JPH0812438B2 - 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 constituting the light receiving layer in the light receiving member for electrophotography, it has high sensitivity and SN
High ratio [photocurrent (Ip) / dark current (Id)], absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves that are irradiated, fast photoresponsiveness, and the desired dark resistance value. Be pollution-free to the human body,
Such characteristics are required. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used as an office machine as an office machine, the pollution-free property at the time of use is an important point.

Amorphous assilicon (hereinafter referred to as A-Si) is a photoconductive material that has recently received attention based on such a point. For example, German Laid-Open Publication No. 2746967 and No. 2855718.
Japanese Patent Application Laid-Open Publication No. HEI 9-26139 describes an application as a light receiving member for electrophotography.

However, a conventional electrophotographic light-receiving member having a light-receiving layer composed of A-Si has electrical, optical, photoconductive and use environment characteristics such as dark resistance, photosensitivity, and photoresponsiveness. In terms of, and stability and durability over time, the characteristics are individually improved,
The reality is that there is room for further improvements in the overall improvement of characteristics.

For example, when applied to a photoreceptive member for electrophotography,
When trying to measure high photosensitivity and high dark resistance at the same time, it is often observed in the past that residual potential remains during use, and if this type of light receiving member is used repeatedly for a long time, fatigue due to repeated use may occur. There are many inconveniences such as accumulation, 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". It is considered that an image defect which is considered to be caused by a general electric discharge breakdown phenomenon, and when a blade is used for the cleaning means, rubbing is caused. Image defects commonly known as "white stripes" have occurred. 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 objects of the present invention are electrical, optical,
The photoconductive properties are almost always stable with almost no dependence on the operating environment, have excellent light fatigue resistance, do not deteriorate even after repeated use, have excellent durability and moisture resistance, and have no residual potential. Another object of the present invention is to provide a photoreceptive member for electrophotography, which has a photoreceptive layer composed of a material having a silicon atom as a base, which is hardly observed.

Another object of the present invention is to provide excellent adhesion between the layer provided on the support and the support or between the layers to be laminated, the structure being dense and stable in terms of structure, and high layer quality. ,
Another object of the present invention is to provide a photoreceptive member for electrophotography having a photoreceptive layer composed of a material having silicon atoms as a base material.

Still another object of the present invention is that, when applied as a photoreceptive member for electrophotography, it has 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 photoreceptive member for electrophotography, which has a photoreceptive layer composed of a material having atoms as a base material.

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

[Structure of Invention]

The light-receiving member for electrophotography of the present invention comprises a support, a long-wavelength light absorption layer (hereinafter sometimes abbreviated as “IR absorption layer”), a charge injection blocking layer, and a charge transport layer on the support. After that, "CT
Abbreviated as "L"), charge generation layer (hereinafter "CGL")
May be abbreviated) and a surface layer and a light-receiving layer having a layer structure laminated in this order from the support side, wherein the surface layer is a silicon atom, and a carbon atom, a nitrogen atom and an oxygen atom. Of the non-single-crystal material containing at least one of a hydrogen atom and a halogen atom, and the long-wavelength light absorption layer, the charge injection blocking layer, the charge transport layer, and the charge generation. The layer is composed of a non-single-crystal material (hereinafter sometimes abbreviated as "Non-Si (H, X)") containing a silicon atom as a host and at least one of a hydrogen atom and a halogen atom. The long-wavelength light absorption layer further contains at least one of a germanium atom and a tin atom, and the charge injection blocking layer is an atom belonging to Group III or Group V of the periodic table (controlling conductivity). Quality), and the charge transport layer contains at least one of a carbon atom, a nitrogen atom and an oxygen atom, and the concentration of the atom belonging to Group III or V of the periodic table is It is characterized by having at least a portion containing in a non-uniform distribution state having a portion increasing or decreasing from the support side in the layer thickness direction.

[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, the effect of residual potential on image formation is practically practically non-existent, its electrical characteristics are stable, and it has high sensitivity and high SN.
Ratio, light fatigue resistance, repeated use characteristics,
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 adopting a function-separated type structure using L and CGL, separate layers are provided with the important functions of the photoreceptive member for electrophotography such as generation of charges (photocarriers) and transport of the generated 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. Also, since the CTL contains at least one of carbon hydrogen, nitrogen atoms and oxygen atoms, 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.

Furthermore, by providing an IR absorption layer between the support and the CTL, even if a long-wavelength light such as a semiconductor laser is used as an exposure light source of an electrophotographic apparatus, absorption is not completed between the incident surface side and the support. Since the long-wavelength light for a minute is also highly efficiently absorbed by the IR absorbing layer, the appearance of an interference phenomenon due to the reflection of the long-wavelength light on the surface of the support can be remarkably prevented, and the image quality is dramatically improved.

Further, since the charge injection blocking layer is provided between the support and the CTL, it is possible to effectively prevent the charge from being injected into the CTL from the support side when subjected to a charging treatment. The charging ability is 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 pressure resistance are improved.

[Specific Description of the Invention]

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

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

The electrophotographic light-receiving member 100 shown in FIG. 1 has an IR absorption layer 103 on a support 101 for the electrophotographic light-receiving member.
And Non-Si (H, X) containing a substance (Mo) that controls conductivity uniformly or non-uniformly in the whole layer region (hereinafter referred to as “Non-Si (H, X
X) ”).
Non-Si (H, X) non-uniform distribution in the layer thickness direction of the substance (M) that contains at least one of carbon atom, nitrogen atom and oxygen atom and controls conductivity. CTL105 which has at least a part containing in the state
And a light-receiving layer 102 having a layer structure including a CGL 106 composed of Non-Si (H, X) and a surface layer 107. Surface layer 1
07 has a free surface 108.

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

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

For example, glass is NiCr, Al, Cr, M on the surface.
Conductivity is imparted by providing a thin film of o, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, InO ₃ , ITO (In ₂ O ₃ + Sn), etc., or a synthetic resin such as polyester film. For films, 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 at a predetermined position of a cutting machine such as a slicing machine or a lathe, and rotating a cylindrical support in accordance with a program designed in advance according to a desire. The surface of the support is precisely cut by moving the support regularly in a predetermined direction while being formed to have a desired uneven shape, pitch, and depth. The inverted V-shaped linear protrusion formed by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped projection may be a double or triple multiple spiral structure or a cross spiral structure.

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

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

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

That is, the first is Non-Si (H, X) that constitutes the light receiving layer.
The layer is structurally sensitive to the shape of the surface on which the layer is formed, and the layer quality greatly changes depending on the surface condition. Therefore, Non-
It is necessary to set the dimension of the unevenness provided on the surface of the support so as not to deteriorate the layer quality of the Si (H, X) light receiving light receiving layer.

Secondly, if the free surface of the light receiving layer has extreme irregularities,
In the cleaning after the image formation, the cleaning cannot be completely performed.

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

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

The maximum depth of the recess is preferably 0.1 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm, optimally 0.6 μm to 2
It is desirable to be set to μm. When the pitch and maximum depth of the concave portion on the surface of the support are within the above range, the inclination of the inclined surface of the concave portion (or 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 difference in layer thickness based on the non-uniformity of the layer thickness of each layer deposited on such a support is preferably 0.1 μm to 2 μm, more preferably 0.1 μm to 1.5 μm, most preferably within the same pitch. Is 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 irregularities finer than the resolving power required for the light receiving member for electrophotography, and the irregularities are caused by a plurality of spherical trace depressions.

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 a support surface, 303
Indicates a rigid spherical body, and 304 indicates a spherical dent.

Further, FIG. 3 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 concavo-convex shape due to the spherical trace dents on the surface of the support of the electrophotographic light-receiving member of the present invention act to prevent the occurrence of interference fringes in the electrophotographic light-receiving member of the present invention. It is an important factor to achieve the effect efficiently. The present inventors have made the following discoveries as a result of various experiments. That is, the radius of curvature R and the width D are as follows: If the above condition is satisfied, there are 0.5 or more Newton rings due to shear ring interference in each of the dents. Furthermore, the following formula: If the above condition is satisfied, there will be one or more Newton rings due to shear ring interference in each of the dent depressions.

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

In addition, the width D of the unevenness due to the trace depression is 500 at the maximum.
about μm, preferably less than 200 μm, more preferably 100
It is desirable that the thickness is not more than μm.

In the example of FIG. 4, an example of using a rigid true sphere having substantially the same radius Ro is shown, but the support in the present invention is not limited to this and achieves the object of the present invention. It is also possible to use a plurality of types of rigid true spheres having different radii Ro while the number and types are controlled within the range.

FIG. 5 shows an IR absorption layer 502, a charge injection blocking layer 503, a CTL 504, a CGL 505, a surface layer 506 on a support 501 prepared by the above method.
An example is shown in which the light receiving layer 500 composed of and is formed. The surface layer 506 has a free surface 507.

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 side is the side opposite to the side where the support is provided (the free surface side of the light receiving layer). Is contained in the IR absorption layer so as to be distributed in a larger amount in the IR absorption layer or in the opposite distribution.

In the electrophotographic light-receiving member of the present invention, as described above, the distribution state of the germanium atoms and / or tin atoms contained in the IR absorption layer has the above-described distribution state in the layer thickness direction, It is desirable to have 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, IR containing atoms (GS)
From the interface position t _B at which the surface where the absorption layer is formed and the surface of the IR absorption layer are in contact to the position t ₁ , the distribution concentration C of the atom (GS) has a constant value C ₁ and the atom ( GS) is formed
It is contained in the IR absorption layer, and the interface position is based on concentration C ₂ rather than position t _1.
It is gradually and continuously reduced until reaching t _T. Interface position
At t _T , the distribution concentration C of atoms (GS) is C ₃ .

In the example shown in FIG. 7, the contained atoms (G
The distribution concentration C of S) is the concentration C ₄ from the position t _B to the position t _T.
A distribution state is formed in which the concentration C ₅ gradually decreases continuously from to reach the concentration C ₅ at the position t _T.

In the case of FIG. 8, from the position t _B to the position T ₂ an atom (G
Distribution concentration C of S) is the concentration C ₆ a constant value, between the position t _T to the position t _2, is gradually reduced continuously, the position t _T
In the above, the distribution concentration C is set to be substantially zero (here, “substantially zero” is the case where the amount is less than the detection limit amount, and the following 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 concentration C ₉ ) between the positions t _B and t ₃ , and is the concentration 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 the atom (GS) decreases linearly so as to reach substantially zero from the position C ₁ of the concentration. .

As described above with reference to FIGS. 6 to 11, some of the typical examples of the state of distribution of 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)
In the IR absorption layer, a distribution state of atoms (GS) is provided on the interface t _T side where the distribution concentration C is considerably lower than on the support side. , 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 C _max of the distribution concentration of the atoms (GS) is preferably 1000 atoms ppm or more, more preferably 5000 atoms with respect to the sum with the silicon atoms. ppm or higher,
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 atoms (GS) contained in the IR absorption layer
The content of is appropriately determined according to the demand so as to effectively achieve the object of the present invention, but is preferably 1 ×
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 is a substance that further controls 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. It is referred to as an atom belonging to Group V of the given periodic table "Group V atom". ) Is used. No. III
Specific examples of the group atom include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium), and B and Ga are particularly preferable. Specific examples of Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth), with P and As being particularly preferred.

In the present invention, the content of the substance (M _R ) for controlling the conductive properties contained in the IR absorption layer 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, the IR absorption layer composed of Non-Si (Gw, Sn) (H, X) has a desired property, for example, by a vacuum deposition film forming method similar to CGL and CTL described later. Are created by appropriately setting the numerical conditions of the film forming parameters. Specifically, for example, a glow discharge method (low-frequency CVD, high-frequency CVD, alternating-current discharge CVD such as microwave CVD, or direct-current discharge CVD), a sputtering method, a vacuum deposition method,
Ion plating method, optical CVD method, thermal CVD method, active species (A) generated by decomposing a raw material gas of a non-single-crystal material, and film formation which chemically interacts with the active species (A) A method for forming a non-single-crystal material by introducing active species (B) generated from a chemical substance for chemicals into a film formation space for forming a deposited film separately and chemically reacting these ( Hereinafter, abbreviated as “HRCVD method)”, in a film formation space for separately forming a deposition film of a source gas of a non-single crystal material and a halogen-based oxidizing gas having a property of oxidizing the source gas. Method of forming a non-single crystal material by introducing these into a substrate and chemically reacting them (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, spattering method, ion plating method, HRCVD 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.
Required by using two or three of the target composed of, or a target composed of the target and Ge and / or Sn, or a mixed target of Si, 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. It can be carried out in the same manner as in the sputtering method except that the source is heated and evaporated by the resistance heating method or the electron beam method (EB method) and the flying evaporates are passed through the desired gas plasma atmosphere. it can.

To form an IR absorption layer composed of Non-Si (Gw, Sn) (H, X) by the HRCVD method, for example, a source gas for supplying Si and a source gas for supplying Ge and / or a source gas for supplying Sn may be used. The raw material gases are introduced separately or together at a desired gas pressure into the activation space provided in the preceding stage in the deposition chamber where the pressure inside can be reduced, and a glow discharge is generated in the activation space. The active species (A) is generated by heating or heating, 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 introduced into another activation space. To generate the active species (B), and the active species (A) and the active species (B) are separately introduced into the deposition chamber, and the non-Si is placed on a predetermined support surface which is installed at a predetermined position in advance. A layer formed of (Ge, Sn) (H, X) may be formed. 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 ( Ge, Sn) (H, X)
It is sufficient to form a layer consisting of.

In order to form an IR absorption layer composed of Non-Si (Ge, Sn) (H, X) by the FOCVD method, for example, a raw material gas for supplying Si and a raw material gas for supplying Ge and / or for supplying Sn may be used. The source gas is introduced into the deposition chamber in which the inside pressure can be reduced separately or together as required, and the halogen (X) gas is introduced into the deposition chamber in a desired gas pressure state separately from the source gas. And chemically react these gases in the deposition chamber to form a layer made of Non-Si (Ge, Sn) (H, X) on the surface of a predetermined support that has been installed in advance at a predetermined position. Just do it. 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.

As a substance that can be used as a raw material gas for supplying Si used in the present invention, silicon hydride (SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc. in a gas state or gasifiable silicon ( Silanes)
Can be used effectively. Especially, in terms of ease of handling during layer formation work and good Si supply efficiency, SiH ₄ , Si
₂ H ₆ is mentioned as a preferable one.

As a substance that can be used as a source gas for Ge supply, 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 and Ge ₉ H _{20 in} a gaseous state or gasifiable germanium hydride are mentioned as being effectively used,
GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are particularly preferable in terms of easiness of handling during layer formation work and good Ge supply efficiency.

As a substance that can be used as a source gas for supplying Sn, 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 and Sn ₉ H _{20 in} the gas state or gasifiable tin hydride are mentioned as being effectively used. Especially, in terms of ease of handling during layer formation work and good Sn supply efficiency, Sn
H 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 the gas state or containing a gasifiable halogen atom can also be mentioned as effective in the present invention.

Specific examples of the halogen compound that can be preferably used in the present invention include halogen gas of fluorine chlorine bromine and iodine, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, IBr, Interhalogen compounds such as

As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, specifically, for example, a silicon halide such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , or SiBr ₄ is preferable. it can.

When forming the characteristic electrophotographic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, it is necessary to supply Ge and / or Sn.
Consisting 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 Si together with the source gas for supply. IR
An absorption layer can be formed.

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.

In addition, each gas may be used alone or in combination of a plurality of gases at a predetermined mixing ratio.

Sputtering method, ion plating method, HRCVD
Method, in order to introduce a halogen atom into the layer formed in any of the FOCVD method, by introducing a gas of the halogen compound or a silicon compound containing the halogen atom into the deposition chamber It is only necessary to form a plasma atmosphere.

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

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, GeHCl ₃ , GeH ₂ Cl ₂ , GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃
Br, GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, etc. Halogenated halides such as germanium hydride and the like, GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ ,
Germanium halide such as GeI ₂ and / or SnHF
₃ , SnH ₂ F ₂ , SnH ₃ F, SnHCl ₃ , SnH ₂ Cl ₂ , SnH ₃ Cl, SnHB
_{r 3, SnH 2 Br 2,} SnH 3 Br, SnHI 3, SnH 2 I 2, SnH 3 1 bract halides components hydrogen atoms such as hydride halogenated tin I like, SnF _4, SnCl _4, SnBr ₄ , SnI ₄ , SnF ₂ , SnCl
Substances in the gas state or gasifiable such as tin halides such as ₂ , SnBr ₂ and SnI ₂ 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.

To structurally introduce hydrogen atoms into the IR absorption layer, in addition to the above, Ge is supplied as H ₂ or silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H _10. For germanium or germanium compounds, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge
Tin or tin compounds for supplying germanium hydride and / or Sn such as ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , 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 _20, etc. tin hydride and silicon or silicon compound for supplying Si in the deposition chamber It can also be carried out by causing the discharge to coexist with.

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 halon 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, in order to make the IR absorption layer contain nitrogen atoms and / or carbon atoms and / or oxygen atoms, IR
A starting material for introducing a nitrogen atom and / or a carbon atom and / or an oxygen atom in the formation of the absorption layer is used together with the above-mentioned starting material for forming the IR absorption layer, and the amount thereof is controlled in the formed layer. It is sufficient to include it.

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.

Starting materials that can be effectively used as a source gas for introducing nitrogen atoms (N) include N as a constituent atom.
Or, having N and H as constituent atoms, for example, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ),
Mention may be made of gaseous or gasifiable nitrogen such as hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen compounds such as nitrides and azides. 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 nitrogen atom (N) and the introduction of the halogen atom (X). Mention may be made of 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.

For example, saturated hydrocarbon having 1 to 4 carbon atoms, 2 to 4 carbon atoms
Ethylene-based hydrocarbons, acetylene-based hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, methane (C
H 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 such as 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 (C ₂ H ₂ ) as acetylene hydrocarbons. , 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 can be introduced in addition to the introduction of the carbon atom (C) and the introduction of the halogen atom (X).
Carbon halide gas such as CF ₃ can be mentioned.

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,
If necessary, a raw material gas containing hydrogen atoms (H) and / or halogen atoms (X) as a constituent atom is mixed and used, or a raw material gas containing silicon atoms (Si) as a constituent atom. And a source gas containing oxygen atoms (O) and hydrogen atoms (H) as constituent atoms, which are also mixed at a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms, It is possible to mix and use a raw material gas having three constituent atoms of silicon atom (Si), oxygen atom (O) and hydrogen atom (H).

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.

A starting material effectively used as a raw material gas for introducing oxygen atoms (O) is, for example, oxygen (O ₂ ),
Ozone (O ₃ ), Nitric oxide (NO), Nitrogen dioxide (N
O ₂ ), nitrogen monoxide (N ₂ O), nitrogen trioxide (N ₂ O ₃ ),
Trinitrous 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 OSi
And lower siloxanes such as H ₃ ).

To form the IR absorption layer by the sputtering method,
When forming the IR absorption layer, a monocrystalline or polycrystalline 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 a mixture of and / or a SiC wafer or a wafer containing a mixture of 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 can be used as separate targets or by using a single target mixture of Si and Si ₃ N ₄ in an atmosphere of diluting gas as a gas for spatula or At least hydrogen atom (H) or /
And sputtering in a gas atmosphere containing a halogen atom (X) as a constituent atom.

Nitrogen atoms, carbon atoms, as the raw material gas for introducing oxygen atoms, the nitrogen atom in the raw material gas shown in the example of the glow discharge method described above, carbon atoms, the raw material gas for introducing oxygen atoms,
It can also be used as an effective gas in the case of sputtering.

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, the distribution concentration C ( N) and / or C (C) and /
Alternatively, the gas of the starting material for introducing the nitrogen atom and / or the carbon atom and / or the oxygen atom whose C (O) should be changed is appropriately changed in accordance with the desired rate-of-change curve, and the gas is placed in the deposition chamber. Made by introducing.

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 nitrogen atom and / or carbon atom and / or oxygen atom in the layer thickness direction is formed.
Alternatively, in order to change C (O) in the layer thickness direction 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, the starting material for introducing nitrogen atoms and / or carbon atoms and / or oxygen atoms 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.

Secondly, the Tagetsuto for Supatsutaringu, for example if using the mixed Tagetsuto of Si and Si ₃ N _4, the mixture ratio of Si and Si ₃ N _4, in the layer thickness direction of Tagetsuto, It is made by changing in advance.

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

The amount of nitrogen atoms (N), the amount of oxygen atoms (O), the amount of carbon atoms (C), the sum of the amounts of nitrogen atoms and oxygen atoms (N + O), or the simple substance 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.
It is desirable that the content is 01 to 40 atomic%, more preferably 0.05 to 30 atomic%, and most preferably 0.1 to 25 atomic%.

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 H
Examples thereof include boron hydride such as ₁₄ and boron halide such as BF ₃ , BCl ₂ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ ,, Ga (C
H _{3) 3,} may also be mentioned InCl _2, TlCl _3, etc..

A starting material for introducing a group V atom is effectively used in the present invention as PH ₃ , P for introducing a phosphorus atom.
Phosphorus hydride such as ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , PB
Examples thereof include phosphorus halides such as r ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , Sb
_{F 5, SbCl 3, SbCl 5} , BiH 3, BiCl 3, BiBr 3 , etc. may also be mentioned as effective starting materials for the group V atoms introduced.

Further, the layer thickness of the IR absorbing layer in the present invention is 0.05 from the viewpoint of obtaining desired electrophotographic characteristics and economic effects.
.About.25 .mu., Preferably 0.07 to 20.mu., optimally 0.1 to 15.mu.

Charge injection blocking layer The charge injection blocking layer is made of Non-SiMo (H, X) as described above.
Composed of. The charge injection blocking layer in the present invention has a function of blocking the injection of charges into the CTL from the support side when the surface of the photoreceptor layer is subjected to a charging treatment of one polarity and the other polarity. Such a function is not exhibited when it is subjected to a charging process, and it has a desired rectifying property. In order to impart such a function, the charge injection blocking layer contains a relatively large amount of a conductivity-controlling substance (M 2 _{O 3} ) which gives one conductivity type.

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

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

The conductivity controlling substance (M 2 _O ) contained in the charge injection blocking layer may have the same polarity as the conductivity controlling substance (M) contained in CTL described later, and They may have different polarities, and may be the same substance or different substances.

However, when subjected to electrification,
To make charge injection into CGL and CTL from the support side more effective, a charge injection blocking layer and CTL
It is preferable that the substances that control the conductivity contained therein have at least different polarities.

These are appropriately determined in consideration of the purpose when the layer of the light-receiving layer is designed. Specific examples of the substance (M 2 _O ) contained in the charge injection blocking layer for controlling conductivity are the above-mentioned substance (M _R ) for controlling conductivity and a substance (M ₂ ) for controlling conductivity described later. ) Can be mentioned.

FIGS. 12 to 16 show typical distribution states in the layer thickness direction of the substance (M _O ) that controls the conductivity when the charge injection blocking layer contains a non-uniform concentration distribution in the layer thickness direction. An example is shown.

In the examples of FIGS. 12 to 16, the horizontal axis represents the distribution concentration C (M _O ) of the substance (M _O ), the vertical axis represents the layer thickness t of the charge injection blocking layer, and t _B is the interface position on the support side. , _{T T} indicates the position of the interface on the side opposite to the support side. That is, the charge injection blocking layer is formed from the t _B side toward the t _T side.

Figure 12 shows the substance (M 2 _O ) contained in the charge injection blocking layer.
The first typical example of the state of distribution in the layer thickness direction is shown.

In the example shown in FIG. 12, from the interface position t _B side to the position t ₄ , the content concentration C (M _O ) of the substance (M 2 _O ) is contained while taking a constant value C ₁₂ from the position t ₄ The distribution concentration C (M _O ) is gradually and continuously reduced from C ₁₃ until reaching the interface position t _T. The distribution concentration C is C _{14 at the} interface position t _T.

In the example shown in FIG. 13, the distribution concentration C (M _O ) of the contained substance (M 2 _O ) gradually decreases continuously from C ₁₅ from position t _B to position t _T, and the distribution concentration C (M _O ) gradually decreases. _The distribution state is such that C ₁₆ is obtained at _T.

In the example shown in FIG. 14, the distribution concentration C of the substance (M 2 _O )
(M _O ) has a constant value of C ₁₇ between position t _B and position t ₅ , and is C _{18 at} position t _T. Position t ₅ and position t _T
Between and, the distribution density C (M _O ) is linearly reduced from the position t ₅ to the position t _T.

In the example shown in FIG. 15, the distribution concentration C (M _O ) has a constant value of C ₁₉ from the position t _B to the position t ₆ and from C ₂₀ to C ₂₁ from the position t ₆ to the position t _T. It is assumed that the distribution state decreases linearly.

In the example shown in FIG. 16, the distribution concentration C (M _O ) has a constant value of C ₂₂ from the position t _B to the position t _T.

In the present invention, when the charge injection blocking layer contains a substance (M 2 _{O 3} ) for controlling conductivity in a distribution state in which a large amount is distributed on the support side, the maximum value of the distribution concentration C (M 2 _O ) of the substance (M 2 _O ) is Preferably 50 atomic ppm or more, more preferably 80 atomic ppm
As described above, it is desirable that the layers are formed so that the distribution state can be optimally 100 atom ppm or more.

In the present invention, the content of the substance (M 2 _O ) contained in the charge injection blocking layer is appropriately determined as desired so that the purpose of the present invention can be effectively achieved, but is preferably 30 to 5 × 10 5. ⁴ atom ppm, more preferably 50 to 1 × 10 ⁴ atom
ppm, optimally 1 × 10 ^{2 to} 5 × 10 ³ atomic ppm is desirable.

Since the charge injection blocking layer contains carbon atoms and / or nitrogen atoms and / or oxygen atoms, the adhesion between the IR absorption layer and the charge injection blocking layer is improved and the charge injection blocking layer and the CTL are concentrated. The adhesion can be improved.

FIGS. 17 to 23 show the distribution of carbon atoms and / or oxygen atoms and / or nitrogen atoms (collectively referred to as “atoms (Z)”) contained in the charge injection blocking layer in the layer thickness direction. A typical example of a condition is shown.

In the examples of FIGS. 17 to 23, the horizontal axis represents the distribution concentration C _Z of atoms (Z), the vertical axis represents the layer thickness t of the charge injection blocking layer,
t _B indicates the interface position on the support side, and t _T indicates the interface position on the side opposite to the support side. That is, the charge injection blocking layer is formed from the t _B side toward t _T.

FIG. 17 shows the atoms (Z) contained in the charge injection blocking layer.
The first typical example of the state of distribution in the layer thickness direction is shown.

In the example shown in FIG. 17, from the interface position t _B to the position t ₇ , the distribution concentration C _Z of atoms (Z) is contained while taking a constant value of C _{23. From the} position t ₇ , the distribution concentration C is the interface position. It is gradually and continuously reduced from C ₂₄ up to t _T. Interface position t
_{At T} , the distribution concentration C is C ₂₅ .

In the example shown in FIG. 18, the distribution concentration C _Z of contained atoms (Z) is C ₂₆ from the position t _B to the position t _T.
The distribution state is gradually reduced from C to C ₂₇ at the position t _T.

In the case of FIG. 19, from the position t _B to the position t ₈ , the distribution concentration C _Z of the atom (Z) is C ₂₈ and has a constant value, and between the positions t ₈ and t _T, it is gradually continuous. The position t _T
Is substantially zero.

To the case of FIG. 20 is atom (Z) reaches the position t _T to the position t _B, the distribution concentration C _Z continuously reduced gradually from C _30, is substantially zero at the position t _T There is.

In the example shown in FIG. 21, the distribution concentration C _Z of atoms (Z)
Is a constant value with C ₃₁ between position t _B and position t ₉ ,
It is C _{32 at the} position t _T. Between the position t ₉ and the position t _T , the distribution concentration C _Z is linearly reduced from the position t ₉ to the position t _T.

In the example shown in FIG. 22, the distribution concentration C _Z of the atom (Z) takes a constant value of C ₃₃ from the position t _B to the position t _10, and C ₃₄ from the position _{T 10} to the position t _T by C _{34. It is} assumed that the distribution state decreases linearly up to ₃₅ .

In the example shown in FIG. 23, the distribution concentration C _Z of atoms (Z) takes a constant value of C ₃₆ from the position t _B to the position t _T.

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

In the present invention, the content of the atom (Z) contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably
The amount is preferably 0.001 to 50 atom%, more preferably 0.002 to 40 atom%, and most preferably 0.003 to 30 atom%.

The hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer in the present invention can compensate for dangling bonds existing in Non-SiM ₀ (H, X) and improve the layer quality.

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

In the present invention, the layer thickness of the charge injection blocking layer is such that desired electrophotographic characteristics can be obtained, and from the viewpoint of economic effect and the like,
It is preferably 0.01 to 10 μ, more preferably 0.05 to 8 μ, and most preferably 0.1 to 5 μ.

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

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

In the CGL of the present invention, as in the case of CTL described later, a substance (M) that controls conductivity, a carbon atom (C),
Neither a nitrogen atom (N) nor an oxygen atom (O) is contained substantially.

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, and most preferably 1 to 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
It can be formed by various thin film deposition methods such as a sputtering method, a sputtering method, a vacuum deposition method, an ion plating method, a photo CVD method, a thermal CVD method, an HRCVD method, and a FOCVD method.

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 under 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. Further, when forming by the sputtering method, for example, using a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, if necessary. , A hydrogen atom (H) or / and a halogen atom (X) is introduced into the deposition chamber for sputtering, and a plasma atmosphere of a desired gas is formed.

In the case of the ion plating method, for example, polycrystal silicon or single crystal silicon is housed in a vapor deposition board as an evaporation source, and this vapor deposition source is heated and evaporated by a resistance heating method or an electron beam method (EB method). In the same manner as in the sputtering method, except that the flying evaporated material is allowed to pass through a desired gas plasma atmosphere. To form CGL composed of Non-Si (H, X) by the HRCVD method, for example, a raw material gas for supplying Si is
The active species (A) is introduced into the activation space provided in the preceding stage in the deposition chamber where the pressure can be reduced under a desired gas pressure condition to cause glow discharge or overheat in the activation space. ) Is generated, 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 introduced into another activation space to generate an active species (B), The species (A) and the active species (B) are separately introduced into the deposition chamber to form a layer made of Non-Si (H, X) on the surface of a predetermined support which is installed at a predetermined position in advance. Just do it. 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 which is installed at a predetermined position in advance. A layer made of -Si (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 gas state or a gasifiable silicon hydride (silane). (E.g.) are used effectively, and in particular SiH ₄ , Si in terms of ease of handling during layer formation work and good Si supply efficiency.
₂ H ₆ is also preferred.

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

The halogen compounds that can be preferably used in the present invention, specifically, fluorine, chlorine, bromine, halogen gas _{iodine, BrF, ClF, ClF 3,} BrF 5, BrF 3, IF 3, IF 7, ICl , IB
and interhalogen compounds such as r.

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 , and SiBr ₄ can be cited as a preferable example. .

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.

CGL containing halogen atom according to glow discharge method
In the case of manufacturing, basically, for example, silicon halide as a raw material gas for supplying Si is introduced into a deposition chamber for forming CGL at a predetermined gas flow rate, and a glow discharge is caused to generate them. It is possible to form CGL on a desired support by forming a plasma atmosphere of the gas described above.However, in order to make it easier to control the introduction ratio of hydrogen atoms, CGL can be formed on these supports. Further, hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed in a desired amount to form a layer.

In addition, each gas may be used alone or in combination of a plurality of gases at a predetermined mixing ratio.

Sputtering method, ion plating method, HRCVD
Method, in order to introduce a halogen atom into the layer formed in any of the FOCVD method, by introducing a gas of the halogen compound or a silicon compound containing the halogen atom into the deposition chamber It is only necessary to form a plasma atmosphere.

Further, in the case of introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or the gases of the above-mentioned silanes are introduced into the deposition chamber for sputtering and the plasma atmosphere of the gases is changed. 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 _{2 and} other halogen-substituted silicon hydrides, etc. Gas state or gasifiable substances are also effective starting points for CGL formation It can be mentioned as a substance. Among these substances, the halides containing hydrogen atoms are introduced because, at the same time as the introduction of halogen atoms into the layer during the formation of CGL, hydrogen atoms that are extremely effective in controlling the electrical or photoelectric properties are also introduced. In the invention, it is used as a preferable raw material for introducing halogen.

In order to 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 Non-Si (H, X) (hereinafter abbreviated as "Non-SiM (C, N, O) (H, X)") and has a charge transport characteristic that satisfies 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

24 to 39 show typical examples of the state of distribution of the substance (M) contained in CTL in the layer thickness direction, which controls the conductivity.

24 to 39, the horizontal axis represents the distribution concentration C of the contained substance (M), the vertical axis represents the layer thickness of CTL, t _B is the position of the end surface of CTL on the support side, and t _T is The position of the end surface of the CTL opposite to the support side is shown. That is, the CTL containing the substance (M) is layered from the t _B side toward the t _T side.

FIG. 24 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. 24, from the interface position t _B where CGL and CTL contact to the position t ₁₁ , the distribution concentration C of the substance (M) is a constant value C ₃₇ , and the substance (M) is constant. There is contained in the CTL being formed, the interface than the concentration C ₃₈ in the position t ₁₆ position t
_It is gradually and continuously reduced until reaching _T. Interface position t
_{At T} , the distribution concentration C of the substance (M) has a value C ₃₉ .

In the example shown in FIG. 25, the distribution concentration C of the contained substance (M) is from the position t _B to the position t _T.
Concentration C _{41 at} position t _T gradually decreases continuously from C ₄₀
A distribution state as follows is formed.

In the case of FIG. 26, from the position t _B to the position t ₁₇ , the distribution concentration C of the substance (M) is set to a constant value with the concentration C _42, and the position t ₁₂
And between the position t _T, is reduced gradually continuously from C _43, at the position t _T, the distribution concentration C is substantially zero (where substantially less than the detection limit amount is zero The same applies to the meaning of "substantially zero" hereafter).

In the case of FIG. 27, 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 _44, it is substantially zero at the position t _T.

In the example shown in FIG. 28, the distribution concentration C of the substance (M)
Between the positions t _B and t ₁₃ has a constant value of the concentration C ₄₅ , and the position t _T has the concentration C ₆₆ . Between the position t ₁₃ and the position t _T , the distribution density C is linearly reduced from the position t ₁₃ to the position t _T.

In the example shown in FIG. 29, 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 ₄₇ to substantially zero. .

In the example shown in FIG. 30, the distribution concentration C of the contained substance (M) is the value C from the position t _B to the position t _T.
A distribution state is formed in which the value gradually decreases continuously from ₄₈ and has a value C ₄₉ at the position t _T.

In the example shown in FIG. 31, the distribution concentration C of the substance (M) has a constant value C ₅₀ from the position t _B to the position t ₁₉ ,
From the position t ₁₄ to the position t _T , the distribution state is such that it decreases linearly from the value C ₇₁ to the value C ₅₂ .

In the example shown in FIG. 32, the distribution concentration C of the substance (M) gradually increases continuously from the position t _B to the position t ₁₅ from the value C ₅₅ to C ₅₄ , and from the position t ₁₅ to C. _It takes a constant value of ₅₃ and forms a distribution state reaching the position t _T.

In the example shown in FIG. 33, the distribution concentration C of the substance (M) forms a distribution state in which it gradually increases continuously from C ₇₇ to C ₅₆ from the position t _B to the position t _T. There is.

In the example shown in FIG. 34, the distribution concentration C of the substance (M) is substantially zero to C ₅₉ from the position t _B to the position t _16.
Gradually increases continuously until it takes a constant value of C ₅₈ from the position t ₂₁ and forms a distribution state reaching the position t _T.

In the example shown in FIG. 35, the distribution concentration C of the substance (M) is substantially zero to C ₆₀ 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. 36, material distribution concentration C (M) is increased from C ₆₂ up to the position t ₁₇ from the position t _B C ₆₁ to a linear function manner, the C ₆₁ is the position t ₁₇ Take a certain value,
The distribution state is formed so as to reach the position t _T.

In the example shown in FIG. 37, the distribution concentration C of the substance (M) is substantially zero to C ₆₃ from the position t _B to the position t _T.
Up to a linear function.

In the example shown in FIG. 38, the distribution concentration C of the substance (M) forms a distribution state in which it gradually and continuously increases from position t _B to position t _T from C ₆₅ to C _64. There is.

In the example shown in FIG. 39, material distribution concentration C (M) is increased from C ₆₈ up to the position t ₁₈ from the position t _B C ₆₇ to a linear function manner, the C ₆₆ is the position t ₁₈ Take a certain value,
The distribution state is formed so as to reach the position t _T.

40 to 49 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.

40 to 49, the horizontal axis represents the distribution concentration C of contained atoms (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 the atom (Y) is layered from the t _B side toward the t _T side.

FIG. 40 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. 40, the distribution concentration C of atoms (Y) is C from the interface position t _B where CGL and CTL contact to the position t _19.
A CTL in which atoms (Y) are formed by creating a certain value of ₆₉
The concentration is gradually increased continuously from the concentration C ₇₀ from the position t ₁₉ to the interface position t _T. At the interface position t _T , the distribution concentration C of atoms (Y) is C ₇₁ .

In the example shown in FIG. 41, the distribution concentration C of contained atoms (Y) is from the position t _B to the position t _T.
Concentration C _{73 at} position t _T gradually decreasing continuously from C ₇₂
A distribution state as follows is formed.

In the case of FIG. 42, from the position t _B to the position t ₂₀ , the distribution concentration C of the atom (Y) is made constant with the concentration C _74, and the position t ₂₀
And between the position t _T, is gradually reduced continuously from C _75, at the position t _T, the distribution concentration C is substantially zero (where substantially less than the detection limit amount is zero Is the case).

In the case of FIG. 43, the distribution concentration C of atoms (Y) is at the position t _B.
Up to more position t _T, is reduced continuously and gradually from the concentration C _76, it is substantially zero at the position t _T.

In the example shown in FIG. 44, the distribution concentration C of atoms (Y)
It is in between position t _B and position t _21, is constant and concentration C _77, is a concentration C ₇₈ in the position t _T. Between the position t ₂₁ and the position t _T , the distribution density C is linearly reduced from the position t ₂₁ to the position t _T.

In the example shown in FIG. 45, 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 ₇₉ to substantially zero.

In the example shown in FIG. 46, the distribution concentration C of the contained atom (Y) is C ₈₀ from the position t _B to the position t _T.
The distribution state is gradually reduced from C to C ₈₁ at the position t _T.

In the example shown in FIG. 47, the distribution concentration C of atoms (Y) takes a constant value of C ₈₂ from the position t _B to the position t _22, and from C ₈₃ to C ₈₄ from the position t ₂₂ to the position t _T. It is assumed that the distribution state decreases linearly until.

In the example shown in FIG. 48, the distribution concentration C of atoms (Y) takes a constant value of C ₈₅ from the position t _B to the position t.

Example shown in FIG. 40 to 48 diagrams, both A shorter 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. 49, the t _T side and the t _B side are reversed in FIG. If, the distribution concentration C up to the position t ₂₃ from the interface position t _B atom (Y) is gradually increased continuously from C _88, the interface position from the C ₈₇ next position t ₂₈ at position t ₂₈ t _T Up to C ₈₆
It becomes a constant value.

Examples of the substance (M) that controls the conductivity include so-called impurities in the field of semiconductors. In the present invention, the periodic table III which gives the p-type conductivity characteristic can be used.
An atom belonging to the group (hereinafter referred to as "group III atom") is used. As the group III atom, specifically, B (boron),
There are Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferable.

In the present invention, the effect of mainly controlling the conductivity type and / or the conductivity and / or the effect of controlling CGL and CTL by containing a Group III atom as the substance (M) controlling conductivity in the entire layer region of CTL. While it is possible to obtain the effect of improving the charge injection property during the period, its content is set to a relatively small amount. The content of the substance (M) is preferably 1
× 10 ^-3 to 1 × 10 ³ atomic ppm, more preferably 5 × 10 ³ to 1 × 10
² atomic ppm, optimally 1 × 10 ^-2 to 50 atomic ppm is desirable.

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%.

The hydrogen atom and / or halogen atom contained in the CTL of the present invention can compensate the dangling bonds 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
It is desirable to be 10 to 30 atom%.

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

In the present invention, in order to introduce the atom (Y) into the CTL, the atom (Y) may be used together with the starting material for CTL formation, 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, a gaseous substance containing at least nitrogen atoms as constituent atoms or a gasified substance that can be gasified is selected from 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.

Starting materials that can be effectively used as a source gas for introducing nitrogen atoms (N) include N as a constituent atom.
Alternatively, for example, nitrogen (N ₂ ) having N and H as constituent atoms,
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 Compounds can be mentioned. In addition, nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F
₄ N ₂ ) and the like.

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 can be effectively used as a source gas for introducing carbon atoms (C) include C and H as constituent atoms, for example, a saturated hydrocarbon having 1 to 4 carbon atoms, and a C 2 to 2 carbon atom.
4, ethylene-based hydrocarbons, acetylene-based hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, methane (C
H ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), and 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), as the acetylenic hydrocarbon, 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 can be introduced in addition to the introduction of the carbon atom (C) and the introduction of the halogen atom (X).
Halocarbon gases CF ₃ and the like.

As a starting material for introducing oxygen atoms in the case of forming a CTL by glow discharge, HRCVD method, FOCVD method, at least a gaseous substance containing oxygen atoms as a constituent atom or a gasified substance that 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 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), and nitrogen dioxide (NO ₂ ). ，
Nitrogen monoxide (N ₂ O), nitrogen trioxide (N ₂ O ₃ ), nitrous oxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₂ ), silicon atom (Si), an oxygen atom (O), a hydrogen atom (H), and a constituent atom such as disiloxane (H ₃
Lower siloxanes such as SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ).

To form CTLs by the sputtering method, a single crystal or polycrystalline Si wafer or Si ₃ N ₄ should be used during CTL formation.
Wafer, or wafer containing Si and Si ₃ N ₄ mixed and / or SiO ₂ wafer, or
By using a wafer containing Si and SiO ₂ as a mixture and / or a SiC wafer or a wafer containing Si and SiC as a target, these are sputtered in various gas atmospheres. Just go.

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 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 source gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms, the source gas for introducing nitrogen atoms, carbon atoms, and oxygen atoms in the source gas shown in the example of the glow discharge method described above,
It can also be used as an effective gas in the case of sputtering.

In the present invention, when the CTL is formed, the distribution concentration C (Y) of the atoms (Y) contained in the layer is changed in the layer thickness direction to obtain a desired distribution state (depth profile) in the layer thickness direction. In order to form a layer having a glow discharge property, in the case of the HRCVD method and the FDCVD method, a starting material gas for introducing atoms (Y) whose distribution concentration C (Y) should be changed, and its gas flow rate are desired. It is made by appropriately changing it according to the change rate curve of 1 and introducing it into the deposition chamber.

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 formed by the sputtering method, the atom (Y)
Of the atom (Y) in the layer thickness direction by changing the distribution concentration C (Y) in the layer thickness direction in the layer thickness direction.
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 formed. Is appropriately changed as desired.

Second, a target for spattering, for example,
If a target containing a mixture of Si and Si ₃ N ₄ is used, the mixing ratio of Si and Si ₃ N ₄ is changed in advance in the layer thickness direction of the target.

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

In CTL, a substance (M) that controls the conduction property, for example,
To structurally introduce a Group III atom or a Group V atom, 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 a deposition chamber during layer formation. ,
It may be introduced together with other starting materials for forming CTL. 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, BR 3, BCl 2, BBr} 3 , etc. Halogen Boron bromide etc. are mentioned. In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₂ ,
Mention may also be made of TlCl _{3 and the} like.

CGL and CTL having properties that can achieve the object of the present invention
In order to select and configure A-Si (hereinafter referred to as "A-Si (H, X)") containing a hydrogen atom and / or a halogen atom as -Si (H, X), the temperature of the support is required. 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.
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 substrate temperature to a high temperature,
In this method, the temperature is set to 0 to 600 ° C., and a film is deposited on the support by a plasma CVD method.

Another method is to first form an amorphous film on the surface of the support, that is, to form a film on the support at a support temperature of, for example, about 250 ° C. by a plasma CVD method, and then subject the amorphous film to an annealing treatment. This is a method to make it poly. The annealing treatment was carried out by adding 400 to the support.
It is carried out by heating to 600600 ° 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.

50 to 59 show carbon atoms and / or nitrogen atoms and / or oxygen atoms (hereinafter,
These are collectively referred to as "atoms (Z)"), and typical examples of the state of distribution in the layer thickness direction are shown.

50 to 59, the horizontal axis represents the distribution concentration C of contained atoms (Z), the vertical axis represents the layer thickness of the surface layer, and t _B
Indicates the position of the end surface of the surface layer on the side opposite to the support side, and t _T indicates the position of the end surface of the surface layer on the side opposite to the support side. That is, the surface layer containing atoms (Z) is formed from the t _B side toward the t _T side.

FIG. 50 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. 50, the distribution concentration C of atoms (Z) gradually increases continuously from C ₁₁₁ to C ₁₁₀ from the position t _B to the position t _29, and from the position t ₂₉ to C. A distribution state is formed such that a constant value of ₁₀₉ is taken and the position reaches t _T.

In the example shown in FIG. 51, 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. 52, the distribution concentration C of atoms (Z) is substantially zero to C from the position t _B to the position t _30.
The distribution 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. 53, the distribution concentration C of atoms (Z) is substantially zero to C ₁₁₆ from the position t _B to the position t _T.
It forms a distribution state that gradually increases continuously until.

In the example shown in FIG. 54, 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 The distribution is formed such that it takes a constant value and reaches the position t _T.

In the example shown in FIG. 55, 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. 56, 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.

Distribution concentration C of the atoms (Z) in the example illustrated in 57 FIG. Up to the position t ₃₂ from the position t _B, until C ₁₂₃ increases a linear function from C _124, the C ₁₂₂ is the position t ₃₂ The distribution is formed such that it takes a constant value and reaches the position t _T.

In the example shown in FIG. 56, 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. 59, the distribution concentration C of atoms (Z) takes a constant value of C ₁₂₈ from position t _B to t ₃₃ ,
Takes a constant value of C ₁₂₇ up to the position t ₃₄ from the position t _33, they form a distribution state such as reaching the position t _T takes a constant value of C ₁₂₆ is the position t _34.

Carbon atoms or / and nitrogen atoms or / and oxygen atoms contained in the entire surface layer region of the present invention are
It mainly produces effects such as high dark resistance and high hardness. The content of atoms (Y) contained in the surface layer is preferably 1 × 10 ^−3.
It is desirable that the content is ˜90 atom%, more preferably 1 × 10 ⁻¹ ˜85 atom%, and optimally 10˜80 atom%.

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

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

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

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 temperature of the support is appropriately selected, but preferably 50 ° C to 400 ° C, 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, optimally 1 × 10 ^-2 1 Torr is desirable.

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 method is to raise the substrate temperature to a high temperature, specifically 400
This is a method in which the temperature is set to about 600 ° C. and a film is deposited on the substrate by the 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. 60 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, the raw material gas for forming each layer of the present invention is sealed, for example 1011 in
SiH ₄ gas (purity 99.999%) cylinder, 1012 H ₂ gas (purity 99.999%) cylinder, 1013 B ₂ H ₆ diluted with H ₂ gas
Gas (purity 99.999% or less abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 1014
Is NO gas (purity 99.5%) cylinder, 1015 is GeH ₄ gas (purity
99.999%) cylinder, 1016 is NH ₃ gas (purity 99.999%) cylinder, and 1017 is CH ₄ gas (purity 99.999%) cylinder.

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

That is, SiH ₄ gas and B ₂ H _{6 are} used as the IR absorption layer forming gas.
/ H ₂ gas, No gas, GeH ₄ gas as charge injection blocking layer forming gas SiH ₄ gas, H ₂ , B ₂ H ₆ / H ₂ gas, NO gas, CTL forming gas SiH ₄ gas, NH ₃ gas, B ₂ H ₆ gas, SiH ₄ gas and H ₂ gas as CGL forming gas, and SiH ₄ gas and CH ₄ gas as surface layer forming gas will be described.

To allow these gases to flow into the reaction chamber 1001, confirm that the valves 1051 to 1057 of the gas cylinders 1011-1017 and the leak valve 1003 of the reaction chamber 1011 are closed, and that the inflow valves 1031 to 1037 and the outflow valve 1041 are closed. ~ 1047, auxiliary valve
Make sure the 1070 is open, then first open the main valve 10
Open 02 to evacuate the reaction chamber 1001 and the gas pipe.

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

After that, from the gas cylinder 1011, SiH ₄ gas, gas cylinder 10
12 from H ₂ gas, gas cylinder 1013 from B ₂ H ₆ / H ₂ gas, gas cylinder 1014 from NO gas, gas cylinder 1015 from 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.

In addition, the base cylinder 1007 installed in the reaction chamber 1001.
Is heated by the heater 1008 to a desired temperature between 50 and 350 ° C.

After the preparation for film formation is completed as described above, the IR absorption layer, the charge injection blocking layer, the CTL, the CGL, and the
Each surface layer is formed.

To form the IR absorption layer, the outflow valves 1041, 1043, 104
4,1045 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, SiH ₄ gas flow rate, B ₂ H ₆ / H ₂ gas flow rate, NO
Adjust the outflow valves 1041, 1043, 1044, and 1045 so that the gas flow rate and GeH ₄ gas flow rate are at the desired values, and also check the vacuum gauge 1004 so that the pressure inside the reaction chamber is at the desired value while checking the 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 forming the desired film thickness, stop the RF glow discharge,
Further, 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.

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

To form the charge injection blocking layer, the outflow valves 1041 and 104
Gradually open 2,1043,1044 and auxiliary valve 1070 to SiH ₄
Gas, H ₂ gas, B ₂ H ₆ / H ₂ gas and NO gas are caused to flow into the reaction chamber 1001. At this time, SiH ₄ gas flow rate, H ₂ gas flow rate, B ₂ H ₆
Adjust the outflow valves 1041, 1042, 1043, 1044 so that the / H ₂ gas flow rate and NO gas flow rate are at the desired values, and while watching the vacuum gauge 1004 so that the pressure in the reaction chamber is at the desired value. Adjust the opening of the main valve 1002. After that, the power source 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber 1001, and the formation of the charge injection blocking layer on the base cylinder is started. After the desired film thickness is formed, the RF glow discharge is stopped, and the outflow valves 1041, 1042, 1043, 1044 are closed to stop the gas from flowing into the reaction chamber, and the formation of the charge injection blocking layer is completed. .

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

To form CTL, gradually open the outflow valves 1041, 1043, 1045 and the auxiliary valve 1070, and SiH ₄ gas, B ₂ H ₆ gas, NH
₃ Gas is allowed to flow into the reaction chamber 1001. At this time, the outflow valves 1041, 1043, 1045 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ gas flow rate, and the NH ₃ gas flow rate have 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 1010
Is set to a desired power to generate an RF glow discharge in the reaction chamber and start forming CTLs on the substrate cylinder. After the desired film thickness is formed, the RF glow discharge is stopped, the outflow valves 1041, 1043, 1045 are closed to stop the gas flow into the reaction chamber, and the CTL formation is completed.

Outflow valves 1041 and 1042 to form CGL on the above CTL
Further, the auxiliary valve 1070 is gradually opened to allow SiH ₄ gas and H ₂ gas to flow into the reaction chamber 1001. At this time, SiH ₄ gas flow rate,
Outflow valves 1041 and 104 so that the flow rate of H ₂ gas reaches a desired value.
2 and adjust the opening of the main valve 1002 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 generate an RF glow discharge in the reaction chamber, and the CG is placed on the base cylinder.
The formation of L begins. After forming the desired film thickness, R
The F 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.

A surface layer is formed on the CGL 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 becomes 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 the outflow valves other than the gas necessary for forming each layer are completely closed, and each gas is in the reaction chamber 1001 and the outflow valve 1041 ~
In order to avoid remaining in the pipe from 1047 to the reaction chamber 1001, the outflow valves 1041 to 1047 are closed and the auxiliary valve 10
If necessary, an operation of opening 70, fully opening the main valve 1002, and once exhausting the system to a high vacuum is performed.

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

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

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

FIG. 61 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the μW glow discharge decomposition method.

In the gas cylinders 2011, 2012, 2013, 2014, 2015, 2016, 2017 in the figure, the raw material gas for forming each layer of the present invention is sealed, for example, in 2011
SiH ₄ gas (purity 99.999%) cylinder, H ₂ gas (purity 99.999%) cylinder for 2012, B ₂ H ₆ diluted with H ₂ gas for 2013
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, and 2017 is CH ₄ gas (purity 99.999%) cylinder.

SiH ₄ gas, B ₂ H ₆ / H ₂ , NO ₂ gas, GeH ₄ gas as the IR absorption layer forming gas as an example of the gas used when forming the photoreceptive member for electrophotography in the apparatus shown in FIG. As a charge injection blocking layer forming gas, SiH ₄ gas, H ₂ , B ₂ H ₆ / H ₂ , N
O gas is used as CTL formation gas, SiH ₄ gas, NH ₃ gas, B ₂ H
_{The case where 6} gases, SiH ₄ gas and H ₂ gas are used as the CGL forming gas, and SiH ₄ gas and CH ₄ gas are used as the surface layer forming gas will be described.

To make these gases flow into the reaction chamber 2001, make sure that the valves 2051 to 2057 of the gas cylinders 2011 to 2017 and the leak valve 2003 of the reaction chamber 2011 are closed, and that the inflow valves 2031 to 2037 and the outflow valve 2041 are closed. ~ 2047, auxiliary valve
Make sure the 2070 is open, then first open the main valve.
Open 2002 and 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 20
12 from H ₂ gas, gas cylinder 2013 from B ₂ H ₆ / H ₂ gas, gas cylinder 2014 from NO gas, gas cylinder 2015 from GeH ₄ gas,
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 2kg / 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.

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

After the preparation for film formation is completed as described above, the IR absorption layer, the charge injection blocking layer, the CTL, the CGL, and the
Each surface layer is formed.

Outflow valves 2041,2043,204 to form the IR absorption layer
4,2045 and auxiliary valve 2070 are gradually opened to SiH ₄ gas,
B ₂ H ₆ / H ₂ gas, NO gas, and GeH ₄ gas are made to flow into the reaction chamber 2001. At this time, SiH ₄ gas flow rate, B ₂ H ₆ / H ₂ gas flow rate, NO
Adjust the outflow valves 2041,2043,2044,2045 so that the gas flow rate and GeH ₄ gas flow rate are the specified values. Also, while watching the vacuum gauge 2004 to see that the pressure in the reaction chamber is the desired value, main Adjust the opening of valve 2002. After that, the microwave power source 2008 is set to a desired power, a μW glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 2010, and the formation of the IR absorption layer on the substrate cylinder is started. After forming the desired film thickness, stop the μW glow discharge,
Further, the outflow valves 2041, 2043, 2044, 2045 are closed to stop the inflow of gas into the reaction chamber, and the formation of the IR absorption layer is completed.

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

To form the charge injection blocking layer, the outflow valves 2041,204
Gradually open 2,2043,2044 and the auxiliary valve 2070 to SiH ₄
Gas, H ₂ gas, B ₂ H ₆ / H ₂ gas, and NO gas are made to flow into the reaction chamber 2001. At this time, SiH ₄ gas flow rate, H ₂ gas flow rate, B ₂ H ₆
While adjusting the outflow valves 2041,2042,2043,2044 so that the / H ₂ gas flow rate and the NO gas flow rate are at the desired values, and also looking at the vacuum gauge 2004 so that the pressure in the reaction chamber is at the desired value. Adjust the opening of the main valve 2002. After that, the microwave power source 2008 is set to a desired power, a μW glow discharge is generated in the reaction chamber 2001 through the waveguide 2009 and the dielectric window 2010, and the formation of the charge injection blocking layer on the substrate cylinder is started. After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valves 2041, 2042, 2043, 2044 are closed to stop the gas from flowing into the reaction chamber 2001 to form the charge injection blocking layer. To finish.

CTL is formed on the charge injection blocking layer formed as described above.
To form. Outflow valves 2041,2043,2 to form CTL
045 and auxiliary valve 2070 are gradually opened to SiH ₄ gas, B ₂ H
₆ gas and NH ₃ gas are made to flow into the reaction chamber 2001. This time,
Adjust the outflow valves 2041, 2043, 2045 so that the SiH ₄ gas flow rate, B ₂ H ₆ gas flow rate, and NH ₃ gas flow rate are at the desired values, and also vacuum so that the pressure in the reaction chamber is at the desired value. Total 2004
Adjust the opening of the main valve 2002 while watching. Then, set the microwave power supply 2008 to the desired power and
A μW glow discharge is generated in the reaction chamber through 2009 and the dielectric window 2010 to initiate the formation of CTL on the substrate cylinder. After the desired film thickness is formed, the μW glow discharge is stopped, the outflow valves 2041, 2043, 2045 are closed to stop the gas flow into the reaction chamber, and the CTL formation is completed.

Outflow valves 2041,2042 to form CGL on the above CTL
Then, the auxiliary valve 2070 is gradually opened to allow SiH ₄ gas and H ₂ gas to flow into the reaction chamber 2001. At this time, SiH ₄ gas flow rate,
Outflow valves 2041 and 204 so that the flow rate of H ₂ gas reaches the desired value
2 is 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 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 CGL is placed on the substrate cylinder.
Start forming. After forming the desired film thickness, μ
The W glow discharge is stopped, and the outflow valves 2041 and 2042 are closed to stop the inflow of gas into the reaction chamber to complete the formation of CGL.

A surface layer is formed on the CGL 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 each gas is in the reaction chamber 2001 and the outflow valves 2041 to 2046.
To avoid remaining in the pipe from the reaction chamber to the reaction chamber 2001, the outflow valves 2041 to 2046 are closed, the auxiliary valve 2070 is opened, and the main valve 2002 is fully opened to temporarily exhaust the system to a high vacuum. Do as needed.

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. 62 shows an apparatus for manufacturing an electrophotographic light-receiving member by the HRCVD method.

In FIG. 62, 3001 is a film forming chamber, 3002 is an activation chamber (A), 3003 and 3018 are microwave plasma generators, 300
4 is a raw material gas introduction pipe of active species (A), 3005 is an active species (A) introduction pipe, 3006 is a motor, 3007 is a heater for heating a cylindrical substrate, 3008 and 3009 are blowing pipes, 301
Reference numeral 0 indicates a cylindrical substrate, and 3011 indicates a main exhaust valve. Further, reference numerals 3012 to 3016 are cylinders for supplying a source gas, 3017 is an activation chamber (B), 3019 is a source gas introduction pipe,
3020 is an active species introduction tube generated from the active chamber (B). A method for producing an electrophotographic light-receiving member having a layer structure according to the present invention on a cylindrical substrate using this apparatus will be specifically described.

As an example, Al is used as the cylindrical substrate, and the IR absorbing layer forming gas is SiH ₄ , GeH ₄ , B ₂ H ₆ , NO, H ₂ ,
The charge injection blocking layer forming gas is SiH ₄ , B ₂ H ₆ , NO, H ₂ and CT.
SiH ₄ , SiF ₄ , CH ₄ , H ₂ and B ₂ H ₆ are used as L forming gas, and CG
SiH ₄ and H ₂ were used as the L forming gas, and SiH ₄ and CH ₄ were used as the surface layer forming gas.

First, the Al cylindrical substrate 3010 is hung in the film forming chamber 3001, a heater 3007 is provided inside the film forming chamber 3001, and a motor 3006 is provided.
And the chamber was evacuated to 5 × 10 ⁻⁶ Torr.

In order to form the IR absorption layer, H ₂ gas is introduced from the cylinder 3012 to the activation chamber (A) through the waveguide 3004, activated by the microwave plasma generator 3003, and activated hydrogen is introduced through the introduction pipe 3005. It was led to a film forming chamber 3001 from a blowoff pipe 3008. On the other hand, SiH ₄ gas from a cylinder 3013, B ₂ H ₆ gas from 3014, NO gas from 3015, CH ₄ gas from 3016, GeH ₄ gas and SiF ₄ gas from a cylinder not shown in an activation chamber (B ) 3017, microwave plasma generator 3018
After being activated by
From 3009 led to the film forming chamber 3001. At this time, the gas flow rate, internal pressure, and microwave power are set to desired values.

The Al cylindrical 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 IR absorption layer was formed.

Similarly, on the above IR absorption layer, a cylinder 3012 produces H ₂ gas, 3013 produces SiH ₄ gas, 3014 produces B ₂ H ₆ gas, and 3015 produces NO.
A gas was supplied to form a charge injection blocking layer.

A cylinder 301 for forming a CTL on the charge injection blocking layer
H ₂ gas from ₂ was introduced into the activation chamber (A) through the introduction pipe 3004, activated by the microwave plasma generator 3003, and active hydrogen was introduced through the introduction pipe 3005 into the film formation chamber 3001 through the blowing pipe 3008. . On the other hand, SiH ₄ gas from the cylinder 3013, B ₂ H ₆ gas from the cylinder 3014, CH ₄ gas from the cylinder 3016, and SiF ₄ gas from the cylinder not shown are introduced into the activation chamber (B) 3017 through the introduction pipe 3019, Wave plasma generator
After the activation treatment by 3018, it was led to the film forming chamber 3001 through the introduction pipe 3020 and the blowing pipe 3009. 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 hawaii gas was exhausted by appropriately adjusting the opening of the main exhaust valve 3011. In this way CTLs were formed. Similarly to above CTL, from cylinder 3012 H
₂ gas, SiH ₄ gas from 3013, CF by supplying SiF ₄ gas from a cylinder not shown, H ₂ gas from the cylinder 3012, SiH ₄ gas from the cylinder 3013, CH ₄ gas from the cylinder 3016 on the CGL The surface layer was sequentially supplied 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. 63 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 each layer of the present invention is sealed, as an example, for example, 4011 SiH ₄ gas (purity 99.999%) bomb, H ₂ gas (99.999% purity) in 4012 bomb in 4013 was diluted with H ₂ B 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%) cylinder, 4016 is CH ₄ gas (purity 99.999%)
The cylinder, 4017, is F ₂ gas (10% He diluted, purity 99.99%).

As IR absorbing layer forming gas, SiH ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, GeH ₄ gas, the F _2, SiH ₄ gas as the charge injection blocking layer forming gas, H ₂ gas, B ₂ H ₆ / H ₂ gas, NO gas, F ₂
SiH ₄ gas, CH ₄ gas, B ₂ H ₆ as CTL forming gas
Gas, F ₂ gas, CGL forming gas SiH ₄ gas, H ₂ gas, F ₂ gas, surface layer forming gas SiH ₄ gas, CH
Let us consider the case of using ₄ gas and F ₂ gas.

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

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

The vacuum chamber 4001 is 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).

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

To introduce gas from cylinders 4011-4016 into 4001, 4001
When the inside of the chamber reaches about 5 × 10 ^-6 Torr, it must be slowly introduced by various valve operations.

In addition, the base cylinder installed in the chamber 4001
The temperature of 4060 may be heated to a desired temperature between 50 and 350 ° C. by the heater 4061.

After the film formation preparation is completed as described above, the IR absorption layer, the charge injection blocking layer, the CTL, and the CGL are formed on the base cylinder 4060 in this order.

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 to release SiH ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, Ge
H ₄ gas is caused to flow into the reaction chamber 4001. At this time, the outflow valves 4031, 4033, 4034, 4035 are adjusted so that the SH 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.
Is adjusted, and the opening of the main valve 4002 is adjusted while observing a vacuum gauge (not shown) at which the pressure in the reaction chamber reaches a desired value.

Next, open 4052, while 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 charge injection blocking layer is formed on the IR absorption layer formed 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.

A valve 404 is used to form a CTL on the charge injection blocking layer.
6-4049,4052 are opened, the outflow valves 4031-4043,4037 and the auxiliary valve 4060 are gradually opened to allow each gas to flow into the reaction chamber 4001. At this time, each outflow valve is adjusted so that the gas flow rate of each gas is a desired value, and the opening of the main valve 4002 is adjusted while observing a vacuum gauge (not shown) where the pressure in the reaction chamber is a desired value. To do.

After the setting of the flow rate is completed and the time for forming the CTL to a desired film thickness is reached, the formation of the CTL is completed.

CGL and a surface layer are formed on the CTL 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 above CTL.

〔Example〕

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

<Example 1> Using the manufacturing apparatus shown in FIG.
A light-receiving member for electrophotography was formed on an aluminum cylinder that had been mirror-finished according to the preparation conditions shown in Tables, 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 deterioration of charging ability, surface scraping, and increase of image defects were investigated after accelerated durability equivalent to 2 million sheets.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 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. 70, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 6, and 7, and the same. Was evaluated.

 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. 70, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Table 1, Table 2, Table 9 and Table 10, and the same. Was evaluated.

 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. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Table 1, Table 2, Table 12, and Table 13, and the same. Was evaluated.

 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. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Table 1, Table 2, Table 15, and Table 16, and the same. Was evaluated.

 The results are shown in Table 17.

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

<Example 6> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Table 1, Table 2, Table 18, and Table 19, and the same. Was evaluated.

 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. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 21, and 22. Was evaluated.

 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. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 24 and 25, and Was evaluated.

 The results are shown in Table 26.

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

<Example 9> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 27 and 28. Was evaluated.

 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. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 30, and 31 and the same. Was evaluated.

 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. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 33 and 34, and Was evaluated.

 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. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 36 and 37. Was evaluated.

 The results are shown in Table 38.

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

<Example 13> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 39 and 40, and Was evaluated.

 The results are shown in Table 41.

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

<Example 14> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 42 and 43, and Was evaluated.

 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. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 45, and 46. Was evaluated.

 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. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 48 and 49, and Was evaluated.

 The results are shown in Table 50.

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

<Example 17> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 51 and 52. Was evaluated.

 The results are shown in Table 53.

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

<Embodiment 18> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 54, and 55. Was evaluated.

 The results are shown in Table 56.

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

<Example 19> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 57 and 58, and the same. Was evaluated.

 The results are shown in Table 59.

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

<Embodiment 20> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Embodiment 1 under the preparation conditions shown in Tables 1, 2, 60, and 61 by RF glow discharge. Was evaluated.

 The results are shown in Table 62.

As shown in Table 62, good results were obtained for all items.

<Example 21> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 63 and 64, and Was evaluated.

 The results are shown in Table 65.

As shown in Table 65, good results were obtained for all items.

<Embodiment 22> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 66 and 67, and Was evaluated.

 The results are shown in Table 68.

As shown in Table 68, good results were obtained for all items.

<Embodiment 23> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 69 and 70. Was evaluated.

 The results are shown in Table 71.

As shown in Table 71, good results were obtained for all items.

<Example 24> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 72 and 73, and Was evaluated.

 The results are shown in Table 74.

As shown in Table 75, good results were obtained for all items.

<Embodiment 25> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 75, and 76, and Was evaluated.

 The results are shown in Table 77.

As shown in Table 77, good results were obtained for all items.

<Example 26> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 78 and 79, and Was evaluated.

 The results are shown in Table 80.

As shown in Table 80, good results were obtained for all items.

<Example 27> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 81 and 82, and Was evaluated.

 The results are shown in Table 83.

As shown in Table 83, good results were obtained for all items.

<Example 28> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 84 and 85, and Was evaluated.

 The results are shown in Table 86.

As shown in Table 86, good results were obtained for all items.

<Example 29> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 87 and 88, and Was evaluated.

 The results are shown in Table 89.

As shown in Table 89, good results were obtained for all items.

<Example 30> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 90, and 91, and Was evaluated.

 The results are shown in Table 92.

As shown in Table 92, good results were obtained for all items.

<Example 31> Using the manufacturing apparatus shown in FIG. 60, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 93, and 94, and Was evaluated.

 The results are shown in Table 95.

As shown in Table 95, good results were obtained for all items.

Example 32 Using the manufacturing apparatus shown in FIG.
The light-receiving member for electrophotography was formed on a mirror-finished aluminum cylinder according to the preparation conditions shown in Tables to 99.

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 100 shows the comprehensive evaluation results.

As shown in Table 100, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 33> Using the manufacturing apparatus shown in FIG.
According to the preparation conditions shown in Table 104, a light-receiving member for electrophotography was formed on a mirror-finished aluminum cylinder. The prepared electrophotographic light-receiving member is set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and under various conditions, an initial charging ability, The electrophotographic characteristics such as sensitivity, residual potential and ghost were checked, and the 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 105 shows the comprehensive evaluation results.

As shown in Table 105, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 34> Using the manufacturing apparatus shown in FIG.
An electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the preparation conditions shown in Table 109.

The prepared electrophotographic light-receiving member is set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source,
Under various conditions, check the electrophotographic characteristics such as initial chargeability, sensitivity, residual potential, ghost, etc., and decrease chargeability, surface scraping, and increase of image defects after 2 million sheets of accelerated real machine durability. Etc.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 110 shows the comprehensive evaluation results.

As shown in Table 110, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 35> A cylinder subjected to mirror surface processing is further subjected to lathe processing with a sword bite having various angles, and a cylinder having a sectional shape as shown in Fig. 68 and various sectional patterns as shown in Table 112 is obtained. I prepared multiple books. The cylinders in turn, 60th
It was set in the manufacturing apparatus shown in the figure, and the drum was manufactured under the manufacturing conditions shown in Table 111. 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 113 were obtained.

<Example 36> The surface of the mirror-finished cylinder was continuously exposed to a large number of bearing balls to be dropped, and a so-called surface dimple treatment for producing innumerable dents on the cylinder surface was performed. A plurality of cylinders having the cross-sectional shape shown in the figure and having various cross-sectional patterns as shown in Table 115 were prepared. The cylinders were sequentially set in the production apparatus shown in FIG. 60 and subjected to the drum production under the production conditions shown in Table 114. The prepared drum was subjected to various evaluations by an electrophotographic apparatus having a halogen lamp as a light source and an electrophotographic apparatus having a digital exposure function having a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 116 were obtained. .

<Example 37> Using the manufacturing apparatus shown in Fig. 60, a drum was prepared in the same manner as in Example 1 under the preparation conditions shown in Tables 117 to 119, and the same evaluation was performed.

 The results are shown in Table 120.

As shown in Table 120, 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. Further, its electrical characteristics are stable, and an image obtained by using it has a high density and a clear halftone, and is very excellent.

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

[Brief description of drawings]

FIG. 1 is a schematic layer structure diagram for explaining a layer structure of a light-receiving member for electrophotography of the present invention, and FIGS. 2 to 5 are uneven shapes on a surface of a support and a method for producing the uneven shapes, respectively. 6 to 11 are explanatory views of the distribution state of atoms (Gs) contained in the IR absorption layer, and FIGS. 12 to 16 are charge injection blocking layers, respectively. And FIG. 17 to FIG. 23 are explanatory views of the distribution state of the substance (M 2 _O ) controlling the conductivity contained therein, respectively, and FIGS. 17 to 23 are the description of the distribution state of the atom (Y) contained in the charge injection blocking layer. Figures 24 to 39 show the distribution of CTL-constituting substances, and Figures 40 to 49 show the distribution of carbon atoms and / or oxygen atoms and / or nitrogen atoms, respectively. FIGS. 50 to 59 are explanatory diagrams for explaining the carbon atoms constituting the surface layer, respectively. Is an explanatory view for explaining a distribution state of oxygen atoms and / or nitrogen atoms, and FIG. 60 is an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography of the present invention, which is a glow using RF. FIG. 61 is a schematic explanatory view of a manufacturing apparatus by a discharge method, and FIG. 61 is an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography of the present invention, which is a schematic view of a manufacturing apparatus by a glow discharge method using microwaves. 62 is a schematic explanatory view of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention, and FIG. 63 is a schematic illustration of a manufacturing apparatus by the HRCVD method, and FIG. 63 is an electrophotography according to the present invention. FIG. 64 is a schematic explanatory view of a manufacturing apparatus by the FOCVD method, which is an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotographic use, and FIG. 64 shows the CTL of the light receiving member for electrophotography of the present invention using RF glow discharge. When forming impurity gas and doping gas when forming FIG. 65 is a diagram showing the flow rate change at the time of film formation of the impurity gas and the doping gas when the CTL of the electrophotographic light-receiving member of the present invention is formed by leaving it in the microwave glow. FIG. 66 shows the impurity gas and the doping concentration when the CTL of the electrophotographic light-receiving member of the present invention is formed by using the HRCVD method.
FIG. 67 is a diagram showing a change in flow rate during gas film formation. FIG. 67 shows 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 where the electrophotographic light-receiving member of the present invention is formed. 69 is an enlarged view of the cylinder cross section in the case of a letter shape, FIG. 69 is an enlarged view of the cylinder cross section when the surface of the cylinder substrate when forming the electrophotographic light-receiving member of the present invention is subjected to so-called dimple processing, 70 The figure is a diagram showing flow rate changes at the time of film formation of an impurity gas and a doping gas in the case of an embodiment in which the CTL of the electrophotographic light-receiving member of the present invention is formed by using RF glow discharge. Regarding Fig. 1, 101 ... Support 102 ... Photoreceptive layer 103 ... IR absorption layer 104 ... Charge injection blocking layer 105 ... CTL 106 ... CGL 107 ... Surface layer 108 ... Free surface Fig. 3 , Fig.4, 301,401 …… Support 302,402 …… Support surface 303,403 …… Rigid spherical sphere 304,404 …… Spherical trace depression About Fig. 500 500 …… Photoreceptive layer 501 …… Support 502 …… IR absorption Layer 503 …… Charge injection blocking layer 504 …… CTL 505 …… CGL 506 …… Surface layer 507 …… Free surface In Fig. 60, 1001 …… Reaction chamber 1002 …… Main exhaust valve 1003 …… Reaction chamber leak valve 1004 …… Vacuum gauge 1007 …… Cylinder base 1008 …… Heater for heating the base 1009 …… Cylinder base rotation motor 1010 …… RF power supply 1011 to 1017 …… Raw material gas cylinder 1021 to 1027 …… Mass flow controller 1031 〜1037 …… Gas inlet valve 1041〜1047 …… Gas outlet valve 1051〜1057 …… Original Gas cylinder valves 1061 to 1067 …… Pressure regulator Fig. 61, 2001 …… Reaction chamber 2002 …… Main exhaust valve 2003 …… Reaction chamber leak valve 2004 …… Vacuum gauge 2005 …… Substrate heating heater 2006 …… Cylindrical substrate 2007 …… Motor for rotating substrate 2008 …… Microwave power source 2009 …… Waveguide 2010 …… Dielectric window 2011 to 2017 …… Gas cylinder 2021 to 2027 …… Mass flow controller 2031 〜2037 …… Gas inflow valve 2041〜2047 …… Gas outflow valve 2051〜2057 …… Valve for gas cylinder 2061〜1267 …… Pressure regulator About Fig. 62, 3001 …… Deposition chamber 3002 …… Activation Chamber (A) 3003,3018 …… Microwave plasma generator 3004,3019 …… Source gas introduction pipe 3005,3020 …… Activated species introduction pipe 3006 …… Motor 3007 …… Cylinder substrate heating heater 3008,3009 …… Blowout Tube 3010 ... cylindrical Body 3011 …… Main exhaust valve 3012 ～ 3016 …… Raw material gas cylinder 3017 …… Activation chamber (B) About Fig. 63, 4001 …… Reaction chamber 4002 …… Main exhaust valve 4011 ～ 4017 …… Raw material gas cylinder 4020, 4021 …… Source gas introduction pipe 4031-4037 …… Outflow valve 4046 〜 4052 …… Inflow valve 4053 〜 4059 …… Mass flow controller 4060 …… Cylindrical substrate 4061 …… Cylinder substrate heater 4062 …… Cylinder Motor for rotating the substrate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryuji Okamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP 62-5248 (JP, A) JP 62 -5247 (JP, A) JP 62-115457 (JP, A) JP 62-115456 (JP, A)

Claims (1)

[Claims] 1. A layer structure in which a support and a long-wavelength light absorption layer, a charge injection blocking layer, a charge transport layer, a charge generation layer and a surface layer are laminated in this order from the support side. And a photoreceptive layer having, wherein the surface layer contains a silicon atom, at least one of a carbon atom, a nitrogen atom and an oxygen atom, and at least one of a hydrogen atom and a halogen atom. The long wavelength light absorbing layer, the charge injection blocking layer, the charge transporting layer and the charge generating layer are made of a material and contain at least one of a hydrogen atom and a halogen atom with a silicon atom as a base material. The long-wavelength light absorption layer is made of a non-single-crystal material and further contains at least one of germanium atom and tin atom, and the charge injection blocking layer is a periodic table.
The charge transport layer further contains an atom belonging to Group III or Group V, and contains at least one of a carbon atom, a nitrogen atom and an oxygen atom.
A photoreceptor for electrophotography, comprising at least a portion containing an atom belonging to Group V 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. Element.