JPH0797233B2 - Photoreceptive member for electrophotography - Google Patents

Description

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

[Description of Prior Art]

In the field of image formation, as a photoconductive material that constitutes the light-receiving layer in the light-receiving member for electrophotography, it has high sensitivity and a high SN ratio [photocurrent (Ip) / dark current (Id)], and It is required to have characteristics such as having absorption spectrum characteristics adapted to the spectrum characteristics, having fast photoresponsiveness and having a desired dark resistance value, and being harmless to a human body during use. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used as an office machine as an office machine, the pollution-free property at the time of use is an important point.

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

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

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

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

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

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

[Object of the Invention]

It is an object of the present invention to solve various problems in a 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, optical, and photoconductive properties are substantially stable regardless of the operating environment, are excellent in light fatigue resistance, and deteriorate even after repeated use. To provide a photoreceptive member for electrophotography having a photoreceptive layer composed of a material having a silicon atom as a base material, which is excellent in durability, moisture resistance, and has no or almost no residual potential observed. is there.

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

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

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

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

[Structure of Invention]

The electrophotographic light-receiving member of the present invention comprises a support and a long-wavelength light absorption layer (hereinafter abbreviated as “IR absorption layer”) on the support,
A charge-generating layer, a charge-transporting layer, and a surface layer, and a light-receiving layer having a layer structure laminated in this order from the support side.
L)) and the charge transport layer (hereinafter abbreviated as “CTL”) have a silicon atom as a matrix and a non-single-crystal material containing at least one of a hydrogen atom and a halogen atom (hereinafter ““ Non-Si (H, X) "), the surface layer has a silicon atom as a matrix, at least one of carbon atoms, nitrogen atoms and oxygen atoms,
It is composed of a non-single crystal material containing at least one of a hydrogen atom and a halogen atom, the long wavelength light absorbing layer further contains at least one of a germanium atom and a tin atom, and the charge transport layer is , A portion containing at least one of a carbon atom, a nitrogen atom and an oxygen atom, and the concentration of an atom belonging to Group III or V of the periodic table increases or decreases in the layer thickness direction from the support side. It is characterized by having at least a portion containing in a non-uniform distribution state.

[Action]

The electrophotographic light-receiving member of the present invention designed so as to have the above-mentioned layer structure can solve all of the above-mentioned problems, and is extremely excellent in electrical, optical and photoconductive properties. The characteristics, durability and operating environment characteristics are shown.

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

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

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

In addition, since the surface layer is provided on the surface, mechanical strength and electrical withstand voltage are dramatically improved, and it is possible to effectively prevent the injection of electric charges from the surface when subjected to a charging treatment. , Charging ability, use environment characteristics, durability and electrical durability are 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.

An electrophotographic light-receiving member 100 shown in FIG. 1 comprises an IR absorbing layer 103 on a support 101 for an electrophotographic light-receiving member,
CGL104 composed of Non-Si (H, X), composed of Non-Si (H, X), containing at least one of carbon, nitrogen and oxygen atoms and controlling conductivity CTL 105 having at least a portion containing the substance (M) in a non-uniform distribution state in the layer thickness direction, and a light receiving layer 102 having a layer structure including a surface layer 106. Surface layer 106
Has a free surface 107.

Support The support used in the present invention may be conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, Al, Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pb
And the like, or alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, 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 having a smooth surface or an uneven surface, a cylindrical shape, or the like, and its thickness is
It is appropriately determined so as to form a desired electrophotographic light-receiving member, but in the case where flexibility as an electrophotographic light-receiving member is required, a range in which the function as a support is sufficiently exhibited. It can be made as thin as possible. However, it is usually 10 μm or more in terms of mechanical strength and the like in manufacturing and handling the support.

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

The unevenness provided on the surface of the support is obtained by fixing a cutting tool having a V-shaped cutting edge to a predetermined position of a cutting machine such as a milling machine or a lathe, and rotating a cylindrical support according to a program designed in advance as desired. However, by regularly moving in a predetermined direction, the surface of the support is accurately cut to form a desired uneven shape, pitch, and depth. The inverted V-shaped linear protrusion formed by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped projection may be a double or triple multiple spiral structure or a cross spiral structure.

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

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

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

That is, the first non-Si (H, X) layer constituting the light receiving layer is structurally sensitive to the state of the surface on which the layer is formed, and the layer quality greatly changes depending on the surface state. Therefore, Non-Si
It is necessary to set the dimension of the irregularities provided on the surface of the support so as not to deteriorate the layer quality of the (H, X) light-receptive light-receiving layer.

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

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

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

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

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

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

Further, FIG. 3 also shows an example of a preferable manufacturing method for obtaining the surface shape of the support. That is, it is shown that the spherical spherical recess 304 can be formed by causing 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 uneven portion, 403 is a rigid spherical body, and 404 is a spherical trace depression.

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

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

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

In the example of FIG. 4, 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 a light-receiving layer 500 comprising an IR absorption layer 502, CGL503, CTL504, and a surface layer 505 on a support 501 prepared by the above method.
An example of forming the is shown. The surface layer 505 has a free surface 506.

IR Absorption Layer The IR absorption layer in the present invention has at least one of a germanium atom (Ge) and a tin atom (Sn) and at least one of a hydrogen atom (H) and a halogen atom (X) as constituent elements. One or the other, preferably a non-single crystal material that also contains silicon atoms (Si) (hereinafter "No
n-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 further has a material for controlling conductivity (M _R ),
It may contain at least one of 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 carried out 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
nCl ₂ , TlCl _{3 and the} like can also be mentioned.

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 CGL composed of Non-Si (H, X), for example, as in the case of the IR absorption layer described above, a glow discharge method (low frequency CVD, high frequency CVD or microwave CVD, etc. AC discharge CVD, DC discharge CVD, etc.), ECR-CVD method,
It can be formed by various thin film deposition methods such as 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.

These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level of capital investment, manufacturing scale, and desired characteristics of the light receiving member to be produced. Since it is relatively easy to control the conditions for manufacturing a photoreceptive member for photography and it is possible to easily introduce halogen atoms and hydrogen atoms together with silicon atoms, the glow discharge method, the sputtering method, etc. Method, ion plating method, ECR-CVD method, HRCVD method, FOCVD
The method is preferred. In some cases, these methods may be used together in the same device system. For example, in order to form a CGL composed of Non-Si (H, X) by the glow discharge method, basically, a raw material gas for supplying Si that can supply silicon atoms (Si) and a 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 in a desired gas pressure state to cause glow discharge in the deposition chamber and predetermined Non-Si on the surface of the specified support installed in the position
A layer made of (H, X) may be formed. In the case of forming by the sputtering method, for example, by using a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, if necessary, , 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, polycrystalline silicon or single crystal silicon is housed in a vapor deposition board as an evaporation source, and this evaporation source is heated and evaporated by a resistance heating method, an electron beam method (EB method), or the like. 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. Composed of Non-Si (H, X) by HRCVD method
To form CGL, for example, a raw material gas for supplying Si is introduced in a desired gas pressure state into an activation space provided in the preceding stage in the deposition chamber where the inside pressure can be reduced, and glow discharge is performed in the activation space. Is generated or is heated to generate an active species (A), and a raw material gas for introducing a hydrogen atom (H) and / or a raw material gas for introducing a halogen atom (X) is similarly activated. To generate an active species (B) by introducing the active species (A) and the active species (B) into the deposition chamber separately, and a predetermined support previously installed at a predetermined position. A layer made of Non-Si (H, X) may be formed on the surface. In order to form CGL composed of Non-Si (H, X) by the FOCVD method, for example, a raw material gas for supplying Si is introduced into a deposition chamber whose inside can be depressurized under a desired gas pressure state, and halogen ( X) A gas is introduced into the deposition chamber in a desired gas pressure state separately from the raw material gas, and these gases are chemically reacted in the deposition chamber to form a non-support on a predetermined support surface installed in advance at a predetermined position. -It is sufficient to form a layer other than Si (H, X).

Examples of the substance that can be used as the raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H _{10 in} a gas state or a gasifiable silicon hydride (silane). Are used effectively. 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.

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

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

Specific examples of the halogen compound which can be preferably used in the present invention include halogen gas of fluorine, chlorine, bromine and iodine, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ and ICl. , IBr and other interhalogen compounds can be mentioned.

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

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.

When producing CGL containing halogen atoms according to the glow discharge method, basically, for example, CG is used so that the silicon halide, which is the raw material gas for supplying Si, has a predetermined gas flow rate.
Introduced into the deposition chamber forming L, by generating a glow discharge to form a plasma atmosphere of these gases,
CGL can be formed on a desired support, but in order to more easily control the introduction ratio of hydrogen atoms, hydrogen gas or a silicon compound containing a hydrogen atom is added to these gases. A desired amount of gas may be mixed to form a layer.

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

Sputtering method, Ion plating method, HRCVD method, F
In 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 silane gases is introduced into the deposition chamber for spattering to change the plasma atmosphere of the gases. Just form it.

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 It can be mentioned as a substance. Among these substances, the halides containing hydrogen atoms are introduced because, at the same time as the introduction of halogen atoms into the layer during the formation of CGL, hydrogen atoms that are extremely effective in controlling the electrical or photoelectric properties are also introduced. In the invention, it is used as a preferable raw material for introducing halogen.

In order to 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.

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

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

The distribution concentration of carbon atoms, nitrogen atoms, and oxygen atoms in the CTL in the layer thickness direction may be uniform, or 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 for controlling the conductivity.

12 to 37, the horizontal axis represents the substance contained (M)
Distribution concentration C, the vertical axis represents the CTL layer thickness, t _B is the position of the end surface of the CTL on the support side, and t _T is the CT on the side opposite to the support side.
The position of the end face of L 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, from the interface position t _B where CGL and CTL contact to the position from t ₁₆ to t ₁₆ , the distribution concentration C of the substance (M) is a constant value C ₅₇ , and the substance (M) is constant. Is contained in the formed CTL, and is gradually and continuously reduced from the concentration C ₅₈ from the position t ₁₆ to the interface position t _T. At the interface position t _T , the distribution concentration C of the substance (M) has a value 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). The same applies to the meaning of "substantially zero" hereinafter when the case is less than).

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 and continuously decreased from the value C ₆₈ to the value t _T from the position t _B to a value C ₆₉ at the position t _T.

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

In the example shown in FIG. 20, the distribution concentration C of the substance (M) gradually and continuously increases from the position t _B to the position t ₂₀ from the value C ₇₅ to C ₇₄ , and from the position t ₂₀ to C. _It takes a constant value of ₇₃ and forms a distribution state reaching the position t _T.

In the example shown in FIG. 21, the distribution concentration C of the substance (M) forms 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. There is.

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 forms a distribution state reaching 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.

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 It takes a constant value and forms a distribution state reaching the position t _T.

In the example shown in FIG. 25, the distribution concentration C of the substance (M) is substantially zero to C ₈₃ from the position t _B to the position t _T.
Up to a linear function.

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 It takes a constant value and forms a distribution state reaching the position t _T.

28 to 37 show carbon atoms and / or nitrogen atoms and / or oxygen atoms (hereinafter collectively referred to as "atoms (Y)") contained in CTL in the layer thickness direction. A typical example of distribution is shown.

28 to 37, the horizontal axis represents the distribution concentration C of the contained atom (Y), the vertical axis represents the layer thickness of CTL, T _B represents the position of the end surface of CTL on the support side, and t _T Indicates the position of the end face of CTL on the side opposite to the support side. 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 where CGL and CTL contact to the position t ₂₄ , the distribution concentration C of the atom (Y) is a constant value C _89, and the atom (Y) is constant. CT formed
It is contained in L, and the concentration is C ₉₀ rather than the position t _{24 and the} interface position t _T
It has been gradually and continuously reduced until. Interface position t
_{At T} , the distribution concentration C of atoms (Y) is C ₉₁ .

In the example shown in FIG. 29, the contained atom (Y)
The distribution concentration C of the concentration C ₉₂ is from the position t _B to the position t _T.
From the concentration C ₉₃ at the position t _T.
The distribution state is such that

In the case of FIG. 30, the distribution concentration C of the atom (Y) is set to a constant value of the concentration C ₉₄ from the position t _B to the position t _25.
It is gradually and continuously decreased from C ₉₅ between ₂₅ and the position t _T, and the distribution concentration C is substantially zero at the position t _T (where substantially zero is the detection limit amount). If less than).

In the case of FIG. 31, the distribution concentration C of the atom (Y) is at the position t _B.
Up to more position t _T, is reduced continuously and gradually from the concentration C _96, it is substantially zero at the position t _T.

In the example shown in FIG. 32, the distribution concentration C of atoms (Y)
Is a constant value with the density C ₉₇ between the position t _B and the position t ₂₆ , and is a density 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. 33, from the position t _B to the position t _T , the distribution concentration C of the atom (Y) is linearly decreased from the concentration C ₉₉ to substantially zero.

In the example shown in FIG. 34, the contained atom (Y)
Distribution concentration C forms a kind of distribution the C ₁₀₁ at position t _T gradually decreases continuously from C ₁₀₀ up to the position t _T to the position t _B.

In the example shown in FIG. 35, the distribution concentration C of the atom (Y) takes a constant value of C ₁₀₂ from the position t _B to the position t ₂₇ ,
From the position t ₂₇ to the position t _T , the distribution state is a linear function decrease from C ₁₀₃ to C ₁₀₄ .

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

Example shown in FIG. 28 through FIG. 38 are all but towards the t _B side of the t _T side is an example distribution concentration C is large atomic (Y) to reverse the t _T side and t _B side at all The distribution concentration C of atoms (Y) may be higher on the t _T side than on the t _B side. For example, in the example shown in FIG.
In the case where the _T-side and t _B side Conversely, the interface position t _B to the position t
The distribution density C of the atoms (Y) up to ₂₈ gradually increases continuously from C _108, C ₁₀₇ next position t ₂₈ at position t ₂₈
From the interface position t _T to the constant value C ₁₀₆ .

Examples of the substance (M) that controls the conductivity include so-called impurities in the field of semiconductors. In the present invention, an atom belonging to Group III of the Periodic Table (hereinafter, referred to as “the A group III atom ”) or an atom belonging to group V of the periodic table (hereinafter referred to as“ group V atom ”) that provides n-type conductivity is used. As the group III atom, specifically, B (boron), Al (aluminum),
There are Ga (gallium), In (indium), Tl (thallium) and the like, and B and Ga are particularly preferable. Specific examples of group V atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi.
(Bismuth) and the like, and P and As are particularly preferable.

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 CTL, 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, most preferably 1 × 10 ^−2. ~ 50 atoms p
pm is preferred.

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

Further, the hydrogen atom contained in the CTL of the present invention or /
And the halogen atom can compensate the dangling bond of the silicon atom 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 CGL is preferably thinner than the layer thickness of CTL.

In the present invention, the layer thickness of CTL is preferably 5 from the viewpoint of obtaining desired electrophotographic characteristics and economic effects.
˜50 μ, more preferably 10 to 40 μ, optimally 20 to 30 μ.

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

To form CTL 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 constituent atoms or a gasified substance which can be gasified Most 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 at a desired mixing ratio and used, or a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing nitrogen raw material (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 ) containing N as a constituent atom or N and H as a constituent atom,
Gaseous or gasifiable nitrogen such as ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen such as nitride and azide A compound can be mentioned. In addition to this, nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ) and the like can be introduced in addition to the introduction of the halogen atom (X) in addition to the introduction of the nitrogen atom (N). Mention may be made of nitrogen halide compounds.

To form CTL by glow discharge method, HRCVD method, FOCVD method As a starting material for introducing carbon atoms, a gaseous substance containing at least carbon atoms as constituent atoms or a gasified substance that can be gasified is selected from Most 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). Is also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) as constituent atoms and three gases 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.

Starting materials that are effectively used as raw material gases for introducing carbon atoms (C) include C and H as constituent atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms and 2 to 4 carbon atoms.
Ethylene-based hydrocarbons, acetylene-based hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, saturated hydrocarbons include methane (CH ₄ ),
Ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n
-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene-based hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C
₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C
₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C
₅ H ₁₀ ), acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), 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 the case of forming a CTL by glow discharge method, HRCVD method, FOCVD method, as a starting material for introducing oxygen atoms, at least a gaseous substance containing oxygen atoms as constituent atoms or a gasified substance capable of being gasified is selected. Most can be used.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (O) as constituent atoms, and, if necessary, hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. A raw material gas is mixed at a desired mixing ratio and used, 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. 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 a silicon atom (Si), an oxygen atom (O), and a hydrogen atom (H) as constituent atoms.

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

Starting materials that are effectively used as raw material gases for introducing oxygen atoms (O) include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ). ，
Nitrogen monoxide (N ₂ O), Trinitrogen dioxide (N ₂ O ₃ ), Nitric oxide (N ₂ O ₄ ), Nitric oxide (N ₂ O ₅ ), Nitric oxide (NO ₂ ), Silicon atom (Si) and oxygen atom (O)
And hydrogen atoms (H) and constituent atoms, for example, disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSi
And lower siloxanes such as H ₃ ).

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.

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

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

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

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

When forming by the sputtering method, the distribution concentration C (Y) of the atom (Y) in the layer thickness direction is changed in the layer thickness direction,
Desired distribution of atoms (Y) in the layer thickness direction (depth profile
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, such as Si
If you are using the mixed Tagetsuto the top of the Si ₃ N ₄ and a mixing ratio of Si and Si ₃ N _4, in the layer thickness direction of Tagetsuto, made by allowed to advance changed.

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

In CTL, a substance (M) that controls conduction characteristics, for example, I-th
To introduce a group II atom or a group V atom structurally,
At the time of layer formation, a starting material for introducing a group III atom or a starting material for introducing a group V in a gas state is introduced into the deposition chamber by CGL.
May be introduced together with other starting materials for forming As a starting material for introducing such a Group III atom, it is desirable to employ a gaseous material at room temperature and atmospheric pressure, or at least a material that can be easily gasified under the layer forming conditions. As a starting material for introducing such a Group III atom, specifically for introducing a boron atom, B ₂ H ₆ , B
_{4 H 10, B 5 H 9} , B 5 H 11, B 6 H 10, B 6 H 12, B 6 H 14 borohydride such as, BF _3, BCl _2, BBr boron halides such as ₃ can be mentioned To be In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₂ , TlCl _{3 and the} like can be used.

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.

CGL102, CTL103 having properties capable of achieving the object of the present invention
In order to select and configure A-Si containing hydrogen atoms and / or halogen atoms as Non-Si (H, X) (hereinafter referred to as "A-Si (H, X)"), 101 temperature,
It is necessary to set the gas pressure appropriately 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 CGL, CTL, polycrystalline silicon containing hydrogen atoms and / or halogen atoms (hereinafter referred to as “poly-Si (H, X)”) is selected. In the case of constituting, there are various methods for forming the layer, and for example, the following method can be mentioned.

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

Another method is to first form an 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.

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

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

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

38 to 47 show carbon atoms and / or nitrogen atoms and / or oxygen atoms (hereinafter collectively referred to as "atoms (Z)") contained in the surface layer in the layer thickness direction. A typical example of distribution is shown.

38 to 47, the horizontal axis represents the contained atom (Z).
Distribution concentration C, the vertical axis represents the layer thickness of the surface layer, t _B is the position of the end surface of the surface layer on the side opposite to the support side, and t _T is the end surface of the surface layer on the side opposite to the support side. Indicates the position. That is, the surface layer containing atoms (Z) is formed from the t _B side toward the t _T side.

FIG. 38 shows a first typical example of the distribution state of atoms (Z) contained in the surface layer in the layer thickness direction.

In the example shown in FIG. 38, the distribution concentration C of atoms (Z) is
Forms a distribution state in which it gradually increases continuously from C ₁₁₁ to C ₁₁₀ from the position t _B to the position t ₂₉ , and takes a constant value of C ₁₀₉ from the position t ₂₉ to reach the position t _T. There is.

In the example shown in FIG. 39, the distribution concentration C of atoms (Z) forms a distribution state in which it gradually increases continuously from C ₁₁₃ to C ₁₁₂ from the position t _B to the position t _T. There is.

In the example shown in FIG. 40, the distribution concentration C of atoms (Z) is substantially zero to C from the position t _B to the position t _30.
A distribution state is formed in which the value gradually increases continuously up to ₁₁₅ , takes a constant value of C ₁₁₄ from the position t ₃₀ and reaches the position t _T.

In the example shown in FIG. 41, the distribution concentration C of atoms (Z) is substantially zero to C from the position t _B to the position t _T.
It forms a distribution state that gradually increases continuously up to ₁₁₆ .

In the example shown in FIG. 42, atomic distribution concentration C of the (Z) is increased from C ₁₁₈ up to the position t ₃₁ from the position t _B C ₁₁₇ to a linear function manner, the C ₁₁₇ is the position t ₃₁ 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. 43, the distribution concentration C of atoms (Z) is substantially zero to C from the position t _B to the position t _T.
Up to _119, a distribution is formed that increases linearly.

In the example shown in FIG. 44, the distribution concentration C of atoms (Z) forms a distribution state in which it gradually increases continuously from C ₁₂₅ to C ₁₂₀ from the position t _B to the position t _T. There is.

In the example shown in FIG. 45, the distribution concentration C of atoms (Z) C
From the position t _B to the position t ₃₂ , increases linearly from C ₁₂₄ to C ₁₂₃ , takes a constant value of C ₁₂₂ from the position t _32, and forms a distribution state such that it reaches the position t _T. There is.

In the example shown in FIG. 46, the distribution concentration C of atoms (Z) takes a constant value of C ₁₂₅ from the position t _B to the position t _T.

In the example shown in FIG. 47, the distribution concentration C of atoms (Z) takes a constant value of C ₁₂₈ from the position t _B to t ₃₃ ,
Take a constant value of C ₁₂₇ from position t ₃₃ to position t ₃₄ ,
A distribution state is formed in which a constant value of C ₁₂₆ is obtained from the position t ₃₄ to reach the position t _T.

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

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

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

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

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

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

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

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

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

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

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

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

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

FIG. 48 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the RF glow discharge decomposition method.

In the gas cylinders 1011, 1012, 1013, 1014, 1015, 1016, 1017 in the figure, raw material gas for forming each layer of the present invention is sealed, for example 1011 Si
H ₄ gas (purity 99.999%) cylinder, 10 12 H ₂ gas (purity 99.999%) cylinder, 10 13 B ₂ diluted with H ₂ gas
H ₆ gas (purity 99.999% or less abbreviated as B ₂ H ₆ / H ₂ ) cylinder,
1014 is a NO gas (purity 99.5%) cylinder, 1015 is a GeH ₄ gas (purity 99.999%) cylinder, and 1016 is an NH ₃ gas (purity 99.999).
%) Cylinder, 1017 is a CH ₄ gas (purity 99.999%) cylinder.

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

That is, SiH ₄ gas and H ₂ gas are used as CGL forming gas.
SiH ₄ gas, NH ₃ gas, B ₂ H ₆ gas as CTL forming gas,
The case where SiH ₄ gas or CH ₄ gas is used as the surface layer forming gas will be described.

A gas cylinder is required to allow these gases to flow into the reaction chamber 1001.
Make sure that valves 1051-1056 of 1011-1016, leak valve 1003 of reaction chamber 1011 are closed, and that inflow valves 1031-1036, outflow valves 1041-1046, and auxiliary valve 10
Make sure 70 is open and then first main valve 1002
To evacuate the inside of 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 1046 are closed.

After that, SiH ₄ gas from the gas cylinder 1011, gas cylinder 1012
H ₂ gas, gas cylinder 1013 to B ₂ H ₆ / H ₂ gas, gas cylinder 1014 to NO gas, gas cylinder 1015 to NH ₃ gas,
CH ₄ gas is introduced from the gas cylinder 1016 by opening valves 1051 to 1056, and the pressure of each gas is adjusted by pressure regulators 1061 to 1066.
Adjust to 2Kg / cm ² .

Next, the inflow valves 1031 to 1036 are gradually opened to introduce the above gases into the mass flow controllers 1021 to 1026.

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, the CGL, the CTL, and the surface layer are formed on the base cylinder 1007.

To form the IR absorption layer, the outflow valve 1041,1043,1044,1
045 and auxiliary valve 1070 are gradually opened to SiH ₄ gas, B ₂ H
₆ / H ₂ gas, NO gas, and GeH ₄ gas are caused to flow into the reaction chamber 1001. At this time, the outflow valve 104 is 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.
Adjust 1,1043,1044,1045, and while watching the vacuum gauge 1004 so that the pressure in the reaction chamber becomes the desired value, main valve
Adjust the opening of 1002. After that, the power source 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber 1001, and the formation of the IR absorption layer on the substrate cylinder is started. After the desired film thickness is formed, the RF glow discharge is stopped, and the outflow valves 1041, 1043, 1044, 1045 are closed to stop the inflow of gas into the reaction chamber and the formation of the IR absorption layer is completed. .

Outflow valves 1041,10 to form CGL on the IR absorption layer
42 and the auxiliary valve 1070 are gradually opened to allow SiH ₄ gas and H ₂ gas to flow into the reaction chamber 1001. At this time, the outflow valve 1041, so that the SiH ₄ gas flow rate and the H ₂ gas flow rate have desired values.
1042 is adjusted, and the opening of the main valve 1002 is adjusted while observing the vacuum gauge 1004 so that the pressure in the reaction chamber becomes a desired value. After that, the power source 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber, and
Initiate CGL formation. 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.

To form the CTL, the outflow valves 1041, 1043, 1045 and the auxiliary valve 1070 are gradually opened to 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, the B ₂ H ₆ gas flow rate, and the NH ₃ gas flow rate reach the desired values, and the pressure in the reaction chamber reaches the desired value. Adjust the opening of the main valve 1002 while watching the vacuum gauge 1004. Then power 10
RF glow discharge is initiated in the reaction chamber with 10 set to the desired power to initiate CTL formation on the substrate cylinder. After the desired film thickness is formed, the RF glow discharge is stopped, the outflow valves 1041, 1043, 1045 are closed to stop the gas flow into the reaction chamber, and the CTL formation is completed.

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

To form the surface layer, the outflow valves 1041 and 1046 and the auxiliary valve 1070 are gradually opened to allow SiH ₄ gas and CH ₄ gas to flow into the reaction chamber 1001. At this time, SiH ₄ gas flow rate, CH ₄
Outflow valves 1041 and 1046 so that the gas flow rate is the desired value
Further, the opening of the main valve 1002 is adjusted while observing the vacuum gauge 1004 so that the pressure in the reaction chamber becomes a desired value. After that, the power source 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber, and the formation of the surface layer on the substrate cylinder is started. After forming the desired film thickness,
The RF glow discharge is stopped, the outflow valves 1041 and 1046 are closed to stop the inflow of gas into the reaction chamber, and the formation of the surface layer is completed.

It goes without saying that all the outflow valves except the gas necessary for forming each layer are closed, and
Each gas is in the reaction chamber 1001 and outflow valves 1041 to 1046
In order to avoid remaining in the piping from the reaction chamber 1001 to the reaction chamber 1001, the outflow valves 1041 to 1046 are closed, the auxiliary valve 1070 is opened, the main valve 1002 is fully opened, and the system is temporarily evacuated to a high vacuum. Do as needed.

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

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

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

FIG. 49 shows an apparatus for manufacturing 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, for example, in 2011, Si is used.
H ₄ gas (purity 99.999%) cylinder, 2012 H ₂ gas (purity 99.999%) cylinder, 2013 B ₂ diluted with H ₂ gas
H ₆ gas (purity 99.999% or less abbreviated as B ₂ H ₆ / H ₂ ) cylinder,
2014 is NO gas (purity 99.5%) cylinder, 2015 is GeH ₄ gas (purity 99.999%) cylinder, 2016 is NH ₃ gas (purity 99.999)
%) Cylinder, 2017 is a CH ₄ gas (purity 99.999%) cylinder.

As an example of the gas used when forming the light receiving member for electrophotography in the apparatus shown in FIG. 49, SiH is used as the gas for forming CGL.
₄ gas, H ₂ gas, SiH ₄ gas, NH ₃ as CTL forming gas
Gas, B ₂ H ₆ gas, and SiH ₄ gas and CH ₄ gas are used as the surface layer forming gas.

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

Next, when the reading of the vacuum gauge 2004 becomes about 5 × 10 ⁻⁶ Torr, the auxiliary valve 2070 and the outflow valves 2041 to 2046 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 and CH ₄ gas from gas cylinder 2017 are 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, the CGL, the CTL, and the surface layer 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 are made to flow into the reaction chamber 2001. At this time, the outflow valve 2 is 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.
041, 2043, 2044, 2045 are adjusted, 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. Then microwave power 2008
Set the desired power, waveguide 2009 and dielectric window 2010
A .mu.W glow discharge is generated in the reaction chamber through and the formation of the IR absorption layer on the substrate cylinder is started. After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valves 2041, 2043, 2044, 2045 are closed to stop the gas from flowing into the reaction chamber, and the formation of the IR absorption layer is completed.

Outflow valves 2041,20 to form CGL on the IR absorption layer
42 and auxiliary valve 2070 are gradually opened to SiH ₄ gas, H ₂
Gas is introduced into the reaction chamber 2001. At this time, the outflow valve 204 is adjusted so that the SiH ₄ gas flow rate and the H ₂ gas flow rate become desired values.
1, 2042 are adjusted, 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 supply 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 microwave is discharged onto the substrate cylinder.
Initiate CGL formation. After the desired film thickness is formed, the μW glow discharge is stopped and the outflow valves 2041 and 204
Close 2 to stop the flow of gas into the reaction chamber and finish the formation of CGL.

CTLs are formed on CGLs formed as above. CT
To form L, the outflow valves 2041, 2043, 2045 and the auxiliary valve 2070 are gradually opened to allow SiH ₄ gas, B ₂ H ₆ gas, and NH ₃ gas to flow into the reaction chamber 2001. At this time, SiH ₄ gas flow rate, B
Adjust the outflow valves 2041, 2043, 2045 so that the ₂ H ₆ gas flow rate and the NH ₃ gas flow rate are at the desired values, and see the vacuum gauge 2004 so that the pressure in the reaction chamber is at the desired value. Adjust the opening of valve 2002. Then microwave power 20
08 is set to the desired power and waveguide 2009 and dielectric window 20
A μW glow discharge is generated in the reaction chamber through 10 to initiate the formation of CTLs on the substrate cylinder. After the desired film thickness is formed, the μW glow discharge is stopped and the outflow valve 20
CT is closed by closing 41,2043,2045 to stop gas from flowing into the reaction chamber.
Finish the formation of L.

A surface layer is formed on the CTL formed as described above. To form the surface layer, the outflow valves 2041 and 2046 and the auxiliary valve 2070 are gradually opened to allow SiH ₄ gas and CH ₄ gas to flow into the reaction chamber 2001. At this time, SiH ₄ gas flow rate, CH ₄
Outflow valves 2041, 2046 so that the gas flow rate is the desired value
Further, 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 micro power source 2008 is set to a desired power, a μw glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 2010, and the formation of the surface layer on the substrate cylinder is started. After forming the desired film thickness, μ
w The glow discharge is stopped, the outflow valves 2041 and 2046 are closed to stop the inflow of gas into the reaction chamber, and the formation of the surface layer is completed.

It goes without saying that all the outflow valves other than the gas necessary for forming each layer are closed, and the respective gases are piped from the outflow valves 2041 to 2046 to the reaction chamber 2001 in the reaction chamber 2001. In order to avoid remaining in the inside, the outflow valves 2041 to 2046 are closed, the auxiliary valve 2070 is opened, the main valve 2002 is fully opened, and the system is temporarily evacuated to a high vacuum as necessary.

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

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

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

FIG. 50 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the HRCVD method.

In FIG. 50, 3001 is a film forming chamber, 3002 is an activation chamber (A),
3003 and 3018 are microwave plasma generators, 3004 is a raw material gas introduction pipe for activated species (A), 3005 is an activated species (A) introduction pipe, 3006 is a motor, 3007 is a heater for heating a cylindrical substrate, 3008, Reference numeral 3009 indicates a blowing pipe, 3010 indicates a cylindrical base body, and 3011 indicates a main exhaust valve.
Further, 3012 to 3016 are cylinders for supplying a raw material gas,
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 the IR absorption layer forming gas is SiH ₄ , GeH ₄ , B ₂ H ₆ , NO, H ₂ and C
SiH ₄ , H ₂ was used as the GL forming gas, and SiH ₄ , SiF ₄ , CH ₄ , H ₂ , 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 heating heater 3007 was provided inside it so that it could be rotated by a motor 3006, and the film formation chamber was evacuated to 5 × 10 ⁻⁶ Torr.

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.

To form CGL on the above IR absorption layer, use a cylinder 3012 for H ₂
The gas is introduced into the activation chamber (A) through the introduction pipe 3004, activated by the microwave plasma generator 3003, and active hydrogen is introduced through the introduction pipe 3005 through the blowing pipe 3008 into the film formation chamber.
Led to 3001. On the other hand, SiH ₄ gas was introduced from the cylinder 3013.
After being introduced into the activation chamber (B) 3017 from 3019 and activated by the microwave plasma generator 3018, the introduction pipe 3020
Through the blowing pipe 3009 to the film forming chamber 3001. At this time, the gas flow rate, internal pressure, and microwave power are set to desired values.

The Al cylindrical substrate 3010 was heated and maintained at a desired temperature by the heater 3007, and the exhaust gas was exhausted by appropriately adjusting the opening of the main exhaust valve 3011. CGL was thus formed. In the same manner as above on CGL, from cylinder 3012 H ₂
Gas, SiH ₄ gas from 3013, B ₂ H ₆ gas from 3014, CH ₄ gas from 3016, SiF ₄ gas from a cylinder (not shown)
Then, H ₂ gas from the cylinder 3012, SiH ₄ from the cylinder 3013, and CH ₄ gas from the cylinder (not shown) were supplied onto the CTL to form a surface layer sequentially to form a light-receiving member for electrophotography. .

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

FIG. 51 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the FOCVD method.

Gas cylinders 4011, 4012, 4013, 4014, 4015, 4016, 4017 in the figure, the source gas for forming the respective layers of the present invention is sealed, as an example, for example, 4011
SiH ₄ gas (99.999% purity) cylinder, H ₂ gas (99.999% purity) in 4012 bomb, B ₂ is the 4013, which is diluted with H ₂
H ₆ gas (purity 99.999% or less abbreviated as B ₂ H ₆ / H ₂ ) cylinder,
4014 is NO gas (purity 99.5%) cylinder, 4015 is GeH ₄ gas (purity 99.999% or less) cylinder, 4016 is CH ₄ gas (purity 9
9.999%) cylinder, 4017 is F ₂ gas (10% He diluted, purity 9
9.99%).

SiH ₄ gas, B ₂ H ₆ / H ₂ gas, NO as the IR absorption layer forming gas
Gas, GeH ₄ gas, F ₂ as SiH ₄ gas, H ₂ as CGL forming gas
Gas, F ₂ gas, SiH ₄ gas, CH ₄ gas, B ₂ H ₆ gas, F ₂ gas as CTL formation gas, SiH ₄ gas as surface layer formation gas
_{Take the} case of using ₄ gas, CH ₄ gas, and F ₂ gas.

The raw material gas filled in the cylinders 4011 to 4015 is 4031.
~ 4035 through each valve, 4053 ~ 4057 Musk low controller through 4020 to 4001 vacuum chamber.

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 exhausted by a vacuum exhaust device (not shown) via the main vacuum valve 4002.

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

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

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

In order to introduce the gases 4011 to 4016 into the 4001, it must be slowly introduced by various valve operations when the inside of the chamber of the 4001 reaches about 5 × 10 ⁻⁶ Torr.

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

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

To form the IR absorption layer, open valves 4046, 4048-4050, and outflow valves 4031, 4033, 4034, 4035 and auxiliary valve 4
Open 060 gradually and 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, the outflow valves 4031, 4033, 4034, 4035 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 reaction The opening of the main valve 4002 is adjusted while observing a vacuum gauge (not shown) where the pressure in the room reaches a desired value.

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.

Valves 4046-4050 to form CGL on the IR absorbing layer
Is opened, and the outflow valves 4031 and 4032 and the auxiliary valve 4060 are gradually opened to allow SiH ₄ gas and H ₂ gas to flow into the reaction chamber 4001. At this time, the outflow valves 4031 and 4032 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 reaches the desired value. Adjust the opening of valve 4002.

Next, open 4051, gradually open the valve of 4036 while watching the mass flow meter 4058 until the desired flow rate is reached, the setting of the flow rate is completed, and CGL is formed at the desired film thickness after a while. To finish.

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

〔Example〕

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

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

The prepared electrophotographic light-receiving member was set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging was performed under various conditions. Check electrophotographic characteristics such as performance, sensitivity, residual potential, ghost, etc.
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. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 5 shows the above-mentioned comprehensive evaluation results.

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

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

The results are shown in Table 8.

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

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

The results are shown in Table 11.

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

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

The results are shown in Table 14.

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

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

The results are shown in Table 17.

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

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

The results are shown in Table 20.

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

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

The results are shown in Table 23.

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

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

The results are shown in Table 26.

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

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

The results are shown in Table 29.

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

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

The results are shown in Table 32.

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

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

The results are shown in Table 35.

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

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

The results are shown in Table 38.

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

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

The results are shown in Table 41.

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

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

The results are shown in Table 44.

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

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

The results are shown in Table 47.

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

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

The results are shown in Table 50.

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

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

The results are shown in Table 53.

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

<Example 18> Using the manufacturing apparatus shown in FIG.
Photoreceptive members for electrophotography were formed on aluminum cylinders that were mirror-finished according to the preparation conditions shown in Tables 55, 56, and 57.

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

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 58 shows the comprehensive evaluation results.

As shown in Table 58, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 19> Table 59 to Table 62 were used by the HRCVD method using the manufacturing apparatus of FIG.
An electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the conditions shown in the table. The prepared electrophotographic light-receiving member was set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging ability was set under various conditions. , Electrophotographic characteristics such as sensitivity, residual potential, and ghost were checked, and deterioration of charging ability, surface scraping, and increase of image defects after 2 million sheets of accelerated real machine durability were examined.

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 63 shows the comprehensive evaluation results.

As shown in Table 63, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 20> Tables 64 to 67 were prepared by the FOCVD method using the manufacturing apparatus shown in FIG.
An electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the conditions shown in the table.

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

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 68 shows the comprehensive evaluation results.

As shown in Table 68, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 21> Mirror-finished cylinders were further subjected to lathe processing with a sword bite having various angles to obtain cylinders having various cross-sectional patterns as shown in Table 69 with a cross-sectional shape as shown in FIG. 56. I prepared multiple books. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 48 and subjected to the drum manufacturing under the manufacturing conditions shown in Table 69. Various evaluations were performed on the produced drum with an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 70 were obtained.

<Example 22> The surface of the mirror-finished cylinder was continuously exposed to the dropping of a large number of bearing balls, and the surface of the cylinder was subjected to a so-called surface dimple forming treatment to produce innumerable dents. A plurality of cylinders having the cross-sectional shapes shown in the figure and having various cross-sectional patterns as shown in Table 47 were prepared.
The cylinders are sequentially set in the manufacturing apparatus shown in FIG.
The drum was produced under the production conditions shown in Table 46. The prepared drum was subjected to various evaluations by 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 48 were obtained. .

<Example 23> Using the manufacturing apparatus shown in Fig. 48, a drum was prepared in the same manner as in Example 1 under the conditions shown in Tables 49, 50, and 51, and the same evaluation was performed.

The results are shown in Table 52.

As shown in Table 52, good results were obtained for all items.

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

In particular, in the present invention, a function-separated type structure using CTL and CGL is used, and the substance (M) that controls conductivity is contained in the CTL in a state of being unevenly or partially unevenly distributed in the layer thickness direction. At the same time, by containing at least one 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.
From TG to CTL is promptly performed, and it has particularly excellent charging ability and sensitivity, little residual potential and ghost, and also has high resolution in images, and high-quality images can be stably repeated. be able to.

[Brief description of drawings]

FIG. 1 is a schematic layer structure diagram for explaining a layer structure of a light-receiving member for electrophotography of the present invention, and FIGS. 2 to 5 are uneven shapes on a surface of a support and a method for producing the uneven shapes, respectively. 6 to 11 are explanatory views of the distribution state of atoms (Gs) contained in the IR absorption layer, and FIGS. 12 to 27 are CTL constituents, respectively. 28 to 37 of the substance for controlling the conductivity, which are illustrated in FIGS. 38 to 47, respectively, are explanatory diagrams for explaining the distribution state of carbon atoms and / or oxygen atoms and / or nitrogen atoms, and FIGS. FIG. 48 is an explanatory view for explaining the distribution state of carbon atoms and / or oxygen atoms and / or nitrogen atoms constituting the surface layer, and FIG. 48 is a view for forming the light receiving layer of the electrophotographic light receiving member of the present invention. Schematic of manufacturing equipment by glow discharge method using RF in one example of equipment Explanatory drawing, FIG. 49 is a schematic explanatory view of a manufacturing apparatus by a glow discharge method using microwave in an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography of the present invention, and FIG. 50 is An example of an apparatus for forming a light-receiving layer of an electrophotographic light-receiving member of the present invention, which is a schematic explanatory view of a manufacturing apparatus by the HRCVD method, and FIG. 51 is a light-receiving layer of the electrophotographic light-receiving member of the present invention. FIG. 52 is a schematic explanatory view of a manufacturing apparatus by the FOCVD method as an example of an apparatus for forming a film, FIG. 52 shows impurity gas and doping when the CTL of the photoreceptive member for electrophotography of the present invention is formed by using RF glow discharge.・ A diagram showing a change in flow rate at the time of forming a film of gas, FIG. 53 is a view of forming an impurity gas and a doping gas when forming the CTL of the electrophotographic light-receiving member of the present invention by using microwave glow discharge Fig. 54 shows the flow rate change in the HRCVD the CTL of the electrophotographic light-receiving member of the
FIG. 55 is a diagram showing flow rate changes during film formation of an impurity gas and a doping gas in the case of forming by using the method, FIG. 55 is a FOCVD of the CTL of the electrophotographic light-receiving member of the present invention.
Showing changes in the flow rates of the impurity gas and the doping gas at the time of film formation in the case of forming by using the method, FIG. 56 shows the cross-sectional shape of the cylinder substrate when forming the photoreceptor member for electrophotography of the present invention is V FIG. 57 is an enlarged view of the cylinder cross section in the case of a letter shape, FIG. 57 is an enlarged view of the cylinder cross section when the surface of the cylinder substrate in forming the electrophotographic light-receiving member of the present invention is subjected to so-called dimple processing, 58 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 Figure 1, 101 ... Support 102 ... Photoreceptive layer 103 ... IR absorption layer 104 ... CGL 105 ... CTL 106 ... Surface layer 107 ... Free surface About Figures 3 and 4, 301,401 …… Support 302,402 …… Support surface 303,403 …… Rigid spherical sphere 304,404 …… Spherical trace dent About Fig. 5, 500 …… Photoreceptive layer 501 …… Support 502 …… IR absorption layer, 503 …… CGL 504 …… CTL 505 …… Surface layer 506 …… Free surface In Fig. 42, 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 …… Gas cylinder 1021-1027 …… Mass flow controller 1031-1037 …… Gas inlet valve 1041-1047 …… Gas Outflow valve 1051 to 1057 …… Source gas cylinder valve 1061 to 1067 …… Pressure adjustment Regarding Fig. 43, 2001: Reaction chamber 2002: Main exhaust valve 2003: Reaction chamber leak valve 2004: Vacuum gauge 2005: Substrate heating heater 2006: Cylindrical substrate 2007: Substrate rotation motor 2008 …… Microwave power supply 2009 …… Waveguide 2010 …… Dielectric window 2011 ～ 2017 …… Gas cylinder 2021 ～ 2027 …… Mass flow controller 2031 ～ 2037 …… Gas inlet valve 2041 ～ 2047 …… Gas outflow valve 2051 to 2057 …… Raw gas gas cylinder valve 2061 to 1267 …… Pressure regulator About Fig. 44, 3001 …… Deposition chamber 3002 …… Activation chamber (A) 3003,3018 …… Microwave plasma Generator 3004,3019 …… Raw material gas introduction pipe 3005,3020 …… Activated species introduction pipe 3006 …… Motor 3007 …… Cylinder substrate heating heater 3008,3009 …… Blowout pipe 3010 …… Cylinder substrate 3011 …… Main Exhaust valve 3012-3016 …… Material gas cylinder 3017 …… Activation chamber (B) About Fig. 45, 4001 …… Reaction chamber 4002 …… Main exhaust valve 4011-4017 …… Source gas cylinder 4020,4021 …… Source gas introduction pipes 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 long-wavelength light absorbing layer on the support,
A light receiving layer having a layer structure in which a charge generating layer, a charge transporting layer and a surface layer are laminated in this order from the support side, and the long wavelength light absorbing layer, the charge generating layer and the charge transporting layer. And a silicon atom as a host, composed of a non-single crystal material containing at least one of a hydrogen atom and a halogen atom, the surface layer is a silicon atom as a host, carbon atoms, nitrogen atoms and oxygen atoms of And at least one of the non-single crystal material containing at least one of a hydrogen atom and a halogen atom,
The long-wavelength light absorption layer further contains at least one of germanium atom and tin atom, and the charge transport layer contains at least one of carbon atom, nitrogen atom and oxygen atom, the periodic table An electrophotographic light having at least a portion containing an atom belonging to group III or group V in a non-uniform distribution state in which the concentration thereof increases or decreases from the support side in the layer thickness direction. Receiving member.