is started on the substrate cylinder. After the desired film thickness is formed, the μW glow discharge is stopped, the outflow valves 2041, 2043, 2045 are closed to stop the gas flow into the reaction chamber and the formation of CTL is completed.

A surface layer is formed on the CTL formed as described above.

To form the surface layer, the outflow valves 2041 and 2047 and the auxiliary valve 2070 are gradually opened to supply SiH ₄ gas and CH ₄ gas to the reaction chamber 2.
Inflow into 001. At this time, the outflow valves 2041 and 2047 are adjusted so that the SiH ₄ gas flow rate and the CH ₄ gas flow rate reach desired values, and the main pressure is adjusted while observing the vacuum gauge 2004 so that the pressure inside the reaction chamber reaches a desired value. Adjust the opening of valve 2002.
After that, the microwave power source 2008 is set to a desired power, a μW glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 2010, and the formation of the surface layer on the substrate cylinder is started. After the desired film thickness is formed, the μW glow discharge is stopped, the outflow valves 2041 and 2047 are closed to stop the gas from flowing into the reaction chamber, and the formation of the surface layer is completed.

It goes without saying that all the outflow valves other than the gas necessary for forming each layer are closed, and the pipes for the respective gases inside the reaction chamber 2001 and from the outflow valves 2041 to 2047 to the reaction chamber 2001. In order to avoid remaining in the interior, the outflow valves 2041 to 2047 are closed, the auxiliary valve 2070 is opened, the main valve 2002 is fully opened, and the system is temporarily evacuated to a high vacuum, if necessary.

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

Needless to say, the above-mentioned gas species and valve operation may be changed according to the preparation conditions of each layer.

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

FIG. 56 shows an apparatus for manufacturing a photoreceptor member for electrophotography by the HRCVD method.

In FIG. 56, 3001 is a film forming chamber, 3002 is an activation chamber (A), 3003 and 3018 are microwave plasma generators, and 300
4 is a raw material gas introduction pipe of active species (A), 3005 is an active species (A) introduction pipe, 3006 is a motor, 3007 is a heater for heating a cylindrical substrate, 3008 and 3009 are blowing pipes, 301
Reference numeral 0 indicates a cylindrical substrate, and 3011 indicates a main exhaust valve. Further, reference numerals 3012 to 3016 are cylinders for supplying a source gas, 3017 is an activation chamber (B), 3019 is a source gas introduction pipe,
3020 is an active species introduction tube generated from the active chamber (B). A method for producing an electrophotographic light-receiving member having a layer structure according to the present invention on a cylindrical substrate using this apparatus will be specifically described.

As an example, Al is used as the cylindrical substrate, and SiH ₄ , B ₂ H ₆ , NO, and NO as the charge injection blocking layer forming gas.
The H _2, a SiH _4, H ₂ as gas CGL formation, the CTL forming gas _{SiH 4, SiF 4, CH 4} , H 2, B a ₂ H _6, SiH ₄ as a gas for surface layer formation , CH ₄ and H ₂ were used.

First, suspend the Al cylindrical base 3010 in the film forming chamber 3001,
A heating heater 3007 was provided inside it so that it could be rotated by a motor 3006, and the film formation chamber was evacuated to 5 × 10 ⁻⁶ Torr.

In order to form the charge injection blocking layer, H ₂ gas is introduced from the cylinder 3012 into the activation chamber (A) through the introduction pipe 3004, activated by the microwave plasma generator 3003, and activated hydrogen is introduced through the introduction pipe 3005. From blowing tube 3008 to deposition chamber 3001
Led to. On the other hand, SiH ₄ gas from cylinder 3013, B ₂ H from 3014
₆ gas, NO gas from 3015 Introducing pipe 3019 Activation chamber (B)
After being introduced into 3017 and activated by a microwave plasma generator 3018, a blowing pipe 3009 is introduced through an introduction pipe 3020.
It led to the film forming chamber 3001. At this time, the gas flow rate, internal pressure, and microwave power are set to desired values.

The Al cylindrical substrate 3010 was heated and maintained at a desired temperature by the heater 3007, and the exhaust gas was exhausted by appropriately adjusting the opening of the main exhaust valve 3011. Thus, the charge injection blocking layer was formed. Similarly, on the above charge injection blocking layer, H ₂ gas from the cylinder 3012 and SiH ₄ gas from the 3013 are supplied to supply CGL, and H ₂ gas from the cylinder 3012 on the CGL and SiH from 3013.
₄ gas, 3014 to B ₂ H ₆ gas, 3016 to CH ₄ gas, SiF ₄ gas from a cylinder (not shown) to supply CTL to the CTL.
The surface layer was sequentially formed by supplying H ₂ gas from 12 and SiH ₄ gas from the cylinder 3013 to form a photoreceptor member for electrophotography.

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

Fig. 57 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the FOCVD method.

Gas cylinders 4011, 4012, 4013, 4014, 4015, 4016, 4017 in the figure, the source gas for forming the respective layers of the present invention is sealed, as an example, for example, 4011
SiH ₄ gas (purity 99.999%) cylinder, 4012 H ₂ gas (purity 99.999%) cylinder, 4013 B ₂ H ₆ gas diluted with H ₂ (purity 99.999%, hereinafter “B ₂ H ₆ / H ₂ ") cylinder, 401
4 is NO gas (purity 99.5%) cylinder, 4015 is PH ₃ gas diluted with H ₂ (purity 99.999%, hereinafter abbreviated as “PH ₃ / H ₂ ”)
Cylinder, 4016 is CH ₄ gas (purity 99.999%) Cylinder, 4017 is F
₂ gases (10% He diluted, purity 99.99%).

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

As an example of forming a light receiving member for electrophotography, SiH ₄ gas, H ₂ gas, B ₂ H _{6 is} used as a charge injection blocking layer forming gas.
/ H ₂ gas, NO gas, F ₂ gas as SiH ₄ gas as CGL gas,
H ₂ gas, F ₂ gas, SiH ₄ gas, CH ₄ as CTL forming gas
Gas, B ₂ H ₆ gas, F ₂ gas as the surface layer forming gas,
Let us consider the case of using SiH ₄ gas, CH ₄ gas, and F ₂ gas.

The source gas filled in the cylinders 4011-4016 is 4031-
Each valve of 4036 and mass flow controller of 4053 to 4058 are introduced into the vacuum chamber of 4020 to 4001.

The F ₂ gas filled in the cylinder of 4017 is introduced into the vacuum chamber of 4001 through 4021 in the same manner as described above.

The vacuum chamber 4001 is connected via the main vacuum valve 4002.
It is exhausted by a vacuum exhaust device (not shown).

Reference numeral 4061 denotes a heater for heating the substrate, which heats the substrate cylinder 4060 to an appropriate temperature during film formation, preheats the substrate cylinder 4060 before film formation, or heats the film after film formation to anneal the film. .

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

Also, the base cylinder 4060 is used to form a uniform film.
It is rotating by the rotating mechanism of 4062.

In order to introduce the gases 4011 to 4017 into the 4001, it must be slowly introduced by various valve operations when the inside of the chamber of the 4001 reaches about 5 × 10 ⁻⁶ Torr.

In addition, the base cylinder 40 installed in the chamber 4001
The temperature of 60 may be heated to a desired temperature between 50 and 350 ° C. by the heater 4061.

After the film formation preparation is completed as described above, the film formation is performed on the base cylinder 4060 in the order of the charge injection blocking layer, CGL, and CTL.

To form the charge injection blocking layer, the valves 4046-4049 are opened and the outflow valves 4031, 4032, 4033, 4034 and the auxiliary valves 4 are opened.
Open 060 gradually to SiH ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, H ₂
Gas is allowed to flow into the reaction chamber 4001. At this time, the outflow valves 4031, 4024033, and 4034 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ / H ₂ gas flow rate, the NO gas flow rate, and the H ₂ gas flow rate have desired values, and the reaction chamber The opening of the main valve 4002 is adjusted while observing a vacuum gauge (not shown) at which the pressure of is a desired value.

Next, open 4052, and while watching the mass flow meter 4059, gradually open the valve of 4037 to the desired flow rate, finish setting the flow rate, and wait until the charge injection blocking layer is formed to the desired film thickness. For example, the formation of the charge injection blocking layer is completed.

CGL, CTL, and surface layer are respectively formed on the charge injection blocking layer formed as described above by the same operation as described above. For each layer, the required gas may be flowed and the valves may be operated in the same manner as the charge injection blocking layer.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

<Example 1> Using the manufacturing apparatus shown in FIG.
A light-receiving member for electrophotography was formed on an aluminum cylinder that was mirror-finished according to the preparation conditions shown in Tables 2, 3, and 4.

The prepared electrophotographic light-receiving member was set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging was performed under various conditions. Check electrophotographic characteristics such as performance, sensitivity, residual potential, ghost, etc.
After the accelerated durability equivalent to 0,000 sheets, the deterioration of charging ability, surface scraping, and increase of image defects were investigated.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 5 shows the above-mentioned comprehensive evaluation results.

As can be seen in Table 5, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 2> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 6 and 7, and the same evaluation was performed.

The results are shown in Table 8.

As can be seen in Table 8, good results were obtained for all items.

<Embodiment 3> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 9 and 10, and the same evaluation was performed.

The results are shown in Table 11.

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

<Embodiment 4> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables, Tables 12 and 13, and the same evaluations were performed.

The results are shown in Table 14.

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

<Embodiment 5> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 15 and 16, and the same evaluations were performed.

The results are shown in Table 17.

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

<Embodiment 6> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 18 and 19, and the same evaluations were performed.

The results are shown in Table 20.

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

<Embodiment 7> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 21 and 22, and the same evaluations were performed.

The results are shown in Table 23.

As shown in Table 23, good results were obtained for all items.

<Embodiment 8> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 24 and 25, and the same evaluation was performed.

The results are shown in Table 26.

As shown in Table 26, good results were obtained for all items.

<Embodiment 9> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, 27 and 28, and the same evaluation was performed.

The results are shown in Table 29.

As shown in Table 29, good results were obtained for all items.

<Embodiment 10> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 30 and 31, and the same evaluation was performed.

The results are shown in Table 32.

As shown in Table 32, good results were obtained for all items.

<Embodiment 11> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 33 and 34, and the same evaluations were performed.

The results are shown in Table 35.

As shown in Table 35, good results were obtained for all items.

<Embodiment 12> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 36 and 37, and the same evaluation was performed.

The results are shown in Table 38.

As shown in Table 38, good results were obtained for all items.

<Embodiment 13> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, 39 and 40, and the same evaluations were performed.

The results are shown in Table 41.

As shown in Table 41, good results were obtained for all items.

<Embodiment 14> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 42 and 43, and the same evaluation was performed.

The results are shown in Table 44.

As shown in Table 44, good results were obtained for all items.

<Embodiment 15> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, Tables 45 and 46, and the same evaluation was performed.

The results are shown in Table 47.

As shown in Table 47, good results were obtained for all items.

<Example 16> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, 48 and 49, and the same evaluation was performed.

The results are shown in Table 50.

As shown in Table 50, good results were obtained for all items.

<Example 17> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables, 51 and 52, and the same evaluation was performed.

The results are shown in Table 53.

As shown in Table 53, good results were obtained for all items.

<Example 18> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, 54 and 55, and the same evaluation was performed.

The results are shown in Table 56.

As shown in Table 56, good results were obtained for all items.

<Embodiment 19> Using the manufacturing apparatus shown in FIG.
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Tables, 57 and 58, and the same evaluations were performed.

The results are shown in Table 59.

As shown in Table 59, good results were obtained for all items.

<Embodiment 20> Using the manufacturing apparatus in FIG.
Photoreceptive members for electrophotography were formed on aluminum cylinders that were mirror-finished according to the preparation conditions shown in Tables 61, 62, and 63.

The prepared electrophotographic light-receiving member was set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging ability was set under various conditions. , Checking electrophotographic characteristics such as sensitivity, residual potential, ghost, etc.
Acceleration equivalent to 0,000 sheets Decreased charging ability after actual machine durability, surface abrasion,
The increase in image defects was investigated.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 64 shows the comprehensive evaluation results.

As shown in Table 64, good results were obtained for all items. In particular, remarkable superiority was observed in initial charging ability and durability.

<Example 21> Using the manufacturing apparatus shown in FIG.
An electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the conditions shown in the table. The prepared electrophotographic light-receiving member was set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging was performed under various conditions. We checked the electrophotographic characteristics such as performance, sensitivity, residual potential, ghost, etc., and investigated the deterioration of charging ability, surface scraping, and increase of image defects after the endurance of an accelerated actual machine equivalent to 2 million sheets.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 69 shows the comprehensive evaluation results.

As shown in Table 69, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

Example 22 Using the manufacturing apparatus shown in FIG.
An electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the conditions shown in the table.

The prepared electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging ability was set under various conditions. We checked the electrophotographic characteristics such as sensitivity, residual potential, and ghost, and examined the deterioration of charging ability, surface scraping, and the increase of image defects after the endurance of 2 million sheets of accelerated real machine.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 74 shows the comprehensive evaluation results.

As shown in Table 74, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 23> A cylinder subjected to mirror surface processing is further subjected to lathe processing with a sword binder having various angles, and a cylinder having a cross-sectional shape as shown in Fig. 42 and various cross-sectional patterns as shown in Table 75 is obtained. I prepared multiple books. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 42 and subjected to the drum manufacturing under the manufacturing conditions shown in Table 76. Various evaluations were performed on the produced drum with an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the results are shown in Table 17.

<Example 24> The surface of a cylinder that has been mirror-finished is continuously exposed to a large number of bearing balls to be dropped, and a so-called surface dimple forming process that causes countless dents on the cylinder surface is performed. A plurality of cylinders having the cross-sectional shape shown in the figure and having various cross-sectional patterns as shown in Table 79 were prepared.
The cylinder is sequentially set in the manufacturing apparatus shown in FIG.
The drum was produced under the production conditions shown in Table 20. The drum thus prepared was subjected to various evaluations using an electrophotographic apparatus using a halogen lamp as a light source and 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 80 were obtained.

<Example 25> Tables 81, 82, 83, 84 using the manufacturing apparatus of FIG.
Drums were prepared and evaluated in the same manner as in Example 1 under the conditions shown in the table.

The results are shown in Table 85.

As shown in Table 85, good results were obtained for all items.

[Summary of Effects of the Invention] The electrophotographic light-receiving member of the present invention has the specific layer structure as described above, thereby solving all the problems in the conventional electrophotographic light-receiving member composed of A-Si. In particular, it has extremely excellent initial charging ability, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics and durability. Also, its electrical characteristics are stable,
An image obtained by using it has a high density and a clear halftone, and is excellent and excellent.

In particular, in the present invention, a function-separated type structure using CTL and CGL is used, and the substance (M) that controls conductivity is contained in the CTL in a state of being unevenly or partially unevenly distributed in the layer thickness direction. At the same time, by containing at least one kind of carbon atom, nitrogen atom, and oxygen atom, it becomes possible to freely design according to the characteristics of each layer, and charge generation and
Immediate injection and transport from CGL to CTL, with excellent chargeability and sensitivity, low residual potential and ghost, high resolution in images, and high quality stable and repeatable images Obtainable.

[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 5 are uneven shapes on a surface of a support and a method for producing the uneven shapes, respectively. FIGS. 6 to 11 are explanatory views for explaining the distribution state of the substance (M ₀ ) controlling the conductivity contained in the charge injection blocking layer, and FIGS. To FIG. 17 are explanatory views for explaining the distribution state of carbon atoms and / or oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer, and FIGS. 18 to 53 are CTLs, respectively. Atom contained in (Y)
FIG. 54 is an example of a device for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention, FIG. 54 is a schematic explanatory view of a manufacturing device by a glow discharge method using RF, FIG. 55 is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention, which is a schematic explanatory view of a manufacturing apparatus by a glow discharge method using microwaves, and FIG. 56 is the present invention. An example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography, which is a schematic explanatory view of a manufacturing apparatus by the HRCVD method, and FIG. 57 shows a light receiving layer of the light receiving member for electrophotography of the present invention. An example of an apparatus for forming, a schematic explanatory view of a manufacturing apparatus by the FOCVD method, FIG. 58 is an impurity gas and doping when forming CTL of the electrophotographic light-receiving member of the present invention using RF glow discharge・ A diagram showing the change in the flow rate during gas film formation. FIG. 60 is a view showing a flow rate change at the time of film formation of an impurity gas and a doping gas when the CTL of the photoreceptive member for photography is formed by using a microwave glow discharge. FIG. 60 shows the photoreceptive member for electrophotography of the present invention. CTL to HRCVD
FIG. 61 is a view showing flow rate changes during film formation of an impurity gas and a doping gas in the case where the CTL of the light receiving member for electrophotography of the present invention is FOCVD
Showing changes in the flow rates of the impurity gas and the doping gas at the time of film formation in the case where the electrophotographic light-receiving member of the present invention is formed. 63 is an enlarged view of the cylinder cross section in the case of a letter shape, FIG. 63 is an enlarged view of the cylinder cross section when the surface of the cylinder substrate in forming the electrophotographic light-receiving member of the present invention is subjected to so-called dimple processing, 64 The figure is a diagram showing flow rate changes at the time of film formation of an impurity gas and a doping gas in the case of an embodiment in which the CTL of the electrophotographic light-receiving member of the present invention is formed by using RF glow discharge. Regarding Fig. 1, 100 ... Photoreceptive layer 101 ... Support 102 ... Photoreceptive layer 103 ... Charge injection blocking layer 104 ... CGL 105 ... CTL 106 ... Surface layer 107 ... Free surface Fig. 3 , Fig. 4, 301,401 …… Support 302,402 …… Support surface 303,403 …… Rigid spherical sphere 304,404 …… Spherical trace depression About Fig. 5, 500 …… Photoreceptive layer 501 …… Support 502 …… Charge injection Blocking layer 503 …… CGL 504 …… CTL 505 …… Surface layer 506 …… Free surface In Fig. 54, 1001 …… Reaction chamber 1002 …… Main exhaust valve 1003 …… Reaction chamber leak valve 1004 …… Vacuum gauge 1007 ...... Cylinder base 1008 ...... Base heating heater 1009 ...... Cylinder base rotation motor 1010 ...... RF power supply 1011 to 1017 …… Raw material gas cylinder 1021 to 1027 …… Mass flow controller 1031 to 1037 …… Gas inflow Valve 1041-1047 …… Gas outflow valve 1051-1057 …… Raw material gas cylinder Valves 1061 to 1067 …… Pressure regulator Fig. 55, 2001 …… Reaction chamber 2002 …… Main exhaust valve 2003 …… Reaction chamber leak valve 2004 …… Vacuum gauge 2005 …… Heater for substrate heating 2006 …… Cylinder Substrate 2007 …… Motor for rotating substrate 2008 …… Microwave power source 2009 …… Waveguide 2010 …… Dielectric window 2011 ～ 2017 …… Gas cylinder 2021 ～ 2027 …… Mass flow controller 2031 ～ 2037… … Gas inflow valves 2041 to 2047 …… Gas outflow valves 2051 to 2057 …… Source gas cylinder valves 2061 to 1267 …… Pressure regulators About Fig. 300 3001 …… Deposition chamber 3002 …… Activation chamber (A ) 3003,3018 …… Microwave plasma generator 3004,3019 …… Raw material gas introduction pipe 3005,3020 …… Activated species introduction pipe 3006 …… Motor 3007 …… Cylinder substrate heating heater 3008,3009 …… Blowout pipe 3010… … Cylindrical substrate 3011 …… Exhaust valve 3012 to 3016 …… Raw material gas cylinder 3017 …… Activation chamber (B) About Fig. 57, 4001 …… Reaction chamber 4002 …… Main exhaust valve 4011 to 4017 …… Raw material gas cylinder 4020,4021 …… Raw material Gas inlet pipe 4031-4037 Outflow valve 4046-4052 Inflow valve 4053-4059 Mass flow controller 4060 Cylinder substrate 4061 Cylinder substrate heater 4062 Cylinder substrate heater .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryuji Okamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP 62-5252 (JP, A) JP 62 -5249 (JP, A) JP 62-5250 (JP, A) JP 62-5253 (JP, A) JP 62-115457 (JP, A) JP 62-115456 (JP, A) )

Claims (1)

[Claims] 1. A support and a charge injection blocking layer on the support,
A photoreceptive layer having a layer structure in which a charge generation layer, a charge transport layer, and a surface layer are laminated in this order from the support side, and the surface layer is composed of silicon atoms, carbon atoms, nitrogen atoms and oxygen atoms. At least one of them, composed of a non-single crystal material containing at least one of a hydrogen atom and a halogen atom, the charge injection blocking layer, the charge generation layer and the charge transport layer is a silicon atom as a host A non-single-crystal material containing at least one of a hydrogen atom and a halogen atom, and the charge injection blocking layer contains an atom belonging to Group III or V of the periodic table, The transport layer contains at least one of carbon atom, nitrogen atom and oxygen atom, and the concentration of atoms belonging to Group III or Group V of the periodic table in the layer thickness direction is An electrophotography characterized in that it has at least a portion containing it in a non-uniform distribution state having a portion increasing or decreasing from the carrier side, and the layer thickness of the charge generation layer is made thinner than the layer thickness of the charge transport layer. Light receiving member.