JPH0797231B2 - Photoreceptive member for electrophotography - Google Patents

Description

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

[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 the following problems in terms of electro-optical and photoconductive properties such as dark resistance, photosensitivity and photoresponsiveness, and operating environment properties. Moreover, in terms of stability over time and durability, each has been individually improved in characteristics, but there is room for further improvement in measuring overall characteristics. .

For example, when it is applied to a photoreceptive member for electrophotography, it is often observed that a residual potential remains in the conventional use when attempting to increase photosensitivity and dark resistance at the same time. However, when it is used repeatedly for a long time, fatigue is accumulated due to repeated use, and a so-called ghost phenomenon that causes an afterimage is generated, which is not a disadvantage.

When the light-receiving layer is made of A-Si material, hydrogen atom (H) or halogen atom (X) such as fluorine atom or chlorine atom is used in order to improve its electrical and photoconductive properties. , 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 the photoconductive 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 chemical composition preparation method of each layer constitution is devised so as to solve all of the above problems. Need to

[Object of the Invention]

It is an object of the present invention to solve various problems in a photoreceptive member for electrophotography having a conventional photoreceptive 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 and photoconductive properties are substantially always stable with little dependence on the use environment, excellent light fatigue resistance, and deterioration phenomenon occurs even after repeated use. Another object of the present invention is to provide a photoreceptive member for electrophotography having a photoreceptive layer composed of a material having a silicon atom as a base material, which has excellent durability and moisture resistance and has no or almost no residual potential 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, which has a photoreceptive layer which is dense and stable in terms of structural arrangement and which has a high layer quality and is made of a material containing silicon atoms as a base material.

Still another object of the present invention is that, when applied as a photoreceptive member for electrophotography, it has a sufficient charge retention ability during charging treatment for electrostatic image formation, and ordinary electrophotography is extremely effective. It is an object of the present invention to provide a photoreceptive member for electrophotography, 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 light-receiving member for electrophotography of the present invention comprises a support, and a long-wavelength light absorption layer (hereinafter abbreviated as “IR absorption layer”) on the support.
And a light-receiving layer having a layer structure in which a charge-generating layer and a charge-transporting layer are stacked in this order from the support side, and the long-wavelength light-absorbing layer has a silicon atom as a base, and a germanium atom and tin. At least one of the atoms,
Non-single crystal material containing at least one of hydrogen atom and halogen atom (hereinafter "Non-Si (Ge, Sn)"
(H, X) ”, the charge generation layer (hereinafter abbreviated as“ CGL ”) and the charge transport layer (hereinafter“ C ”).
Abbreviated as "TL") is a non-single crystal material (hereinafter abbreviated as "Non-Si (H, X)") containing a silicon atom as a host and containing at least one of a hydrogen atom and a halogen atom. And the charge transport layer comprises a carbon atom,
Heterogeneous containing at least one of nitrogen atom and oxygen atom, and having a portion in which the concentration of atoms belonging to Group III or V of the periodic table increases or decreases in the layer thickness direction from the support side. The present invention is characterized in that it has at least a portion contained in various distribution states.

[Operation] The electrophotographic light-receiving member of the present invention designed so as to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has an extremely excellent electrical, optical, Photoconductive property Shows durability and use environment characteristics.

In particular, there is practically no effect of residual potential on image formation, its electrical characteristics are stable, it has high sensitivity and high SN ratio, and it has light fatigue resistance, repeated use characteristics, Since it has excellent moisture resistance and electrical withstand voltage, it is possible to stably repeat high-quality images with high density, clear halftone and high resolution.

Furthermore, 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, a charge transport layer (hereinafter abbreviated as “CTL”) and a charge generation layer (hereinafter “C”).
Abbreviated as “GL”), a function-separated type structure is used, so that the important functions of the photoreceptive member for electrophotography such as generation of electric charges (photocarriers) and transport of the generated electric charges are provided in different layers. By having in, the degree of freedom of layer design is greater than having both functions in one layer,
Can have excellent characteristics. Also, since the CTL contains at least one of carbon atom, nitrogen atom and oxygen atom, it is possible to reduce the relative dielectric constant of CTL, so that the capacity per layer thickness can be reduced and the charging ability can be reduced. The sensitivity can be improved, the pressure resistance against high voltage can be improved, and the durability can be 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, by providing an IR absorption layer between the support and the CGL, even if long-wavelength light such as a semiconductor laser is used as an exposure light source of an electrophotographic apparatus, absorption is not completed between the incident surface side and the support. Since the long-wavelength light for a minute is also highly efficiently absorbed by the IR absorbing layer, the appearance of an interference phenomenon due to the reflection of the long-wavelength light on the surface of the support can be remarkably prevented, and the image quality is 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 comprises an IR absorbing layer 102 on a support 101 for the electrophotographic light-receiving member.
And CGL103 composed of Non-Si (H, X), Non-Si (H, X)
And a portion containing at least one kind of carbon atom, nitrogen atom and oxygen atom, and containing a substance (M) for controlling conductivity in a non-uniform distribution state in the layer thickness direction. And a photoreceptive layer having a layer structure including at least CTL104. The CTL 104 has a free surface 105.

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,
Examples include metals such as Pb and 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, ceramic, 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 imparted by providing a thin film made of Au, Ir, Nb, Ta, V, Ti, Pt, Pd, 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 shape or a cylindrical shape having a smooth surface or an uneven surface, and the thickness thereof is appropriately determined so that a desired electrophotographic light-receiving member can be formed. When flexibility as a light receiving member for electrophotography is required, it can be made as thin as possible within a range in which the function as a support is sufficiently exhibited. However, in view of manufacturing and handling of the support, mechanical strength, etc., it is usually 10 μm or more.

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

The unevenness provided on the surface of the support is such that a cutting tool having a V-shaped cutting edge is fixed at a predetermined position of a cutting machine such as a milling machine or a lathe, and a cylindrical support is rotated 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 protrusions created by the irregularities formed by such a cutting method have a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped projection may be a double or triple multiple spiral structure or a cross spiral structure.

Alternatively, 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 adhesion and desired electrical contactability, it is formed in 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, an isosceles triangle and a right triangle are particularly 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 IR absorbing layer and the light receiving layer made of the materials described later is structurally sensitive to the state of the surface on which the layer is formed, and the surface state The layer quality greatly changes depending on the. Therefore, IR absorption layer and Non-Si (H,
X) It is necessary to set the dimension of the unevenness provided on the surface of the support so as not to deteriorate the layer quality of the light receiving layer.

Second, if the free surface of the light-receiving layer has extreme irregularities, the cleaning cannot be completely performed in the cleaning after the 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, problems in the process of 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-uniform layer pressure of each layer deposited on such a support is preferably 0.1 μm to 2 μm, more preferably 0.1 μm to 1.5 μm, within the same pitch. It is desirable that the thickness is 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.

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

FIG. 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 Ro and dropping them from 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 It is possible to form a plurality of spherical trace depressions 304 having the same width D.

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 concave and convex 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 are as follows: If the above condition is satisfied, there are 0.5 or more Newton rings due to shear ring interference in each of the dents. Furthermore, the following formula: If the above condition is satisfied, there will be one or more Newton rings due to shear ring interference in each of the dent depressions.

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, a rigid true sphere having substantially the same radius Ro is used, but the support in the present invention is not limited to this, and the object of the present invention is achieved. Radius with the number and types managed within the range
It is also possible to use a plurality of types of rigid true spheres having different Ro.

FIG. 5 shows an example in which a light-receiving layer 500 composed of IR absorption layers 502, CGL503 and CTL504 is formed on the support 501 prepared by the above method. CTL 504 has a free surface 505.

IR Absorption Layer The IR absorption layer in the present invention has, as constituent elements, at least one of a silicon atom, a germanium atom (Ge) and a tin atom (Sn), and a hydrogen atom (H) and a halogen atom (X). And a non-single-crystal material containing silicon atoms (Si) (hereinafter abbreviated as “Non-Si (Ge, Sn) (H, X)”).

The germanium atoms and / or tin atoms contained in the IR absorption layer may be uniformly distributed in the IR absorption layer, or may be uniformly contained in the entire layer region of the IR absorption layer. However, the distribution concentration in the layer thickness direction may be non-uniform. However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary for the content to be evenly distributed in a uniform manner from the viewpoint of achieving uniform properties in the in-plane direction. That is, the IR absorbing layer is uniformly contained in the layer thickness direction, and the support is provided on the side opposite to the side where the support is provided (the free surface side of the light receiving layer). It is contained in the IR absorption layer so that it is distributed more on the body side or in the opposite distribution.

In the electrophotographic light-receiving member of the present invention, as described above, the germanium atom contained in the IR absorption layer and / or
Alternatively, it is desirable that the tin atoms have the above-described distribution in the layer thickness direction and a uniform distribution in the in-plane direction parallel to the surface of the support.

In one of the preferred embodiments, the distribution state of germanium atoms and / or tin atoms in the IR absorption layer is such that germanium atoms and / or tin atoms are continuously and evenly distributed in the entire layer region. Since the distribution concentration of atoms and / or tin atoms in the layer thickness direction decreases from the support side toward CGL, the affinity between the IR absorption layer and CGL is excellent, and as described later, By increasing the distribution concentration of germanium atoms at the end on the support side extremely, the long-wavelength side light that cannot be completely absorbed from CTL to CGL when using a semiconductor laser or the like is substantially absorbed in the IR absorption layer. It can be completely absorbed, and interference can be prevented by reflection from the support surface.

6 to 11 show the light receiving member of the present invention.
A typical example is shown in which the distribution state of germanium atoms and / or tin atoms contained in the IR absorption layer in the layer thickness direction is non-uniform.

6 to 11, the horizontal axis represents the distribution concentration C of germanium atoms and / or tin atoms (hereinafter abbreviated as “atoms (GS)”), and the vertical axis represents the layer thickness of the IR absorption layer.
_B indicates the position of the end surface of the IR absorption layer on the support side, and t _T indicates the position of the end surface of the IR absorption layer on the side opposite to the support side. That is,
The IR absorption layer containing atoms (GS) is formed from the t _B side toward the t _T side.

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

In the example shown in FIG. 6, from the interface position t _B where the surface of the IR absorbing layer containing atoms (GS) is formed and the surface of the IR absorbing layer to t _{1 to} the position of the atom (GS ) Is contained in the IR absorption layer where atoms (GS) are formed with a constant concentration C of C ₁ and is gradually continuous from the concentration C ₂ from the position t ₁ to the interface position t _T. Has been reduced. At the interface position t _T , the distribution concentration C of atoms (GS) is C ₃ .

In the example shown in FIG. 7, the contained atoms (GS)
Distribution concentration C is the concentration C ₄ up to the position t _T to the position t _B
From the above, a distribution state is formed in which the concentration gradually decreases continuously to reach the concentration C ₅ at the position t _T.

In the case of FIG. 8, the position t _B to the position T ₂ to the atom (G
The distribution concentration C in S) is set to a constant value with the concentration C _6, and is gradually and continuously reduced between the position t ₂ and the position t _T, and the distribution concentration C is substantially zero at the position t _T. (Here, substantially zero is the case of less than the detection limit amount,
The subsequent meaning of "substantially zero" is also the same. ).

In the case of FIG. 9, the distribution concentration C of atoms (GS) is at the position t _B.
Up to more position t _T, it is reduced continuously and gradually than the concentration C _8, and is substantially zero at the position t _T.

In the example shown in FIG. 10, the distribution concentration C of atoms (GS) is
Is a constant value with the density C ₉ ) between the positions t _B and t ₃ , and is the density C _{10 at the} position t _T. Between the position t ₃ and the position t _T , the distribution concentration C is linearly reduced from the position t ₃ to the position t _T.

In the example shown in FIG. 11, from the position t _B to the position t _T , the distribution concentration C of atoms (GS) is linearly reduced from the position C ₁ to substantially zero. .

As described above with reference to FIGS. 6 to 11, some typical examples of the distribution state of the atoms (GS) contained in the IR absorption layer in the layer thickness direction are explained. Contains silicon atoms and has a distributed concentration C of atoms (GS)
At the interface t _T , the distribution concentration C is considerably lower than that on the support side. When the distribution state of atoms (GS) is provided in the IR absorption layer, It is mentioned as one of the suitable examples. In this case, as the distribution state of the atoms (GS) in the layer thickness direction, the maximum value Cmax of the distribution concentration of the atoms (GS) is preferably 1000 atom ppm or more, more preferably 5000 atom ppm with respect to the sum with the silicon atom. that's all,
Optimally, it is desirable that the layers are formed so that the distribution state may be 1 × 10 ⁴ atomic ppm or more.

In the present invention, the content of atoms (GS) contained in the IR absorption layer is appropriately determined as desired so that the object of the present invention can be effectively achieved, but preferably 1 to 10
It is desirable that the concentration is × 10 ⁵ atomic ppm, more preferably 100 to 9.5 × 10 ⁵ atomic ppm, and most preferably 500 to 8 × 10 ⁵ atomic ppm.

The IR absorption layer may further contain at least one of a conductivity controlling substance (M _R ), an oxygen atom (O), a nitrogen atom (N ₁ ), and a carbon atom (C).

Further, as the substance (M _R ) that controls the conductivity,
In the field of semiconductors, so-called impurities can be mentioned. In the present invention, an atom belonging to Group III of the periodic table (hereinafter referred to as “Group III atom”) or an n-type conductivity which gives p-type conductivity is described. An atom belonging to Group V of the given periodic table (hereinafter referred to as “Group V atom”) is used.
Specific examples of the group III atom include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl.
(Thallium) and the like, and B and Ga are particularly preferable. As the group V atom, specifically, P (phosphorus), As (arsenic), Sb
(Antimony), Bi (bismuth) and the like, and P and As are particularly preferable.

In the present invention, the content of the substance (M _R ) contained in the IR absorption layer for controlling the conductive property is preferably 0.01
〜5 × 10 ⁵ atom ppm, more preferably 0.5〜1 × 10 ⁴ atom pp
m, optimally 1 to 5 × 10 ³ atomic ppm is desirable.

In the present invention, composed of Non-Si (Ge, Sn) (H, X)
The IR absorption layer is formed by, for example, a vacuum deposition film forming method similar to that of CGL and CTL described later, in which numerical conditions of film forming parameters are appropriately set so that desired characteristics can be obtained.
Specifically, for example, glow discharge method (low frequency CVD, high frequency
By decomposing the source gas of non-single-crystal material, such as alternating current discharge CVD such as CVD or microwave CVD, or direct current discharge CVD), sputtering method, vacuum deposition method, ion plating method, optical CVD method, thermal CVD method In order to form a deposited film, the active species (A) generated and the active species (B) generated from a chemical substance for film formation that chemically interacts with the active species (A) are formed separately. The method of forming a non-single-crystal material by introducing it into the film forming space of (1) and chemically reacting these (hereinafter abbreviated as "HRCVD method"), the source gas of the non-single-crystal material, and the oxidizing action on the source gas. A method of forming a non-single-crystal material by introducing halogen-based oxidizing gas having different properties into the deposition space for forming a deposited film separately and chemically reacting these (hereinafter, referred to as “FOCVD
Abbreviated as “method”). These thin film deposition methods are
It is appropriately selected and adopted depending on factors such as the load of capital investment, manufacturing scale, and desired characteristics of the light receiving member to be created. Conditions for manufacturing a light receiving member having desired characteristics Is relatively easy to control, and it is possible to easily introduce halogen atoms and hydrogen atoms together with silicon atoms. Therefore, glow discharge method, sputtering method, ion plating method, HRCLD method, FOCVD method Is preferred. Then, these methods may be used in combination in the same device system.

For example, by glow discharge method, Non-Si (Ge, Sn)
In order to form an IR absorption layer composed of (H, X), basically, a source gas for Si supply that can supply silicon atoms (Si) and a Ge supply gas that can supply germanium atoms (Ge) Can be supplied with the source gas and / or tin atom (Sn)
The source gas for supplying Sn and, if necessary, the source gas for introducing hydrogen atoms (H) and / or the source gas for introducing halogen atoms (X) can be decompressed in the inside of the deposition chamber in a desired gas pressure state. Then, a glow discharge is generated in the deposition chamber, and a layer made of Non-Si (Ge, Sn) (H, X) may be formed on the surface of a predetermined support that is installed at a predetermined position in advance. . Further, in order to contain the germanium atom and / or the tin atom in a non-uniform distribution state, while controlling the gas flow rate of the source gas for Ge supply and / or Sn supply according to the desired rate-of-change curve, the non-Si (Ge , Sn) (H, X) may be formed. Further, when forming by the sputtering method, for example, Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases is used.
, Or two or three of the target and a target composed of Ge and / or Sn, or a mixture of Si and Ge and / or Sn. Depending on the requirement, a raw material gas for Ge supply and / or Sn supply diluted with a diluting gas such as He or Ar may be supplied with a gas for introducing hydrogen atoms (H) or / and halogen atoms (X) as necessary. It is formed by introducing it into a deposition chamber for sputtering and forming a plasma atmosphere of a desired gas. Germanium atom and /
Or, if the distribution of tin atoms is to be non-uniform,
The target may be sputtered while controlling the gas flow rate of the source gas for supplying and / or supplying Sn according to a desired change rate curve.

In the case of the ion plating method, for example, polycrystal silicon or single crystal silicon and polycrystal germanium or monocrystal germanium and / or polycrystal tin or monocrystal tin are housed in a vapor deposition board as evaporation sources, and the vaporization is performed. The source is heated and evaporated by a resistance heating method, an electron beam method (EB method), or the like, and the flying evaporated material is passed through a desired gas plasma atmosphere.
It can be carried out in the same manner as in the case of the sputtering method.

I composed of Non-Si (Ge, Sn) (H, X) by HRCVD I
In order to form the R absorption layer, for example, the raw material gas for supplying Si and the raw material gas for supplying Ge and / or the raw material gas for supplying Sn can be separately separated as necessary, or together, the inside of the deposition chamber can be depressurized. Is introduced into the activation space provided in the preceding stage in a desired gas pressure state to generate a glow discharge or heat in the activation space to generate active species (A), and hydrogen atoms are generated. The raw material gas for introducing (H) and / or the raw material gas for introducing halogen atom (X) is similarly introduced into another activation space to generate active species (B), and active species (A) and active species ( B) may be separately introduced into the deposition chamber to form a layer made of Non-Si (Ge, Sn) (H, X) on a surface of a predetermined support which is installed at a predetermined position in advance. Further, in order to contain germanium atoms and / or tin atoms in a non-uniform distribution state, while controlling the gas flow rate of the raw material gas for Ge supply and / or Sn supply according to a desired rate-of-change curve, Non-Si ( A layer made of Ge, Sn) (H, X) may be formed.

I composed of Non-Si (Ge, Sn) (H, X) by FOCVD method I
To form the R absorption layer, for example, the raw material gas for supplying Si, the raw material gas for supplying Ge and / or the raw material gas for supplying Sn may be separately or together, if necessary, placed in a deposition chamber. Introduced under a desired gas pressure condition, further introducing halogen (X) gas into the deposition chamber under a desired gas pressure condition separately from the raw material gas, and chemically reacting these gases within the deposition chamber to a predetermined position. A layer made of Non-Si (Ge, Sn) (H, X) may be formed on the surface of a predetermined support placed in the. Further, in order to contain the germanium atom and / or the tin atom in a non-uniform distribution state, while controlling the gas flow rate of the source gas for Ge supply and / or Sn supply according to the desired rate-of-change curve, Non-Si (Ge, Sn)
A layer of (H, X) may be formed.

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 gaseous state or a gasifiable silicon hydride ( Silanes) can be used effectively. Especially, SiH ₄ and Si ₂ H in terms of ease of handling during layer formation work and good Si supply efficiency.
₆ is mentioned as a preferable one.

GeH ₄ and Ge ₂ are the substances that can be used as the source gas for Ge supply.
_{H 6, Ge 3 H 8,} Ge 4 H 10, Ge 5 H 12, Ge 6 H 14, Ge 7 H 16, Ge
Germanium hydride in a gas state such as ₈ H ₁₈ or Ge ₉ H ₂₀ or which can be gasified can be effectively used. Particularly, it is easy to handle during layer formation work, and has good Ge supply efficiency. Then, GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferable.

The substances that can be used as the source gas for Sn supply are SnH ₄ and Sn _{2
H 6, Sn 3 H 8,} Sn 4 H 10, Sn 5 H 12, Sn 6 H 14, Sn 7 H 16, Sn
₈ H _18, hydrogenated tin can or gasified gas state such as Sn ₉ H ₂₀ may be mentioned as being effectively used, in particular layers making work at ease of handling, in terms of good, such as the Sn supply efficiency so
SnH ₄ , Sn ₂ H ₆ and Sn ₃ H ₈ are preferred.

As a raw material gas for introducing a halogen atom used in the present invention, many halogen compounds can be cited, for example, a halogen gas, a halide, an interhalogen compound, a halogen-substituted silane derivative or the like in a gas state or a gas. Preferred examples thereof include halogen compounds that can be converted.

Further, a silicon hydride compound containing a silicon atom and a halogen atom in a gas state or containing a gasifiable halogen atom 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 fluorine chlorine bromine, halogen gas of iodine, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Interhalogen compounds such as

As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, specifically, a halogenated silicon such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiBr ₄ may be mentioned as a preferable example. it can.

In the case of forming the characteristic electrophotographic light-receiving member of the present invention by the glow discharge method using such a silicon compound containing a halogen atom, Si is used together with the source gas for supplying Ge and / or Sn. Forming an IR absorption layer composed of Non-Si (Ge, Sn) (H, X) containing halogen atoms on a desired support without using silicon hydride gas as a source gas capable of supplying hydrogen You can

When an IR absorption layer containing halogen atoms is manufactured according to the glow discharge method, basically, for example, a silicon halide serving as a raw material gas for supplying Si and a germanium hydride and / or Sn serving as a raw material gas for supplying Ge are basically used. Introduce tin hydride, which is the raw material gas for supply, to the deposition chamber that forms the IR absorption layer at a predetermined mixing ratio and gas flow rate, and causes glow discharge to form a plasma atmosphere of these gases. By doing so, it is possible to form an IR absorption layer on a desired support, but in order to make it easier to control the introduction ratio of hydrogen atoms, hydrogen gas or hydrogen atom is added to these gases. It is also possible to form a layer by mixing a desired amount of a gas of a silicon compound containing a gas.

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

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

Further, when hydrogen atoms are introduced, a source gas for introducing hydrogen atoms, for example, H ₂ or the above-mentioned gas such as silanes and / or germanium hydride is introduced into the deposition chamber for spattering. It suffices to form a plasma atmosphere of gases.

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 I ₂ , SIH ₂ Cl ₂ , SiHCl ₂ , SiH ₂ Br ₂ , SiHBr _{2 and} other halogen-substituted silicon hydrides, and GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F, GeHC
l ₃ , GeH ₂ Cl ₂ , GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂
I ₂ , GeH ₃ I, etc. Halogen halides such as germanium halide, GeF ₄ ,, GeC
_{l 4, GeBr 4, GeI 4} , GeF 2, GeCl 2, GeBr 2, germanium halide such GeI ₂ or / and _{SnHF 3, SnH 2 F 2,} SnH 3 F,, Sn
HCl ₃ , SnH ₂ Cl ₂ ,, SnH ₃ Cl, SnHBr ₃ , SnH ₂ Br ₂ , SnH ₃ Br, SnHI ₃ , Sn
H ₂ I _2, SnH ₃ 1 bract halides components hydrogen atoms such as hydride halogenated tin I like, SnF _4, SnCl _4, SnB
Substances in the gas state or gasifiable such as tin halides such as r ₄ , SnI ₄ , SnF ₂ , SnCl ₂ , SnBr ₂ , SnI _{2 and the} like can also be mentioned as effective starting materials for forming the IR absorption layer. Among these substances, the halogen atom-containing halide is introduced into the layer at the same time as the introduction of the halogen atom into the layer during the formation of the IR absorption layer, since the hydrogen atom, which is extremely effective in controlling the electrical or photoelectric properties, is also introduced. In the present invention, it is preferably used as a raw material for introducing halogen.

In order to structurally introduce hydrogen atoms into the IR absorption layer, in addition to the above, Ge is supplied as H ₂ or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc. With germanium or germanium compounds, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge
_{4 H 10, Ge 5 H 12} , Ge 6 H 14, Ge 7 H 16, Ge 8 H 18, Ge 9 H 20 , etc. tin or tin compound for supplying germanium hydride and / or Sn between, or SnH ₄ , Sn ₂ H ₆ , Sn
₃ H ₈ ,, Sn ₄ H ₁₀ ,, Sn ₅ H ₁₂ ,, Sn ₆ H ₁₄ ,, Sn ₇ H ₁₆ ,, Sn ₈ H ₁₈ ,, Sn ₉ H
It can also be performed by causing tin hydride such as ₂₀ and silicon or a silicon compound for supplying Si to coexist in the deposition chamber to cause discharge.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms contained in the IR absorbing layer of the electrophotographic light-receiving member to be formed. (H + X) is preferably 0.01 to 40 atom%, more preferably 0.05 to 30 atom%, most preferably 0.1 to 25 atom%.
It is preferably set to atomic%.

In order to control the amount of hydrogen atoms (H) and / or halogen atoms (X) contained in the IR absorption layer, for example, the temperature of the support or / and hydrogen atoms (H), or halogen atoms (X) are contained. It suffices to control the amount of the starting material used for this purpose to be introduced into the deposition apparatus system, the discharge power, and the like.

In the present invention, a nitrogen atom and / or a carbon atom and / or an oxygen atom may be contained in the IR absorption layer by introducing a starting material for introducing a nitrogen atom and / or a carbon atom and / or an oxygen atom during the formation of the IR absorption layer. The substance may be used together with the above-mentioned starting material for forming the IR absorption layer, and the amount thereof may be controlled and contained in the formed layer.

To form IR absorption layer by glow discharge method, HRCVD method, FOCVD method As a starting material for introducing nitrogen atoms, at least a gaseous substance containing nitrogen atoms as a constituent atom or a gasified substance that can be gasified is used. 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. And, also in the desired mixing ratio, or silicon atoms (Si)
It is possible to mix and use a raw material gas having a constituent atom of and a raw material gas having three constituent atoms of a silicon atom (Si), a nitrogen atom (N) and a hydrogen atom (H).

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) is, for example, nitrogen (N ₂ ) or ammonia (having N as a constituent atom or N and H as a constituent atom). NH ₃ ), hydrazine (H ₂ NN
H ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N
₃ ) such as gaseous or gasifiable nitrogen, nitrogen compounds such as nitrides and azides. In addition to this, in addition to the introduction of the nitrogen atom (N), the introduction of the halogen atom (X) can also be performed, so that nitrogen trifluoride (F ₃
N), nitrogen tetrafluoride (F ₄ N ₂ ) and other nitrogen halide compounds.

To form the IR absorption layer by glow discharge method, HRCVD method, FOCVD method As a starting material for introducing carbon atoms, at least a gaseous substance containing carbon atoms as constituent atoms or a gasified substance that 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 carbon atoms (C) 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 carbon atoms (C) 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 atoms of silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H). It can be used by mixing with a raw material gas containing as 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 carbon atoms (C) as constituent atoms.

The starting material effectively used as a raw material gas for introducing carbon atoms (C) has C and H as constituent atoms.

Examples thereof include saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and acetylene hydrocarbons having 2 to 3 carbon atoms.

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

The source gas containing Si, C and H as constituent atoms is Si
Examples thereof include alkyl silicide such as (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

In addition to this, CF ₄ , CCl ₄ , CH ₃ CF ₃ can be introduced in addition to the introduction of halogen atoms (X) in addition to the introduction of carbon atoms (C).
And other halogenated carbon gases.

In order to form an IR absorption layer by glow discharge method, HRCVD method, FOCVD method, as a starting material for introducing oxygen atoms, a gaseous substance containing at least oxygen atoms as a constituent atom or a gasifiable substance is gasified. Most of the things 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 hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms as necessary. 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 in a desired mixing ratio, or a raw material gas containing silicon atoms (Si) as constituent atoms, and three atoms of silicon atoms (Si), oxygen atoms (O) and hydrogen atoms (H). It can be used by mixing with a raw material gas containing as 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 a raw material gas for introducing oxygen atoms (O) include, for example, oxygen (O ₂ ),
Ozone (O ₃ ), Nitric oxide (NO), Nitrogen dioxide (N
O ₂ ), nitrogen monoxide (N ₂ O), trinitrogen dioxide (N
₂ O ₃ ), trinitrogen oxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂
O ₅ ), nitric oxide (NO ₂ ), silicon atom (Si), oxygen atom (O), hydrogen atom (H) and constituent atoms, for example, disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H
₃ SiOSiH ₂ OSiH ₃ ) and other lower siloxanes.

To form the IR absorption layer by the sputtering method, use the IR
In forming the absorption layer, a single crystal or polycrystal Si wafer or Si ₃ N ₄ wafer, or a wafer containing Si and Si ₃ N ₄ mixed and / or a SiO ₂ wafer, or Si and SiO ₂ A wafer containing mixed and / or SiC wafer or a wafer containing mixed Si and SiC as a target,
These may be performed by spattering in various gas atmospheres.

For example, if a Si wafer is used as a target to contain nitrogen atoms, the raw material gas for introducing nitrogen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluting gas as needed. Then, the Si wafer is introduced into a deposition chamber for sputter, and gas plasma of these gases is formed to sputter the Si wafer.

Alternatively, Si and Si ₃ N ₄ may be used as separate targets or by using a single target mixture of Si and Si ₃ N ₄ in a diluting gas atmosphere as a gas for the spatula or It is formed by sputtering in a gas atmosphere containing at least hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms.

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

In the present invention, when the IR absorption layer is formed, the distribution concentration C (N) and / or C (C) and / or C (of nitrogen atom and / or carbon atom and / or oxygen atom contained in the layer is formed. O) in the layer thickness direction to form a layer having a desired depth profile in the layer thickness direction, in the case of glow discharge method, HRCVD method, FOCVD method,
A gas as a starting material for introducing nitrogen atoms and / or carbon atoms and / or oxygen atoms whose distribution concentration C (N) and / or C (C) and / or C (O) is to be changed, and its gas flow rate is desired. It is made by introducing it into the deposition chamber while appropriately changing it according to the change rate curve of.

For example, an 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 ordinary method such as manual operation or an external drive motor.

When formed by the sputtering method, the distribution concentration C (N) and / or C (C) and / or C (O) of nitrogen atoms and / or carbon atoms and / or oxygen atoms in the layer thickness direction is changed in the layer thickness direction. In order to form a desired depth profile of nitrogen atoms and / or carbon atoms and / or oxygen atoms in the layer thickness direction, first, as in the case of the glow discharge method, And / or by using a starting material for introducing carbon atoms and / or oxygen atoms in a gas state and appropriately changing the gas flow rate when introducing the gas into the deposition chamber.

Second, a target for sputtering, for example,
If a target in which Si and Si ₃ N ₄ are mixed is used, the mixing ratio of Si and Si ₃ N ₄ is changed in advance in the layer thickness direction of the target.

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

Amount of nitrogen atom (N), amount of oxygen atom (O), amount of carbon atom (C), or sum of amount of nitrogen atom and oxygen atom (N + O), or nitrogen contained in the IR absorption layer The sum of the amounts of atoms and carbon atoms (N + C), the sum of the amounts of carbon atoms and oxygen atoms (C + O), or the sum of the amounts of nitrogen atoms, carbon atoms and oxygen atoms (N + C + O) is preferably 0.01.
~ 40 atom%, more preferably 0.05-30 atom%, optimally
It is desirable to be 0.1 to 25 atom%.

In order to structurally introduce a substance (M _R ) that controls the conduction characteristics into the IR absorption layer, for example, a Group III atom or a Group V atom, a group III atom for introducing a group III atom may be used during layer formation. The starting material or the starting material for introducing the group V gas may be introduced into the deposition chamber in a gas state together with other starting materials for forming the IR absorption layer. As a material that can be used as a starting material for introducing the Group III atoms, it is desirable to employ a material that is gaseous at room temperature and atmospheric pressure or that can be easily gasified under at least the layer forming conditions. As such a starting material for introducing a Group III atom, specifically for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₇
Examples thereof include boron hydride such as H ₁₄ and halogenated boron such as BF ₃ , BCl ₂ and BBr ₃ . Besides this, AlCl ₃ ,, GaCl ₃ ,, Ga (CH ₃ ) ₃ ,, I
Examples thereof include nCl ₂ and TlCl ₃ .

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

Furthermore, the layer thickness of the IR absorption layer in the present invention is 0.05 to 0.05 from the viewpoint of obtaining desired electrophotographic characteristics and economic effects.
It is desirable that the thickness is 25 μ, preferably 0.07 to 20 μ, and optimally 0.1 to 15 μ.

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 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 is preferably 1 to 40 atom%, more preferably 5 to 30 atom%, and most preferably 10 to 20 atom%. desirable.

In the present invention, the layer thickness of CGL depends on the absorption coefficient of light of the light source used in the electrophotographic image forming apparatus so that desired electrophotographic characteristics can be obtained and economic effects, particularly sufficient charge generating ability can be obtained. It is appropriately determined according to the desire, and is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm, most preferably 1
It is desirable that the thickness is -10 μm.

In the present invention, in order to form a CGL composed of Non-Si (H, X), for example, a glow discharge method (low frequency CVD, high frequency CVD or microwave CVD) is used as in the case of the IR absorption layer described above.
AC discharge CVD, etc., or DC discharge CVD, etc.), ECR-CVD
It can be formed by various thin film deposition methods such as a sputtering method, a sputtering method, a vacuum deposition method, an ion plating method, a photo CVD method, a thermal CVD method, an HRCVD method, and a FOCVD method.

For example, in order to form CGL composed of Non-Si (H, X) by the glow discharge method, basically, silicon atoms (S
i) Supply source gas for supplying Si and hydrogen atom (H)
A raw material gas for introduction and / or a raw material gas for introducing a halogen atom (X) is introduced into a deposition chamber whose inside can be decompressed under a desired gas pressure state to cause glow discharge in the deposition chamber, and predetermined A layer made of Non-Si (H, X) may be formed on the surface of a predetermined support placed at a position. When the sputtering method is used, for example, a target made of Si is used in an atmosphere of an inert gas such as Ar or He or a mixed gas containing these gases as a base. , A hydrogen atom (H) or / and a halogen atom (X) is introduced into the deposition chamber for sputtering, and a plasma atmosphere of a desired gas is formed.

In the case of the ion plating method, for example, polycrystal silicon or single crystal silicon is accommodated in a vapor deposition board as an evaporation source, and this evaporation source is heated and vaporized by a resistance heating method or an electron beam method (EB method). In the same manner as in the sputtering method, except that the flying evaporated material is allowed to pass through a desired gas plasma atmosphere. In order to form CGL composed of Non-Si (H, X) by the HRCVD method, for example, the raw material gas for supplying Si can be a desired gas in the activation space provided in the previous stage in the deposition chamber where the pressure inside can be reduced. It is introduced under pressure to generate glow discharge or overheat in the activation space to generate active species (A), and a raw material gas for introducing hydrogen atom (H) and / or halogen. Similarly, the raw material gas for introducing the atom (X) is introduced into another activation space to generate the active species (B), and the active species (A) and the active species (B) are separately provided in the deposition chamber. After introduction, a layer made of Non-Si (H, X) may be formed on the surface of a predetermined support which is installed at a predetermined position in advance. Non-Si by FOCVD method
To form CGL composed of (H, X), for example, a raw material gas for supplying Si is introduced into a deposition chamber where the inside can be depressurized at a desired gas pressure state, and a halogen (X) gas is further added to the raw material gas. Separately from the above, the gas is introduced into the deposition chamber in a desired gas pressure state, these gases are chemically reacted in the deposition chamber, and No.
A layer other than n-Si (H, X) may be formed.

As the substance that can be used as the raw material gas for supplying Si used in the present invention, those in the gas state or gasifiable silicon hydrides (silanes) mentioned in the description of the IR absorption layer are effectively used. In particular, SiH ₄ and Si ₂ H ₆ are preferable as they are easy to handle during layer formation work and have good Si supply efficiency.

As a raw material gas for introducing a halogen atom used in the present invention, a halogen compound in a gas state or a gasifiable compound or a silicon hydride compound containing a halogen atom, which are mentioned in the description of the IR absorption layer, are preferably mentioned.

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 halogen atoms, basically, for example, in a deposition chamber for forming CGL by adjusting a predetermined gas flow rate of silicon halide as a raw material gas for supplying Si. It is possible to form CGL on a desired support by introducing and inducing a glow discharge to form a plasma atmosphere of these gases, but it becomes easier to control the introduction ratio of hydrogen atoms. To achieve this, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer.

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

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

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 I 2} , SiH 2 Cl 2, SiHCl 2, SiH 2 Br 2, SiHBr halogenated hydride such as ₂ silicon, starting for or gasification substance capable also valid CGL formation etc. gaseous state Can be listed 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 structurally introduce hydrogen atoms into CGL, in addition to the above, H ₂ or silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ and Si are supplied. It can also be carried out by causing the above-mentioned silicon or silicon compound to coexist in the deposition chamber to cause discharge.

In order to control the amount of hydrogen atoms (H) and / or halogen atoms (X) contained in CGL, for example, the temperature of the support or / and hydrogen atoms (H) or halogen atoms (X) are contained. 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 of the present invention comprises, 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 Si (H, X) (hereinafter abbreviated as "Non-SiM (C, N, O) (H, X)") and has charge transport characteristics satisfying desired electrophotographic characteristics. The carbon atoms, nitrogen atoms or oxygen atoms contained in the CTL may be contained in the CTL in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. It may be contained so that there may be a part. The substance (M) which controls the conductivity is contained in a state of being non-uniformly distributed in the layer thickness direction. That is,
The substance (M) is contained in a non-uniform distribution state such that the concentration of the substance (M) increases or decreases from the support side in the layer thickness direction. In any case, the substance (M) that controls conductivity,
When all of carbon atoms, nitrogen atoms and oxygen atoms are contained, they are contained in the entire layer region of CTL. In order that the distribution concentration of the substance controlling the conductivity (M) in the layer thickness direction of CTL becomes non-uniform in at least a part of the layer region of CTL,
The substance (M) is contained in CTL.

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

12 to 27 show typical examples of the state of distribution of the substance (M) contained in CTL in the layer thickness direction, which controls the conductivity.

12 to 27, the horizontal axis represents the distribution concentration C of the contained substance (Y), the vertical axis represents the layer thickness of CTL, t _B is the position of the end surface of CTL on the support side, and t _T is The position of the end surface of the CTL opposite to the support side is shown. That is, the CTL containing the substance (M) is layered from the t _B side toward the t _T side.

FIG. 12 shows a first typical example of the state of distribution of the substance (M) contained in CTL in the layer thickness direction.

In the example shown in FIG. 12, the distribution concentration C of the substance (M) has a constant value C ₅₇ from the interface position t _B where CGL and CTL contact to the position t ₁₆ and the substance (M) has a constant value. CT formed
It is contained in L and the concentration is C ₅₈ from the position t _{10 and the} interface position t _T from the position C _58.
It has been gradually and continuously reduced until. Interface position t
_{At T} , the distribution concentration C of the substance (M) is C ₅₉ .

In the example shown in FIG. 13, substances contained (M)
The distribution concentration C of C is the concentration C ₆₀ from the position t _B to the position t _T.
Gradually decreasing continuously from the concentration C ₆₁ at the position t _T.
The distribution state is such that

In the case of FIG. 14, the distribution concentration C of the substance (M) is constant with the concentration C ₆₂ from the position t _B to the position t _17.
It is gradually and continuously reduced from C ₆₃ between ₁₇ and the position t _T, and the distribution concentration C is substantially zero at the position t _T (here, substantially zero is the detection limit amount). In the case of FIG. 15, the distribution concentration C of the substance (M) is at the position t _B.
Up to more position t _T, is reduced continuously and gradually from the concentration C _64, it is substantially zero at the position t _T.

In the example shown in FIG. 16, the distribution concentration C of the substance (M)
Between the positions t _B and t ₁₈ has a constant value of the density C ₆₅ , and the position t _T has the density C ₆₆ . 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. 17, from the position t _B to the position t _T , the distribution concentration C of the substance (M) is linearly decreased from the concentration C ₆₇ to substantially zero.

In the example shown in FIG. 18, substances contained (M)
The distribution density C of C is gradually reduced from C ₆₈ until it reaches the position t _T from the position t _B, and becomes a distribution state where it becomes C ₆₉ at the position t _T.

In the example shown in FIG. 19, the distribution concentration C of the substance (M) takes a constant value of C ₇₀ from the position t _B to the position t ₁₉ .
From the position t ₁₉ to the position t _T , the distribution state is such that it decreases linearly from C ₇₁ to C ₇₂ .

In the example shown in FIG. 20, the distribution concentration C of the substance (M) gradually and continuously increases from C ₇₅ to C ₇₄ from the position t _B to the position t _20, and from the position t ₂₀ to C _73. A distribution state is formed such that a constant value of t reaches the position t _T.

In the example shown in FIG. 21, the distribution concentration C of the substance (M)
Has a distribution state in which it gradually increases continuously from C ₇₇ to C ₇₆ from the position t _B to the position t _T.

In the example shown in FIG. 22, the distribution concentration C of the substance (M) is substantially zero to C from the position t _B to the position t _21.
The distribution gradually increases continuously up to ₇₉ , takes a constant value of C ₇₈ from the position t _21, and reaches the position t _T.

In the example shown in FIG. 23, the distribution concentration C of the substance (M) is substantially zero to C ₈₀ from the position t _B to the position t _T.
It forms a distribution state that gradually increases continuously until.

In the example shown in FIG. 24, material distribution concentration C (M) is increased from C ₈₂ up to the position t ₂₂ from the position t _B C ₈₁ to a linear function manner, the C ₈₁ is the position t ₂₂ A distribution state is formed such that a constant value is obtained and the position reaches the position t _T.

In the example shown in FIG. 25, the distribution concentration C of the substance (M)
Is substantially zero to C ₈ from the position t _B to the position t _T.
A distribution state is formed which increases linearly up to 3.

In the example shown in FIG. 26, the distribution concentration C of the substance (M) 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. 27, material distribution concentration C (M) 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 A distribution state is formed such that a constant value is obtained and the position reaches the position t _T.

28 to 37 show carbon atoms (C) contained in CTL,
A typical example of the distribution state of nitrogen atoms (N) and oxygen atoms (O) in the layer thickness direction is shown. In the following explanation,
For convenience, the carbon atom (C), the nitrogen atom (N) and the oxygen atom (O) are collectively referred to as “atom (Y)”.

28 to 37, the horizontal axis represents the distribution concentration C of contained atoms (Y), the vertical axis represents the layer thickness of CTL, t _B is the position of the end surface of CTL on the support side, and t _T is The position of the end surface of the CTL opposite to the support side is shown. That is, the CTL containing atoms (Y) is layered from the t _B side toward the t _T side.

FIG. 28 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. 28, from the interface position t _B to the position t ₂₄ , the layer in which the atom (Y) is formed while the distribution concentration C of the atom (Y) has a constant value C ₈₉ . It is contained in the region (Y), and the interface concentration t _T from the distribution concentration value C ₉₀ from the position t ₂₄
It has been gradually and continuously reduced until. Interface position t
_{At T} , the distribution concentration C of atoms (Y) has a value C ₉₁ .

In the example shown in FIG. 29, the contained atom (Y)
The distribution density C is gradually decreased continuously from the distribution density value C ₉₂ to the position t _T from the position t _B, and becomes the distribution density value C ₉₃ at the position t _T.

In the case of FIG. 30, from the position t _B to the position t ₂₅ , the distribution concentration C of the atom (Y) is a constant value with the distribution concentration value C ₄₂ ,
Between the position t ₂₅ and position t _T, is gradually reduced continuously, at position t _T, the distribution concentration C is substantially zero (where substantially less than the detection limit amount is zero The same applies to the meaning of "substantially zero" hereafter). In the case of FIG. 31, the distribution concentration C of the atom (Y) is continuously and gradually reduced from the concentration value C ₉₆ from the position t _B to the position t _T , and becomes substantially zero at the position t _T. Has been done.

In the example shown in FIG. 32, the distribution concentration C of atoms (Y)
Between the position t _B and the position t ₂₆ , the distribution density value C ₉₇
Is a constant value, and is a distribution density value C _{98 at} the position t _T. Between the position t ₂₆ and the position t _T , the distribution concentration C is linearly reduced from the position t ₂₆ to the position t _T.

In the example shown in FIG. 22, from the position t _B to the position t _T , the distribution concentration C of the atom (Y) decreases linearly as the distribution concentration value C99 reaches substantially zero. There is.

In the example shown in FIG. 34, the contained atom (Y)
The distribution density C of the value C ₁₀₀ from the position t _B to the position t _T
A distribution state is formed in which the value C ₁₀₁ gradually decreases continuously from the value of C ₁₀₁ at the position t _T.

In the example shown in FIG. 35, the distribution concentration C of atoms (Y) has a constant value C ₁₀₂ from the position t _B to the position t _27, and the value C ₁₀₃ from the position t ₂₇ to the position t _T. The distribution state is a linearly decreasing value up to the value C ₁₀₄ .

In the example shown in FIG. 36, the distribution concentration C of the atom (Y) has a constant value C ₁₀₅ from the position t _B to the position t _T.

The examples shown in FIGS. 28 to 35 are all t _T
Although the distribution concentration C of the atom (Y) is higher on the t _B side than on the t side, the t _T side and the t _B side are completely reversed, and the t _T side is on the t _T side rather than the t _B side. The distribution density C may be large. For example, in the example shown in FIG. 37, when the t _T side and the t _B side are reversed in FIG. 12, the distribution concentration C of atoms (Y) is the value C from the interface position t _B to the position t _{28. 108}
And a constant, becomes C ₁₀₇ at position t ₂₉ gradually increases continuously from C ₁₀₈ to t ₂₉ from t _28, a constant value until the value C ₁₀₆ interface position t _T from the position t _29.

Examples of the substance (M) that controls the conductivity include the same substances as the substances (M _R ) that control the conductivity described in the description of the IR absorption layer.

In the present invention, by containing a group III atom or a group V atom as the substance (M) for controlling conductivity in the entire layer region of CTL3, the effect of mainly controlling the conductivity type and / or the conductivity 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, and most preferably 1 × 10 ^−2. ~ 50 atoms
It is desirable to be ppm.

In addition, the whole layer region of CTL3 in 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%, Preferably 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 /
Also, halogen atoms can compensate for dangling bonds of silicon atoms to 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 μ from the viewpoint of obtaining desired electrophotographic characteristics and economic effects.
Is desirable.

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.

The starting materials for introducing nitrogen atoms, for introducing carbon atoms, and for introducing oxygen atoms, which are used when forming a CTL by glow discharge method, HRCVD method, FOCVD method, are the same as those mentioned in the description of the IR absorption layer. You can list the concrete ones.

To form a CTL by the sputtering method, a single crystal or polycrystal 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 Si and SiC mixed therein may be used as a target, and these may be sputtered in various gas atmospheres.

For example, if a Si wafer is used as a target to contain nitrogen atoms, the raw material gas for introducing nitrogen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluting gas as needed. Then, the Si wafer is introduced into a deposition chamber for sputter, and gas plasma of these gases is formed to sputter the Si wafer.

In addition, separately, Si and Si ₃ N ₄ are used as separate targets or by using a single target in which Si and Si ₃ N ₄ are mixed, in a diluting gas atmosphere as a gas for spatters. Alternatively, the sputtering is performed in a gas atmosphere containing at least a hydrogen atom (H) and / or a halogen atom (X) as constituent atoms.

As the raw material gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms, even 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, It can 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 a layer having the above, in the case of glow discharge method HRCVD method or FDCVD method, a starting material gas for introducing atoms (Y) whose distribution concentration C (Y) is to be changed, and the gas flow rate thereof are desired. It is made by appropriately changing it according to the rate of change curve and introducing it into the deposition chamber.

For example, an 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 ordinary 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
In order 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 flow rate when the gas is introduced into the deposition chamber. Is appropriately changed as desired.

Second, a target for sputtering, for example,
If a target in which Si and Si ₃ N ₄ are mixed is used, the mixing ratio of Si and Si ₃ N ₄ is changed in advance in the layer thickness direction of the target.

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 the conduction property, for example,
Structurally introducing a group III atom or a group V atom, the starting material or group V
The starting material for introducing the group may be introduced into the deposition chamber in a gas state together with other starting materials for forming CTL.

Non-Si CGLCTL with properties that can achieve the object of the present invention
A-Si containing a hydrogen atom and / or a halogen atom as (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 1 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 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, most preferably 1 × 10 ^−2. ~ 1 Torr is desirable.

In the present invention, the above-mentioned ranges are mentioned as the desirable numerical ranges of the support temperature and the gas pressure for producing each of the layers, but these layer-forming 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.

As Non-Si (H, X) constituting CGLCTL, polycrystalline silicon containing hydrogen atoms and / or halogen atoms (hereinafter referred to as “poly-Si (H, X)”) is selected and configured. In this case, there are various methods for forming the layer, and for example, the following method can be given.

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 amorphous film on the surface of the support, that is, form a film on the support whose temperature is about 250 ° C. by a plasma CVD method and subject the amorphous 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.

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.

Next, a method for manufacturing a photoconductive member formed by a high frequency (hereinafter abbreviated as RF) glow discharge decomposition method will be described.

FIG. 38 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 in the figure, the raw material gas for forming the respective layers of the present invention is sealed, and as an example, for example, 1011 SiH ₄ gas ( Purity 99.999% cylinder, 1012 H ₂ gas (purity 99.99%)
9%) cylinder, 1013 is B ₂ H ₆ gas diluted with H ₂ gas (purity 99.999% or less abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 1014 is N
O gas (purity 99.5%) cylinder, 1015 is GeH ₄ gas (purity 99.
999%) cylinder, 1016 is 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.

As an example of forming a light receiving member for electrophotography, IR
The absorbent layer forming gas, SiH ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, GeH ₄ gas, SiH ₄ gas as a gas for CGL form, H ₂ gas, SiH ₄ gas as a CTL forming gas , NH ₃ gas, B ₂ H ₆
Take the case of using / H ₂ gas.

A gas cylinder is required to allow these gases to flow into the reaction chamber 1001.
Check that the valves 1051 to 1057 of 1011 to 1017 and the leak valve 1003 of the reaction chamber 1011 are closed, and the inflow valves 1031 to 1037, the outflow valves 1041 to 1047, and the auxiliary valve 1070.
After confirming that is opened, first, the main valve 1002 is opened to exhaust 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
From H ₂ gas, gas cylinder 1013 from B ₂ H ₆ / H ₂ gas, gas cylinder 1014 from NO gas, gas cylinder 1015 from GeH ₄ gas,
NH ₃ gas from gas cylinder 1016 and CH ₄ gas from gas cylinder 1017 are introduced by opening valves 1051 to 1054, 1056, 1057, and each gas pressure is adjusted to 2 kg / g by pressure regulators 1061 to 1065, 1066, 1067.
Adjust to cm ² .

Next, the inflow valves 1031 to 1037 are gradually opened to introduce the above gases into the mass flow controllers 1021 to 1027.

Further, 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 IR absorption layer and the CGLCTL layers are formed on the base cylinder 1007.

Outflow valves 1041, 1043, 1044, 10 for forming IR absorption layer
45 and auxiliary valve 1070 are gradually opened to SiH ₄ gas, B ₂
H ₆ / H ₂ gas NO gas GeH ₄ gas is caused to flow into the reaction chamber 1001. At this time, the outflow valves 1041, 1043, 1044, 1045 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 GeH ₄ gas flow rate have the desired values, and the reaction The opening of the main valve 1002 is adjusted while observing the vacuum gauge 1004 so that the pressure in the room 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 1001, and the formation of the IR absorption layer on the substrate cylinder is started. After the desired film layer is formed, the RF glow discharge is stopped, and the outflow valves 1041, 1043, 1044, 1045 are closed to stop the gas flow into the reaction chamber, and the formation of the IR absorption layer is completed.

CGL is formed on the IR absorption 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 100.
Inflow into 1. 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 are at desired values, and the main while watching the vacuum gauge 1004 so that the pressure in the reaction chamber is at 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, 1045 are adjusted so that the SiH ₄ gas flow rate B ₂ H ₆ gas flow rate NH ₃ gas flow rate becomes a desired value, and the reaction chamber pressure becomes a desired value. While watching the vacuum gauge 1004, adjust the opening of the main valve 1002. 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 CTL on the substrate cylinder is started. 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.

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 pipes from the outflow valves 1041 to 1046 to the reaction chamber 1001. In order to avoid remaining in the inside, the outflow valves 1041 to 1046 are closed, the auxiliary valve 1070 is opened, the main valve 1002 is fully opened, and the operation of temporarily exhausting the system to a high vacuum is performed.

Further, 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. 39 shows an apparatus 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, and as an example, SiH ₄ gas is used in 2011. (Purity 99.999%) cylinder, H ₂ gas in 2012 (Purity 99.999%)
999%) cylinder, B ₂ H ₆ gas diluted with H ₂ gas in 2013 (purity 99.999%, hereinafter abbreviated as “B ₂ H ₆ / H ₂ ”) cylinder, NO gas in 2014 (purity 99.5%) Cylinder, 2015 is GeH ₄ gas (purity 99.999%), 2016 is NH ₃ gas (purity 99.999%)
Cylinder 2017 is a CH ₄ gas (purity 99.999%) cylinder.

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

As an example of forming a light receiving member for electrophotography, IR
SiH ₄ gas B ₂ H ₆ / H ₂ gas NO gas GeH _{4 as the} absorption layer forming gas
The case where SiH ₄ gas H ₂ gas is used as the CTL forming gas and SiH ₄ gas NH ₃ gas B ₂ H ₆ / H ₂ gas is used as the CTL forming gas will be described.

A gas cylinder is required to allow these gases to flow into the reaction chamber 2001.
Confirm that valves 2051 to 2057 of 2011-2017 and leak valve 2003 of reaction chamber 2011 are closed, and that inflow valves 2031 to 2037, outflow valves 2041 to 2047, and auxiliary valve 2070.
After confirming that the reactor is opened, the main valve 2002 is first opened 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
H ₂ gas, B ₂ H ₆ / H ₂ gas from gas cylinder 2013, NO gas from gas cylinder 2014, GeH ₄ gas from gas cylinder 2015,
NH ₃ gas from gas cylinder 2016, CH ₄ from gas cylinder 2017
Gas is introduced by opening valves 2051 to 2057 and pressure regulator 20
Adjust each gas pressure to 2 Kg / cm ² by 61-2067.

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 IR absorption layer, GCL, and CTL layers are formed on the base cylinder 1007.

To form the IR absorption layer, the outflow valves 2041,2043,2044,2
045 and auxiliary valve 2070 are gradually opened to SiH ₄ gas, B ₂
H ₆ / H ₂ gas NO gas GeH ₄ gas is caused to flow into the reaction chamber 2001. At this time, the outflow valves 2041, 2043, 2044, 2045 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 GeH ₄ gas flow rate have desired values, and The opening of the main valve 2002 is adjusted while observing the vacuum gauge 2004 so that the pressure in the reaction chamber becomes a desired value. After that, the microwave power source 2008 is set to a desired power, and a μW glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 2010,
Start forming the charge injection blocking layer on the substrate cylinder.
After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valves 2041, 2043, 2044, 2045 are closed to stop the gas from flowing into the reaction chamber, and the formation of the charge injection blocking layer is completed. .

CGL is formed on the IR absorption layer formed as described above.

In order to form CGL, the outflow valve 20412042 and the auxiliary valve 2070 are gradually opened to supply SiH ₄ gas and H ₂ gas to the reaction chamber 2001.
Let it flow in. 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 reach desired values, and the pressure inside the reaction chamber is adjusted to a desired value while observing the vacuum gauge 2004. Adjust the opening of the main 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 CGL on the substrate cylinder is started. After the desired film thickness is formed, the μW glow discharge is stopped, the outflow valves 2041 and 2042 are closed to stop the gas inflow into the reaction chamber, and the CGL formation is completed.

CTLs are formed on CGLs formed as above.

To form the CTL, the outflow valves 2041, 2043, 2045 and the auxiliary valve 2070 are gradually opened to SiH ₄ gas, B ₂ H ₆ gas NH
₃ Gas is flowed into the reaction chamber 2001. At this time, the outflow valves 2041, 2043, and 2045 are adjusted so that the SiH ₄ gas flow rate and the B ₂ H ₆ gas flow rate NH ₃ gas flow rate have desired values, and the pressure in the reaction chamber reaches a 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 forming the desired film thickness, stop the μW glow discharge,
The outflow valves 2041, 2043, 2045 are closed to stop the inflow of gas into the reaction chamber, and the formation of CTL is completed.

It goes without saying that all the outflow valves other than the gas necessary for forming the respective layers are closed, and the respective gas flows from the outflow valves 2041 to 2046 into the reaction chamber 2001 inside the reaction chamber 2001.
To avoid remaining in the piping leading to 2001, close the outflow valves 2041 to 2046, open the auxiliary valve 2070, and fully open the main valve 2002 to temporarily exhaust the system to a high vacuum as necessary. Do it.

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.

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 the electrophotographic light-receiving member formed by the HRCVD method will be described.

FIG. 40 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the HRCVD method.

In FIG. 40, 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, and 3020 is an activated species introduction pipe generated from the activation chamber (B). A method for producing an electrophotographic light-receiving member having a layer structure according to the present invention on a cylindrical substrate using this apparatus will be specifically described.

In a row, Al is used as the cylindrical substrate, and SiH ₄ , GeH ₄ , B ₂ H ₆ , NO as the IR absorption layer forming gas.
H ₂ , SiH ₄ H ₂ was used as the CGL forming gas, and SiH ₄ , SiF ₄ , CH ₄ H ₂ , and B ₂ H ₆ were used as the CTL forming gas.

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

To form the IR absorption 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 blown out through the introduction pipe 3005. A tube 3008 led to a film forming chamber 3001. On the other hand, from the cylinder 3013 SiH ₄ gas, from 3014 B ₂ H ₆
Gas from 3015, NO gas from 3016, CH ₄ gas from 3016, and GeH ₄ gas and SiF ₄ gas from a cylinder (not shown) are introduced into the activation chamber (B) 3017 through an introduction pipe 3019, and a microwave plasma generator 3018 is introduced.
After the activation treatment by, the gas was introduced into the film forming chamber 3001 through the introduction pipe 3020 and the blowing pipe 3009. At this time, the gas flow rate,
The internal pressure and the microwave power are set to desired values.

The Al cylindrical base 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, H ₂ gas from a cylinder 3012 and SiH ₄ gas from 3013 were supplied on the above IR absorption layer to obtain CGL.
On the CGL, from the cylinder 3012 to H ₂ gas 3013 to SiH ₄ gas
A B ₂ H ₆ gas from 3014, a CH ₄ gas from 3016, and a SiF ₄ gas from a cylinder (not shown) were supplied to sequentially form CTLs, thereby forming a light receiving member for electrophotography.

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

Fig. 41 shows an apparatus for manufacturing a light receiving member for electrophotography by the FOCVD method.

Gas cylinders 4011, 4012, 4013, 4014, 4015, 4016, 4017 in the figure, the source gas for forming each layer of the present invention is sealed, as an example, for example 4011 SiH ₄
Gas (99.999% purity) cylinder, in 4012 H ₂ gas (purity 9
9.999%) cylinder, 4013 is B ₂ H ₆ gas diluted with H ₂ (purity 99.999% or less, abbreviated as “B ₂ H ₆ / H ₂ ”) cylinder, 4
014 is a NO gas (purity 99.5%) cylinder, 4015 is a GeH ₄ gas (purity 99.999% or less) cylinder, 4016 is CH ₄ gas (purity 99.99%).
99%) cylinder, 4017 is F ₂ gas (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 specifically described.

As an example of forming a light receiving member for electrophotography, IR
SiH ₄ gas, B ₂ H ₆ H ₂ gas, NO gas, GeH for absorption layer forming gas
₄ gases, F ₂ gas as CGL forming gas, SiH ₄ gas, H ₂ gas, F ₂ gas as CTL forming gas SiH ₄ gas, CH ₄ gas, B ₂
Take the case of using H ₆ 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 ~ 4058 are introduced into the vacuum chamber of 4020 ~ 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 substrate heating heater that heats the substrate 4060 to an appropriate temperature during film formation, preheats the substrate 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) via a lead wire (not shown).

In addition, the base cylinder 4060 is used to form a uniform film.
It is rotated by 62 rotation mechanisms.

In order to introduce the gas of 4011 to 4017 into 4001, it has to be introduced slowly by various valve operations when the inside of the chamber of 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 by the heater 4061 to a desired temperature between 50 and 350 ° C.

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 IR absorption layer, CGL, and CTL.

To form the IR absorption layer, the valves 4046 to 4049 are opened, and the outflow valves 4031, 4033, 4034, 4035 and the auxiliary valve 4060 are gradually opened to SiH ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, GeH. ₄ Gas is allowed to flow into the reaction chamber 4001. At this time, SiH ₄ gas flow rate, B ₂
Adjust the outflow valves 4031, 4032, 4033, 4034, 4035 so that the H ₆ / H ₂ gas flow rate, the NO gas flow rate, and the GeH ₄ gas flow rate reach the desired values, and set the pressure in the reaction chamber to the desired value. Adjust the opening of the main valve 4002 while watching the vacuum gauge (not shown).

Next, open the 4052, watching the mass flow meter 4059,
The valve of 4037 is gradually opened to the desired flow rate, the setting of the flow rate is completed, and the formation of the IR absorption layer is completed after the time for forming the IR absorption layer to the desired film thickness.

A CGL layer is formed on the IR absorption layer prepared as described above by the same operation as described above. With respect to each layer, a required gas may be allowed to flow, and valves may be operated in the same manner as the IR absorption layer.

〔Example〕

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

<Example 1> Using the manufacturing apparatus shown in FIG. 38, an electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished by RF glow discharge according to the preparation conditions shown in Table 1 Table 2 and Table 3.

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 conditions were set under various conditions. Check the electrophotographic characteristics such as charging ability, sensitivity, residual potential, ghost, etc.
The decrease in charging ability after acceleration durability equivalent to 0,000 sheets, surface abrasion, increase in image defects, etc. were investigated.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Furthermore, the scratch resistance was examined by applying a constant load to a needle with a spherical tip to scratch 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. 38, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Table 1, Table 2, Table 6 and Table 7, and the same evaluation was performed. I went.

The results are shown in Table 8.

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

<Example 3> Using the manufacturing apparatus shown in Fig. 38, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Table 1, Table 2, Table 9 and Table 10, and the same evaluation was performed. I went.

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. 39, the photoreceptive material for electrophotography was placed on an aluminum cylinder mirror-finished by the microwave CVD method according to the conditions shown in Table 12, Table 13, Table 14 and Table 15. The member was formed.

The prepared electrophotographic light-receiving member is 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 is performed under various conditions. Performance, sensitivity, residual potential,
The electrophotographic characteristics such as ghost were checked, and the deterioration of charging ability, surface scraping, increase of image defects, etc. were investigated after 2 million sheets worth of accelerated real machine durability.

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 16 shows the comprehensive evaluation results.

As shown in Table 16, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 5> Using the manufacturing apparatus shown in FIG. 40, a photoreceptive member for electrophotography was formed on an aluminum cylinder that was mirror-finished by the HRCVD method according to the conditions shown in Tables 17 to 20. 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. , The electrophotographic characteristics such as sensitivity, residual potential, and ghost were checked, and the deterioration of charging ability, surface scraping, increase of image defects, etc. were examined 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. Furthermore, the scratch resistance was examined by applying a constant load to a needle having a spherical tip to scratch the drum surface. Table 21 shows the comprehensive evaluation results.

As shown in Table 21, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 6> Using the manufacturing apparatus shown in FIG.
The light-receiving member for electrophotography was formed on an aluminum cylinder that was mirror-finished according to the preparation conditions shown in Tables, 24, and 25.

The prepared electrophotographic light-receiving member is 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,
Under various conditions, check the electrophotographic characteristics such as initial chargeability, sensitivity, residual potential, ghost, etc., and also reduce chargeability, surface abrasion, and increase of image defects after 2 million sheets of accelerated real machine durability. Etc.

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 26 shows the comprehensive evaluation results.

As shown in Table 26, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Embodiment 7> Mirror-finished cylinders are further subjected to lathe processing with a sword bite having various angles to obtain cylinders having various sectional patterns as shown in Table 28 with a sectional shape as shown in FIG. 46. I prepared multiple books. The cylinder was sequentially set in the manufacturing apparatus shown in FIG. 38 and subjected to drum making under the making conditions shown in Table 27. The drums thus prepared were subjected to various evaluations by 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 shown in Table 29 were obtained.

<Embodiment 8> The surface of a cylinder that has been mirror-finished is continuously exposed to the dropping of a large number of bearing balls, and a so-called surface dimple forming treatment that causes innumerable dents on the cylinder surface is performed. A plurality of cylinders having the cross-sectional shape shown in the figure and various cross-sectional patterns as shown in Table 31 were prepared.
The cylinder is sequentially set in the manufacturing apparatus shown in FIG.
The drums were prepared under the preparation conditions shown in Table 30. The drums thus prepared were 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 32 were obtained.

<Example 9> Using the manufacturing apparatus shown in Fig. 38, a drum was prepared in the same manner as in Example 1 under the conditions shown in Table 33, Table 34, Table 35, and Table 36, and the same evaluation was performed.

The results are shown in Table 37.

As shown in Table 37, 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, durability and the like. Further, its electrical characteristics are stable, and an image obtained by using it has a high density and a clear halftone, and is very 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 of carbon atom, nitrogen atom, and oxygen atom, it is possible to freely design according to the characteristics of each layer, and to generate electric charge and CGL to C
Immediate injection and transport to TL, especially excellent chargeability sensitivity, little residual potential ghost, high resolution in images, and stable and repeatable high quality images .

[Brief description of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of a light-receiving member for electrophotography of the present invention, and FIGS. 2 to 5 are each a concavo-convex shape on the surface of a support and a method for producing the concavo-convex shape. 6 to 11 are explanatory views for explaining the distribution state of atoms (GS) contained in the IR absorption layer, and FIGS. 12 to 27 are respectively Explanatory drawing of distribution state of substance (M) contained in CTL, FIGS. 28 to 37 illustrate distribution state of carbon atom and / or oxygen atom and / or nitrogen atom contained in CTL, respectively. 38 is an example of a device 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 device by a glow discharge method using RF, The figure shows an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention. Schematic explanatory view of the manufacturing apparatus by glow discharge method using microwave, FIG. 40 is an example of the apparatus for forming the light-receiving layer of the light-receiving member for electrophotography of the present invention, of the manufacturing apparatus by HRCVD method FIG. 41 is a schematic explanatory view of an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention. FIG. 42 is a schematic explanatory view of a manufacturing apparatus by the FOCVD method, and FIG. FIG. 43 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 electrophotographic light-receiving member is formed by using RF glow discharge, and FIG. 43 shows the electrophotographic light-receiving member of the present invention. FIG. 44 is a diagram showing changes in the flow rate of an impurity gas and a doping gas during film formation when a CTL is formed by using a microwave glow discharge. FIG. 44 shows the CTL of the photoreceptive member for electrophotography according to the present invention.
Showing changes in the flow rate of the impurity gas and the doping gas during the film formation when 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. FIG. 47 is an enlarged view of a cylinder cross section in the case of a letter shape, FIG. 47 is an enlarged view of a cylinder cross section when the surface of the cylinder substrate when forming the electrophotographic light-receiving member of the present invention is subjected to so-called dimple processing, 48 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. About Fig. 1, 100 ... Photoreceptive layer 101 ... Support 102 ... IR absorption layer 103 ... CGL 104 ... CTL 105 ... Free surface About Fig. 3, Fig. 4, 301401 ... Support 302402 ... … Support surface 303403 …… Rigid spherical sphere 304404 …… Spherical trace depression About Figure 5, 500 …… Photoreceptive layer 501 …… Support 502 …… IR absorption layer 503 …… CGL 504 …… CTL 505 …… Free Surface In Fig. 38, 1001 ...... Reaction chamber 1002 ...... Main exhaust valve 1003 ...... Reaction chamber leak valve 1004 ...... Vacuum gauge 1007 ...... Cylinder substrate 1008 ...... Heater for substrate heating 1009 ...... Cylinder substrate rotation motor 1010 …… RF power supply 1011-1017 …… Raw gas cylinder 1021 ～ 1027 …… Mass flow controller 1031 ～ 1037 …… Gas inlet valve 1041 ～ 1047 …… Gas outlet valve 1051 ～ 1057 …… For raw material gas cylinder Valves 1061 to 1067 ...... Pressure regulator Regarding Fig. 39, 2001 ...... Reaction 2002 …… Main exhaust valve 2003 …… Reaction chamber leak valve 2004 …… Vacuum gauge 2005 …… Base heating heater 2006 …… Cylinder base 2007 …… Base rotation motor 2008 …… Microwave power supply 2009 …… Waveguide Tube 2010 …… Dielectric window 2011 ～ 2017 …… Raw material gas cylinder 2021 ～ 2027 …… Mass flow controller 2031 ～ 2037 …… Gas inflow valve 2041 ～ 2047 …… Gas outflow valve 2051 ～ 2057 …… Raw material gas ・Cylinder valves 2061 to 1267 ...... Pressure regulator Regarding Fig. 40, 3001 …… Film formation chamber 3002 …… Activation chamber (A) 30033018 …… Microwave plasma generator 30043019 …… Raw material gas introduction pipe 30053020 …… Active Seed introduction pipe 3006 …… Motor 3007 …… Cylinder substrate heating heater 30083009 …… Blowout pipe 3010 …… Cylinder substrate 3011 …… Main exhaust valve 3012-3016 …… Source gas cylinder 3017 …… Activation chamber (B ) Regarding Fig. 41, 4001 ...... Reaction chamber 4002 ...... Main exhaust valve 4011-4017 …… Raw material gas cylinder 40204021 …… 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 rotation motor

 ─────────────────────────────────────────────────── ─── 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 62-5253 (JP, A) JP 62-5250 (JP, A) JP 62-115457 (JP, A) JP 62-115456 (JP, A) )

Claims (1)

[Claims] 1. A support and a light-receiving layer having a layer structure in which a long-wavelength light absorption layer, a charge generation layer and a charge transport layer are laminated in this order from the support side. Having, the long-wavelength light absorption layer is a silicon atom as a matrix, at least one of a germanium atom and a tin atom,
It is composed of a non-single crystal material containing at least one of a hydrogen atom and a halogen atom, and the charge generation layer and the charge transport layer have a silicon atom as a matrix, and at least one of a hydrogen atom and a halogen atom. And a charge-transporting layer containing at least one of a carbon atom, a nitrogen atom and an oxygen atom, and containing a group III or V group of the periodic table.
A photoreceptive member for electrophotography, comprising at least a portion containing an atom belonging to the group in a non-uniform distribution state having a portion whose concentration increases or decreases from the support side in the layer thickness direction.