JPH0797229B2 - Photoreceptive member for electrophotography - Google Patents

Description

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

[Description of Prior Art]

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

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

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

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

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

That is, for example, the photoconductive layer formed by photoirradiation does not have a sufficient life in the photoconductive layer, or the image transferred to the transfer paper is commonly referred to as "white blank", 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 object of the present invention is that electrical, optical, and photoconductive properties are substantially stable regardless of the operating environment, are excellent in light fatigue resistance, and deteriorate even after repeated use. To provide a photoreceptive member for electrophotography, which has a photoreceptive layer composed of a material having a silicon atom as a base material, which does not cause deterioration, is excellent in durability and moisture resistance, and has no or almost no residual potential observed. It is in.

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

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

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

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

[Structure of Invention]

The light-receiving member for electrophotography of the present invention comprises a support and a non-single-crystal material containing a silicon atom as a base material and at least one of a hydrogen atom and a halogen atom on the support (hereinafter referred to as “Non -Si (H, X)]). In a light-receiving member for electrophotography, the light-receiving layer comprises a charge injection blocking layer and a charge generation layer (hereinafter referred to as "Si (H, X)]". CGL]) and a charge transport layer (hereinafter abbreviated as “GTL”) are laminated.
The charge injection blocking layer further contains an atom belonging to Group III or Group V of the periodic table, and the charge transport layer contains at least one of a carbon atom, a nitrogen atom and an oxygen atom. At least a portion containing atoms belonging to Group III or V of the table in a layer thickness direction having a concentration increasing or decreasing portion in the layer thickness direction from the support side, and The charge generation layer is characterized by being made thinner than the charge transport layer.

[Action]

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

In addition, since the charge injection blocking layer is provided between the support and CGL, when subjected to a charging treatment, the charge injection blocking layer is applied from the support side.
The charge can be effectively prevented from being injected into the CGL, and the charging ability is dramatically improved.

In particular, there is practically no effect of residual potential on image formation, its electrical characteristics are stable, and it has high sensitivity and high SN ratio. Since it is excellent in moisture resistance and electric resistance, 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 images based on digital signals 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, CTL as a photoreceptive layer
By providing a function-separated structure using CGL and CGL, separate layers should have the important functions of the photoreceptive member for electrophotography such as generation of electric charges (photocarriers) and transport of the generated electric charges. Therefore, the degree of freedom in layer design is greater than that in which one layer has both functions, and the one with excellent characteristics can be obtained. Further, since the CTL contains at least one kind of carbon atom, nitrogen atom and oxygen atom, the relative permittivity of the CTL can be reduced,
The capacity per layer thickness can be reduced, the chargeability and the sensitivity can be improved, the withstand voltage against a high voltage can be improved, and the durability can be improved. In addition, by containing a substance that controls conductivity in the CTL in a non-uniform distribution state in the layer thickness direction, it is possible to design a CTL having an optimum charge transporting ability as desired.

Furthermore, 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.

[Specific Description of the Invention]

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

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

The electrophotographic light-receiving member 100 shown in FIG. 1 has a light-receiving layer 102 made of Non-Si (H, X) on a support 101 for the electrophotographic light-receiving member. The layer 102 is composed of Non-Si (H, X) (hereinafter abbreviated as "Non-SiMo (H, X)") that contains a substance (Mo) for controlling conductivity evenly or nonuniformly in the entire layer region. Charge injection blocking layer 103, CGL104 composed of Non-Si (H, X), and Non-Si (H, X), and at least one of carbon atom, nitrogen atom and oxygen atom. CTL105 containing at least a portion containing a substance (M) containing and controlling conductivity in a non-uniform distribution state in the layer thickness direction. CTL105
Has a free surface 106.

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

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

For example, in the case of glass, NiCr, Al, Cr, Mo,
Conductivity is imparted by directing a thin film made of Au, Ir, Nb, Ta, V, Ti, Pt, Pd, InO ₃ , ITO (In ₂ O ₃ + Sn), etc., or with a synthetic resin film such as polyester film. If available, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Tl, Pt
A thin film of a metal such as is provided on the surface by vacuum deposition, electron beam deposition, sputtering, or the like, or the surface is laminated with the metal to impart conductivity to the surface.
The shape of the support may be a plate-like endless belt having a smooth surface or an uneven surface, a cylindrical shape, or the like, and its thickness is
The amount is appropriately determined so that a desired electrophotographic light-receiving member can be formed, 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, in view of production and handling of the support, functional strength and the like, it is usually 10 μm or more.

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

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

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

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

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

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

Second, 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 performing blade cleaning, there is a problem that damage to the blade becomes faster.

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

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

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

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

That is, the surface of the support has irregularities smaller than the resolving power required for the electrophotographic light-receiving member, and the irregularities are caused by a plurality of spherical dents.

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

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

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

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

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

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

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

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

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

In the example of FIG. 4, a rigid true sphere having substantially the same radius Ro is used, but the support in the present invention is not limited to this and achieves the object of the present invention. With the number and types managed in the range, the radius Ro
It is also possible to use a plurality of types of rigid true spheres of different types.

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

Charge Injection Blocking Layer The charge injection blocking layer 103 is made of Non-SiMo (H, X) as described above.
Composed of. The charge injection blocking layer 103 in the present invention is
When the surface of the light-receiving layer 101 is subjected to a charging treatment of one polarity, it has a function of preventing charges from being injected into the CGL 104 from the support 101 side, and when receiving a charging treatment of the other polarity. Has a so-called rectification property that does not exhibit such a function. In order to impart such a function, the charge injection blocking layer 103 contains a relatively large amount of a substance (Mo) that controls one conductivity type and gives conductivity.

The substance (Mo) that controls conductivity is uniformly contained in the layer interface direction of the charge injection blocking layer 103, but its distribution concentration C (Mo) is uniform in the layer thickness direction. May be non-uniform. However, in any case, it is contained in the entire region of the charge injection blocking layer 103.

When the distribution concentration C (Mo) is non-uniform, it is preferable that the distribution concentration C (Mo) is contained so as to be distributed more on the support 101 side.

The conductivity controlling substance (Mo) contained in the charge injection blocking layer 103 may have the same polarity as the conductivity controlling substance (M) contained in the CTL 105, which will be described later.
They may have different polarities, and may be the same substance or different substances.

However, in order to make charge injection into the photoreceptive layer 102 more effectively from the free surface 106 side and the support 101 side when subjected to the charging treatment, the charge injection blocking layers 103 and C
The substances that control the conductivity contained in TL105 are, respectively,
At least polarities are preferably different.

These are appropriately determined in consideration of the purpose in designing the layer of the light receiving layer 102. Charge injection blocking layer 10
As the substance (Mo) contained in 3 for controlling conductivity, the same substance as the substance (M) for controlling conductivity described later can be specifically mentioned.

6 to 10 show typical examples of the state of distribution of the substance (Mo) controlling the conductivity in the layer thickness direction when the charge injection blocking layer contains a non-uniform concentration distribution in the layer thickness direction. Is shown.

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

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

In the example shown in FIG. 6, from the interface position t _B side to the position t ₄ , the content concentration C (Mo) of the substance (Mo) is contained while taking a constant value of C ₁₂ , and the distribution concentration from the position t ₄ C (Mo) 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. 7, the substance contained (Mo)
Distribution concentration C (Mo) of C ₁₅ from position t _B to position t _T
A distribution state is formed such that it gradually decreases continuously from and becomes C ₁₆ at the position t _T.

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

In the example shown in FIG. 9, the distribution concentration C (Mo) takes a constant value of C ₁₉ from the position t _B to the position t ₆ , and from the position t ₆ to the position t _T from C ₂₀ to C ₂₁ It is considered to be a distribution state that decreases functionally.

In the example shown in FIG. 10, the distribution concentration C (Mo) takes 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 (Mo) that controls conductivity, in a distribution state in which a large amount is distributed on the support side, the maximum concentration C (Mo) of the substance (Mo) is preferably 50 atoms. ppm or more, more preferably 80 atomic ppm or more,
Optimally, it is desirable to form a layer so that the distribution state may be 100 atom ppm or more.

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

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

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

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

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

11 distribution concentration C than is contained position t ₇ distribution density Cz is while taking a constant value that is C ₂₃ position to the atom (Z) of t ₇ from the interface position t _B in the example shown in the figures interface position t _It gradually decreases continuously from C ₂₄ until reaching _T. Interface position t _T
In, the distribution concentration C is C ₂₅ .

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

In the case of FIG. 13, from the position t _B to the position t ₈ is an atom (Z).
The distribution concentration Cz of C has a constant value at the position C _28, and the position t _B and the position t
_It is gradually and continuously reduced between _T and _T , and is substantially zero at the position t _T.

In the case of FIG. 14, the atom (Z) is continuously and gradually decreased from C ₃₀ until it reaches the position t _T from t _B , and is substantially zero at the position t _T.

In the example shown in FIG. 15, the distribution concentration Cz of atoms (Z) is Cz.
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 Cz is linearly reduced from the position t ₉ to the position t _T.

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

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

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

In the present invention, the content of the atom (Z) contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably 0.
The content is preferably 001 to 50 atomic%, more preferably 0.002 to 40 atomic%, and most preferably 0.003 to 30 atomic%.

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

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

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

The charge injection blocking layer 103 is formed by a vacuum deposition film forming method similar to that of the CGL 104 and CTL 105, which will be described later, by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained.

CGL CGL104 in the present invention is composed of Non-Si (H, X),
It has the desired photoconductive properties, especially charge generation properties.

In the CGL104 of the present invention, as in the case of the CTL105 described later, any of the substance (M), the carbon atom (C), the nitrogen atom (N) and the oxygen atom (O) which control the conductivity is substantially contained. Not contained in.

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

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

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

In the present invention, to form CGL composed of Non-Si (H, X), for example, glow discharge method (low frequency CVD, high frequency CV
AC discharge CVD such as D or microwave CVD, or DC discharge CVD), ECR-CVD method, sputtering method, vacuum deposition method, ion plating method, optical CVD method, thermal CVD method, etc. Can be formed.

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

In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon is housed in a vapor deposition board as an evaporation source, and this evaporation source is heated and vaporized by a resistance heating method, an electron beam method (EB method), etc. It can be carried out in the same manner as in the sputtering method except that the evaporate is passed through a desired gas plasma atmosphere. To form CGL composed of Non-Si (H, X) by the HRCVD method, for example, the desired gas pressure can be set in the activation space provided in the previous stage in the deposition chamber where the source gas for Si supply can be depressurized. Introduced in a state, a glow discharge is generated in the activation space or heated to generate an active species (A), and a raw material gas for introducing a hydrogen atom (H) and / or a halogen atom Similarly, the raw material gas for introducing (X) is introduced into another activation space to generate the active species (B), and the active species (A) and the active species (B) are separately introduced into the deposition chamber. Then, a layer made of Non-Si (H, X) may be formed on the surface of a predetermined support which is installed at a predetermined position in advance. 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 at a desired gas pressure, and halogen is further added. (X) The 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). Are used effectively. Especially, SiH ₄ and Si ₂ H in terms of ease of handling during layer work and good Si supply efficiency.
₆ is mentioned as a preferable one.

As a raw material gas for introducing a halogen atom used in the present invention, many halogen compounds can be 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 halogen atom capable of being gasified or gasified, which has silicon atoms and halogen atoms as constituent elements, can be mentioned as an effective one in the present invention.

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

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

When manufacturing CGL containing halogen atoms according to the glow discharge method, basically, for example, a silicon halide serving as a raw material gas for supplying Si is introduced into a deposition chamber for forming CGL at a predetermined gas flow rate. Then, by causing a glow discharge to form a plasma atmosphere of these gases, it is possible to form CGL on the desired support,
In order to control the introduction ratio of hydrogen atoms more easily, hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed in a desired amount with these gases to form a layer.

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

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

When hydrogen atoms are introduced, a raw material gas for introducing hydrogen atoms, for example, H ₂ or the above-mentioned silane gases is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gases. You can do 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} , the starting material of _{SIH 2 Cl 2, SiHCl 2,} SiH 2 Br 2, SiHBr 2 and halogen-substituted hydrogen silicon of, etc. for substances that may or gasified gas state is also enabled CGL form Can be mentioned as. Among these substances, a halide containing a hydrogen atom is introduced into the layer at the same time as the introduction of the halogen atom into the layer during the formation of CGL, so that a hydrogen atom extremely effective in controlling the electrical or photoelectric properties is also introduced. In this case, it is used as a preferable raw material for introducing halogen.

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

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

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

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

FIGS. 18 to 33 show distribution states of the substance (M), the carbon atom (C), the nitrogen atom (N) and the oxygen atom (O) contained in CTL in the layer thickness direction, which control the conductivity. A typical example is shown. In the following description, the substance (M), carbon atom (C), nitrogen atom (N) and oxygen atom (O) are collectively referred to as “atom (Y)” for convenience.

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

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

In the example shown in FIG. 18, from the interface position t _B to the position t ₁₁ , the layer region where the atom (Y) is formed while the distribution concentration C of the atom (Y) takes a constant value C _37. It is contained in (Y) and gradually and continuously decreases from the distribution concentration value C ₃₈ from the position t ₁₁ to the interface position t _T. At the interface position t _T , the distribution concentration C of atoms (Y) has a value C ₃₉ .

In the example shown in FIG. 19, the contained atom (Y)
Distribution density C of the distribution density value from position t _B to position t _T
A distribution state is formed in which the distribution concentration value C ₄₁ gradually decreases continuously from C ₄₀ and becomes the distribution concentration value C ₄₁ at the position t _T.

In the case of FIG. 20, from the position t _B to the position t ₁₂ , the distribution concentration C of the atom (Y) is a constant value with the distribution concentration value C ₄₂ ,
The distribution concentration C is gradually and continuously reduced between the position t ₁₂ and the position t _T, and the distribution concentration C is substantially zero at the position t _T (where substantially zero is less than the detection limit amount). The same applies to the meaning of "substantially zero" hereafter.) 21st
In the case of figure, the distribution concentration C of the atoms (Y) is continuously reduced gradually from the density value C ₄₄ up to the position t _T to the position t _B, and is substantially zero at the position t _T .

In the example shown in FIG. 22, the distribution concentration C of atoms (Y)
Is a constant value with the distribution concentration value C ₄₅ between the position t _B and the position t ₁₃ , and is a distribution concentration value C _{46 at} the position t _T.
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. 23, the distribution concentration C of the atom (Y) decreases linearly from the distribution concentration value C ₄₇ to substantially zero from the position t _B to the position t _T. .

In the example shown in FIG. 24, the contained atom (Y)
The distribution density C of C is gradually and continuously decreased from the value C ₄₈ until reaching the position t _T from the position t _B, and a distribution state in which the value C ₄₉ is obtained at the position t _T is formed.

In the example shown in FIG. 25, the distribution concentration C of the atom (Y) has a constant value C ₅₀ from the position t _B to the position t _14, and the value C ₅₁ from the position t ₁₄ to the position t _T. It is assumed that the distribution state decreases linearly up to the value C ₅₂ .

In the example shown in FIG. 26, the distribution concentration C of the atom (Y) gradually increases continuously from C ₅₅ to C ₅₄ from the position t _B to the position t _15, and from the position t ₁₅ to C _53. Takes a constant value of
The distribution state is formed so as to reach the position t _T.

In the example shown in FIG. 27, the distribution concentration C of atoms (Y) forms a distribution state in which it gradually increases continuously from C ₅₇ to C ₅₆ from the position t _B to the position t _T. There is.

In the example shown in FIG. 28, the distribution concentration C of the atom (Y) gradually and continuously increases from zero to C ₅₉ from the position t _B to the position t ₁₆ , and is lower than the position t _21. The distribution state is formed such that a constant value of C ₅₈ is taken and the position reaches t _T.

In the example shown in FIG. 29, the distribution concentration C of atoms (Y) forms a distribution state in which it gradually and continuously increases from zero to C ₆₀ from the position t _B to the position t _T. is doing.

In the example shown in FIG. 30, the distribution concentration C of atoms (Y)
Increases linearly from C ₆₂ to C ₆₁ from position t _B to position t ₂₂ and takes a constant value of C ₆₁ from position t ₁₇
It has a distribution that reaches t _T.

In the example shown in FIG. 31, the distribution concentration C of the atom (Y) 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. 32, the distribution concentration C of the atom (Y) forms a distribution state in which it gradually increases continuously from C ₆₅ to C ₆₄ from the position t _B to the position t _T. ing.

In the example shown in FIG. 33, the distribution concentration C of atoms (Y)
The position t C ₆₇ to increase a linear function from C ₆₈ to 32 reach the position t _{18 B,} is the position t ₂₃ takes a constant value of C _66, the position t _T
It forms a distribution state that leads to.

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

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

In addition, the entire layer region of CTL105 in the present invention contains carbon atoms and / or oxygen atoms and / or nitrogen atoms, which mainly contributes to high dark resistance and control of spectral sensitivity and improvement of adhesion between CGL and CTL. You can measure The content of carbon atom, oxygen atom or nitrogen atom, or when at least two of them are contained, the total content thereof is preferably 1 × 10 ^{−3 to} 5 × 10 atom%. , More preferably 5 × 10 ^-2 to 4 × 10 atomic%, optimally 1 × 10 ^{-1 to} 3
It is desirable that the content be × 10 atom%.

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

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

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

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

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

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

For example, a raw material gas containing silicon atoms (Si) as a constituent atom and a raw material gas containing nitrogen atoms (N) as a constituent atom, and if necessary, a hydrogen atom (H) or a halogen atom (X).
Or a raw material gas containing Si as a constituent atom is used at a desired mixing ratio, or a raw material gas containing a silicon atom (Si) as a constituent atom and a nitrogen raw material (N) and a hydrogen atom (H) as constituent atoms. Or a raw material gas containing silicon atoms (Si) as constituent atoms, and silicon atoms (Si), nitrogen atoms (N) and hydrogen atoms (H). ) Can be used as a mixture with a raw material gas having three of the constituent atoms.

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

A starting material effectively used as a raw material gas for introducing a nitrogen atom (N) includes N as a constituent atom, or N and H as a constituent atom, such as nitrogen (N ₂ ) and 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.

In order to form a CTL by the glow discharge method HRCVD method or 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 source gas containing silicon atoms (Si) as constituent atoms, and three atoms of silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H). It is possible to mix and use a raw material gas that is a constituent atom.

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

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

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

As a source gas containing Si, C and H as constituent atoms, Si (C
Alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ can be mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

OGL104, CTL105 having properties capable of achieving the object of the present invention
In order to select and configure A-Si containing hydrogen atoms and / or halogen atoms as Non-Si (H, X) (hereinafter referred to as "A-Si (H, X)"), It is necessary to properly set the temperature and gas pressure of 101 as desired.

The support temperature (Ts) is appropriately selected in accordance with the layer design, but in the usual case, it is 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 usual case, it is 1 × 10 ^{−4 to} 10 Torr, preferably 1 × 10 ⁻³ Torr, optimally 1 × 10 ⁻² to It is desirable to set it to 1 Torr.

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

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

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

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

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

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

FIG. 34 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the RF glow discharge decomposition method.

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

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

As an example of forming a light receiving member for electrophotography, SiH ₄ gas, H ₂ gas, B ₂ H ₆ gas / H ₂ gas and NO gas are used as a charge injection blocking layer forming gas and SiH is used as a CGL forming gas. ₄ gas, H
₂ gas, SiH ₄ gas as a CTL forming gas, NH ₃ gas, B ₂ H
_The case of using ₆ gas is taken up.

A gas cylinder is required to allow these gases to flow into the reaction chamber 1001.
Make sure that valves 1051-1057 of 1011-1017, leak valve 1003 of reaction chamber 1001 are closed, and that inflow valves 1031-1037, outflow valves 1041-1047, and auxiliary valve 10
Make sure 70 is open, then first open 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, SiH ₄ gas from the gas cylinder 1011, gas cylinder 1012
H ₂ gas, gas cylinder 1013 B ₂ H ₆ gas, gas cylinder
Valves 1051-1054, 1056, 1057 for NO gas from 1014, NH ₃ gas from gas cylinder 1016, CH ₄ gas from gas cylinder 1017
Is introduced and the pressure of each gas is adjusted to ² Kg / cm ² by pressure regulators 1061 to 1064, 1066, 1067.

Next, gradually open the inflow valves 1031 to 1034, 1036, and 1037 to supply the above gases to the mass flow controllers 1021 to 102.
Installed within 24,1026,1027.

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

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

To form the charge injection blocking layer, the outflow valves 1041, 1042,
1043, 1044 and the auxiliary valve 1070 are gradually opened to allow SiH ₄ gas, H ₂ gas, B ₂ H ₆ / H ₂ gas, and NO gas to flow into the reaction chamber 1001. At this time, SiH ₄ gas flow rate, H ₂ gas flow rate, B ₂ H ₆ /
Adjust the outflow valves 1041, 1042, 1043, 1044 so that the H ₂ gas flow rate and the NO gas flow rate are at desired values, and watch the vacuum gauge 1004 so that the pressure in the reaction chamber is at a desired value. Adjust the opening of the in-valve 1002. After that, the power supply 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber 1001 to start the formation of the charge injection blocking layer on the substrate cylinder. 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. .

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

In order to form CGL, the outflow valves 1041 and 1042 and the auxiliary valve 1070 are gradually opened to supply SiH ₄ gas and H ₂ gas to the reaction chamber 10.
Inflow into 01. At this time, adjust the outflow valves 1041 and 1042 so that the SiH ₄ gas flow rate and the H ₂ gas flow rate become desired values,
Also, use a vacuum gauge 1004 to adjust the pressure in the reaction chamber to the desired value.
While watching, adjust the opening of the main valve 1002. After that, the power source 1010 is set to a desired power to generate an RF glow discharge in the reaction chamber, and the formation of CGL on the substrate cylinder is started. After the desired film thickness is formed, the RF glow discharge is stopped, and the outflow valves 1041 and 1042 are closed to stop the inflow of gas into the reaction chamber to complete the formation of CGL.

CTLs are formed on CGLs formed as above. CT
To form L, the outflow valves 1041, 1043, 1045 and the auxiliary valve 1070 are gradually opened, and SiH ₄ gas, B ₂ H ₆ gas, NH
₃ Gas is allowed to flow into the reaction chamber 1001. At this time, the outflow valves 1041, 1043, 1045 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ gas flow rate, and the NH ₃ gas flow rate reach the desired values, and the pressure inside the reaction chamber reaches the desired value. Adjust the opening of the main valve 1002 while watching the vacuum gauge 1004. Then power 10
RF glow discharge is initiated in the reaction chamber with 10 set to the desired power to initiate CTL formation on the substrate cylinder.
After the desired film thickness is formed, the RF glow discharge is stopped, the outflow valves 1041, 1043, 1045 are closed to stop the gas flow into the reaction chamber, and the CTL formation is completed.

Needless to say, all of the outflow valves other than the required gas are closed when forming each layer, and each gas is supplied in the reaction chamber 1001 and outflow valves 1041 to 1041 ...
In order to avoid remaining in the pipe from 1046 to the reaction chamber 1001, the outflow valves 1041 to 1046 are closed and the auxiliary valve 1070 is used.
Then, the main valve 1002 is fully opened, and the system is once evacuated to a high vacuum, if necessary.

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

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

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

FIG. 35 shows an apparatus for producing 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, as an example, in 2011
SiH ₄ gas (purity 99.999%) cylinder, H ₂ gas (purity 99.999%) cylinder in 2012, B ₂ H ₆ diluted with H ₂ gas in 2013
Gas (purity 99.999% or less, abbreviated as “B ₂ H ₆ / H ₂ ”) and cylinder, 2014 is NO gas (purity 99.5%) cylinder, 2015 is PH ₃ gas diluted with H ₂ gas (purity 99.999%, Below "PH ₃ lH ₂ "
Abbreviated), 2016 NH ₃ gas (99.999% purity) cylinder, 2017
Is a CH ₄ gas (purity 99.999%) cylinder.

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

As an example of forming a photoreceptive member for electrophotography, SiH ₄ gas, H ₂ gas, B ₂ H ₆ / H _{2 is} used as a charge injection blocking layer forming gas.
Gas and NO gas are used as CGL forming gas, SiH ₄ gas and H ₂ gas, and CTL forming gas, SiH ₄ gas, NH ₃ gas, and B ₂ H ₆ gas are used.

A gas cylinder is required to allow these gases to flow into the reaction chamber 2001.
Make sure that valves 2051 to 2057 of 2011-2017, leak valve 2003 of reaction chamber 2001 are closed, and also inflow valves 2031 to 2037, outflow valves 2041 to 2047, and auxiliary valve 20.
Make sure 70 is open, then first main valve 2002
Open and evacuate into the reaction chamber 2001 and the gas pipe. Next, when the reading of the vacuum gauge 2004 reaches about 5 × 10 ⁻⁶ Torr, the auxiliary valve 2070 and the outflow valves 2041 to 2047 are closed.

After that, from gas cylinder 2001 SiH ₄ gas, gas cylinder 2012
From H ₂ gas, gas cylinder 2013 From B ₂ H ₆ gas, gas cylinder
From 2014, NO gas, from gas cylinder 2015, PH ₃ / M ₂ gas, from gas cylinder 2016, NH ₃ gas, from gas cylinder 2017, CH ₄ gas was introduced by opening valves 2051 to 2057, and pressure regulator 2061
To adjust each gas pressure to 2Kg / cm ² by ～2067.

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

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

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

To form the charge injection blocking layer, the outflow valves 2041, 2042,
2043, 2044 and the auxiliary valve 2070 are also gradually opened to allow SiH ₄ gas, H ₂ gas, B ₂ H ₆ / H ₂ gas, and NO gas to flow into the reaction chamber 2001. At this time, SiH ₄ gas flow rate, H ₂ gas flow rate, B ₂ H ₆ /
Adjust the outflow valves 2041, 2042, 2043, 2044 so that the H ₂ gas flow rate and the NO gas flow rate are at desired values, and check the vacuum gauge 2004 so that the pressure in the reaction chamber is at a desired value. Adjust the opening of the in-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 and the charge injection blocking layer is completed.

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

To form CGL, the outflow valves 2041 and 2042 and the auxiliary valve 2070 are gradually opened, and SiH ₄ gas and H ₂ gas are added to the reaction chamber 20.
Inflow into 01. At this time, the outflow valves 2041 and 2042 are adjusted so that the SiH ₄ gas flow rate and the H ₂ gas flow rate are at desired values, and while watching the vacuum gauge 2004 so that the pressure in the reaction chamber is at a 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 through the waveguide 2009 and the dielectric window 2010, and the formation of CGL on the substrate cylinder is started. After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valves 2041 and 2042 are closed to stop the inflow of gas into the reaction chamber to complete the formation of CGL.

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

It goes without saying that all the outflow valves except the gas necessary for forming each layer are closed, and
Outflow valves 2041 to 2046 for each gas in the reaction chamber 2001
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.

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

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

FIG. 36 shows an apparatus for manufacturing an electrophotographic light-receiving member by the HRCVD method.

In FIG. 36, 3001 is a film forming chamber, 3002 is an activation chamber (A), 3003 and 3018 are microwave plasma generators, and 300
4 is a raw material gas introduction pipe of active species (A), 3005 is an active species (A) introduction pipe, 3006 is a motor, 3007 is a heater for heating a cylindrical substrate, 3008 and 3009 are blowing pipes, 301
Reference numeral 0 indicates a cylindrical substrate, and 3011 indicates a main exhaust valve. Further, reference numerals 3012 to 3016 are cylinders for supplying a source gas, 3017 is an activation chamber (B), 3019 is a source gas introduction pipe, and 3020 is an activated species introduction pipe generated from the activation chamber (B). A method for producing an electrophotographic light-receiving member having a layer structure according to the present invention on a cylindrical substrate using this apparatus will be specifically described.

As an example, Al is used as the cylindrical substrate and SiH ₄ , B ₂ H ₆ , N as the charge injection blocking layer forming gas.
SiH ₄ and H ₂ were used as o and H ₂ as CGL forming gas, and SiH ₄ , SiF ₄ , CH ₄ , H ₂ and B ₂ H ₆ were used as CTL forming gas.

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

To form the charge injection blocking layer, H ₂ gas is introduced from the cylinder 3012 into the activation chamber (A) through the introduction pipe 3004, activated by the microwave plasma generator 3003, and activated hydrogen is blown out through the introduction pipe 3005. A tube 3008 led to a film forming chamber 3001. On the other hand, the SiH ₄ gas from the cylinder 3013, the B ₂ H ₆ gas from 3014, and the NO gas from 3015 are introduced from the introduction pipe 3019 into the activation chamber (B) 301.
After being introduced into No. 7 and activated by a microwave plasma generator 3018, it was led to a film forming chamber 3001 through an inlet pipe 3020 through a blow pipe 3009. At this time, the gas flow rate, the inner thickness, and the microwave power are set to desired values.

The Al cylindrical base 3010 was heated and maintained at a desired temperature by the heater 3007, and the exhaust gas was exhausted by appropriately adjusting the opening of the main exhaust valve 3011. Thus, the charge injection blocking layer was formed. Similarly, H ₂ gas from the cylinder 3012 and SiH ₄ gas from 3013 are supplied on the charge injection blocking layer, and CGL is placed on the CGL from the cylinder 3012 to H ₂ gas and 3013 to SiH 4.
₄ gas, 3014 to B ₂ H ₆ gas, 3016 to CH ₄ gas SiF ₄ gas was supplied from a cylinder (not shown) to sequentially form CTLs to form an electrophotographic light receiving member.

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

FIG. 37 shows an apparatus for manufacturing an electrophotographic light-receiving member by the FOCVD method.

In the gas cylinders 4011, 4012, 4013, 4014, 4015, 4016, 4017 in the figure, the raw material gas for forming each layer of the present invention is sealed, as an example, for example, 4011
SiH ₄ gas (purity 99.999%) cylinder, 4012 is H ₂ gas (purity
99.999%) cylinder, 4013 is B ₂ H ₆ gas diluted with H ₂ (purity 99.999% or less, abbreviated as “B ₂ H ₆ / H ₂ ”) cylinder, 4014 is
NO gas (purity 99.5%) cylinder, 4015 PH diluted with H _2
3 gas (purity 99.999% or less abbreviated as “PH ₃ / H ₂ ”) cylinder,
4016 is a CH ₄ gas (purity 99.999%) cylinder, and 4017 is F ₂ gas (10% He dilution purity 99.99%).

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

As an example of forming a photoreceptive member for electrophotography, SiH ₄ gas, H ₂ gas, B ₂ H ₆ / H _{2 is} used as a charge injection blocking layer forming gas.
Gas, NO gas, F ₂ gas, SiH ₄ gas, H ₂ gas as CGL forming gas, and SiH ₄ gas, CH ₄ gas, B ₂ H ₆ gas, F ₂ gas as CTL forming gas I'll pick it up.

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

The F ₂ gas filled in the cylinder of 4017 is the same as above.
Introduce to vacuum chamber 4001 through 4021.

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

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

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

The base 4060 is rotated by the rotating mechanism 4062 to form a uniform film.

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

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

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

To form the charge injection blocking layer, open valves 4046 to 4049 and open the outflow valves 4031, M4032, 4033, 4034 and auxiliary valves.
Open 4060 gradually and SiH ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, H
₂ Gas is allowed to flow into the reaction chamber 4001. At this time, the outflow valves 4031, 4032, 4033, 4034 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ / H ₂ gas flow rate, the NO gas flow rate, and the H ₂ gas flow rate reach desired values, and the reaction chamber The opening of the main valve 4002 is adjusted while observing a vacuum gauge (not shown) at which the pressure of is a desired value.

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

A CGL layer is formed on the charge injection blocking layer formed as described above by the same operation as described above. With respect to each layer, a required gas may be flowed and the valve may be operated in the same manner as the charge injection blocking layer.

〔Example〕

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

<Example 1> Using the manufacturing apparatus shown in FIG.
A light-receiving member for electrophotography was formed on an aluminum cylinder that was mirror-finished according to the preparation conditions shown in Tables, 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 under various conditions, The chargeability, sensitivity, residual potential, ghost, and other electrophotographic characteristics were checked, and the decrease in chargeability after accelerated durability equivalent to 2 million sheets, surface abrasion, and increase in image defects were investigated.

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

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

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

The results are shown in Table 8.

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

<Embodiment 3> Using the manufacturing apparatus shown in FIG.
Drums were produced in the same manner as in Example 1 under the production conditions shown in Tables, Tables 9 and 10, and the same evaluations were performed.

The results are shown in Table 11.

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

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

The results are shown in Table 14.

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

<Embodiment 5> Using the manufacturing apparatus shown in FIG.
An electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the conditions shown in Tables 6 and 7.

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, respectively, and subjected to initial conditions under various conditions. Check the electrophotographic characteristics such as charging ability, sensitivity, residual potential, ghost, etc.
We investigated the deterioration of charging ability, surface scraping, and increase in image defects after the endurance of an accelerated machine equivalent to 2 million sheets.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 19 shows the comprehensive evaluation results.

As shown in Table 19, good results were obtained for all items. In particular, remarkable superiority was observed in initial charging ability and durability.

Example 6 Using the manufacturing apparatus shown in FIG. 36, an electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished by the HRCVD method according to the conditions shown in Tables 20 to 23. The prepared electrophotographic light-receiving member was set in an electrophotographic device using a halogen lamp as a light source and an electrophotographic device using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging was performed under various conditions. We checked the electrophotographic characteristics such as performance, sensitivity, residual potential, ghost, etc., and investigated the deterioration of charging ability, surface scraping, and increase of image defects after the endurance of an accelerated actual machine equivalent to 2 million sheets.

Also, the dielectric strength voltage was examined by applying a DC high voltage to the drum. Furthermore, the scratch resistance was examined by applying a constant load to a needle with a spherical tip to scratch the drum surface. Table 24 shows the comprehensive evaluation results.

As shown in Table 24, good results were obtained for all items. In particular, remarkable superiority was observed in initial charging ability and durability.

Example 7 Using the manufacturing apparatus shown in FIG. 37, the FOCVD method was applied to the 25th, 26th, 27th, 28th
An electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the conditions shown in the table.

The prepared electrophotographic light-receiving member 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, the initial chargeability, sensitivity, residual potential,
We checked the electrophotographic characteristics such as ghosts, and investigated the deterioration of charging ability, surface scraping, and increase of image defects after 2 million sheets worth of accelerated real machine durability.

Also, the dielectric strength voltage was examined by applying a DC high voltage to the drum. Furthermore, the scratch resistance was examined by applying a constant load to a needle with a spherical tip to scratch the drum surface. Table 29 shows the comprehensive evaluation results.

As shown in Table 29, good results were obtained for all items. In particular, remarkable superiority was observed in initial charging ability and durability.

<Embodiment 8> Mirror-finished cylinders are further subjected to lathe processing with a sword bite having various angles to obtain cylinders having various cross-sectional patterns as shown in Table 31 with a cross-sectional shape as shown in FIG. 42. I prepared multiple books. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 34 and subjected to the drum manufacturing under the manufacturing conditions shown in Table 30. The drum thus prepared was evaluated variously by an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 32 were obtained.

<Example 9> The surface of a 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 surface of the cylinder was performed. A plurality of cylinders having the cross-sectional shape shown in the figure and various cross-sectional patterns as shown in Table 34 were prepared.
The cylinder is sequentially set in the manufacturing apparatus shown in FIG.
The drum was produced under the production conditions shown in the table. Various evaluations were performed on the thus-formed drum using an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus having a digital exposure function using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 35 were obtained.

<Example 10> Using the manufacturing apparatus shown in FIG. 36, a drum was prepared in the same manner as in Example 1 under the conditions shown in Tables 36, 37, 38 and 39, and the same evaluation was performed.

The results are shown in Table 40.

As shown in Table 40, good results were obtained for all items.

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

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

[Brief description of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic light-receiving member of the present invention, and FIGS. 2 to 5 are respectively the uneven shape of the support surface and the method for producing the uneven shape. 6 to 11 are explanatory diagrams for explaining the distribution state of the substance (Mo) controlling the conductivity contained in the charge injection blocking layer, and FIGS. FIG. 17 is an explanatory diagram for explaining the distribution state of carbon atoms and / or oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer, and FIGS. 18 to 33 are CTLs, respectively. Atoms contained (Y)
FIG. 34 is an example of a device for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention, FIG. 34 is a schematic explanatory view of a manufacturing device by a glow discharge method using RF, FIG. 35 is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention, which is a schematic explanatory view of a manufacturing apparatus by a glow discharge method using microwaves, and FIG. An example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography, which is a schematic explanatory view of a manufacturing apparatus by the HRCVD method, and FIG. 37 shows a light receiving layer of the light receiving member for electrophotography of the present invention. An example of an apparatus for forming, a schematic explanatory view of a manufacturing apparatus by the FOCVD method, FIG. 38 is an impurity gas and doping when forming CTL of the electrophotographic light-receiving member of the present invention using RF glow discharge・ A diagram showing the change in the flow rate during gas film formation. Fig. 39 shows the electric current of the present invention. FIG. 40 is a view showing flow rate changes during film formation of an impurity gas and a doping gas when a CTL of a photographic light-receiving member is formed by using a microwave glow discharge, and FIG. 40 shows an electrophotographic light-receiving member of the present invention. CTL to HRCVD
FIG. 41 is a view showing flow rate changes during film formation of an impurity gas and a doping gas in the case where the CTL of the light receiving member for electrophotography of the present invention is FOCVD
Showing changes in the flow rates of the impurity gas and the doping gas at the time of film formation when the electrophotographic light receiving member of the present invention is formed. FIG. 43 is an enlarged view of the cylinder cross section in the case of a letter shape, FIG. 43 is an enlarged view of the cylinder cross section when the surface of the cylinder substrate in forming the electrophotographic light-receiving member of the present invention is subjected to so-called dimple processing, 44 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 using RF glow discharge. About Fig. 1 100 ... Photoreceptive layer 101 ... Support 102 ... Photoreceptive layer 103 ... Charge injection blocking layer 104 ... CGL 105 ... CTL 106 ... Free surface About FIGS. 3 and 4 , 301, 401 …… Support 302, 402 …… Support surface 303, 403 …… Rigid spherical sphere 304, 404 …… Spherical trace depression About the Fig. 5, 500 …… Photoreceptive layer 501 …… Support 502 …… Charge injection blocking layer 503 …… CGL 504 …… CTL 505 …… Free surface In Fig. 34, 1001 …… reaction chamber 1002 …… main exhaust valve 1003 …… reaction chamber leak valve 1004 …… vacuum gauge 1007 …… cylinder substrate 1008 …… for substrate heating Heater 1009 …… Cylinder substrate rotation motor 1010 …… RF power supply 1011 to 1017 …… Raw material gas cylinder 1021 to 1027 …… Mass flow controller 1031 to 1037 …… Gas inflow valve 1041 to 1047 …… Gas outflow valve 1051 ~ 1057 …… Raw material gas cylinder valve 1061 ~ 1067 …… Pressure Section 35 About Fig. 35, 2001 ... Reaction chamber 2002 ... Main exhaust valve 2003 ... Reaction chamber leak valve 2004 ... Vacuum gauge 2005 ... Substrate heating heater 2006 ... Cylindrical substrate 2007 ... Substrate rotation Motor 2008 …… Microwave power source 2009 …… Waveguide 2010 …… Dielectric window 2011 to 2017 …… Source gas cylinder 2021 to 2027 …… Mass flow controller 2031 to 2037 …… Gas inlet valve 2041 to 2047… … Gas outflow valve 2051 to 2057 …… Source gas cylinder valve 2061 to 1267 …… Pressure regulator Regarding Fig. 36, 3001 …… Deposition chamber 3002 …… Activation chamber (A) 3003,3018 …… Microwave Plasma generator 3004,3019 …… Raw material gas introduction pipe 3005,3020 …… Activated species introduction pipe 3006 …… Motor 3007 …… Cylinder substrate heating heater 3008,3009 …… Blowout pipe 3010 …… Cylinder substrate 3011 …… Main exhaust valve 3012-3016 ... Material gas cylinder 3017 …… Activation chamber (B) About Fig. 37, 4001 …… Reaction chamber 4002 …… Main exhaust valve 4011-4017 …… Source gas cylinder 4020,4021 …… Source gas introduction pipes 4031-4037 …… Outflow valve 4046-4052 …… Inflow valve 4053-4059 …… Mass flow controller 4060 …… Cylinder substrate 4061 …… Cylinder substrate heater 4062 …… Cylinder substrate rotation motor

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

Claims (1)

[Claims] 1. An electron having a support and a photoreceptive layer formed on the support and made of a non-single-crystal material containing a silicon atom as a host and at least one of a hydrogen atom and a halogen atom. In the photographic light-receiving member, the light-receiving layer has a layer structure in which a charge injection blocking layer, a charge generation layer and a charge transport layer are laminated in this order from the support side, and the charge injection blocking layer is further composed of a periodic table. Containing an atom belonging to Group III or Group V, the charge transport layer is a carbon atom,
A non-uniform structure containing at least one of a nitrogen atom and an oxygen atom and having an atom belonging to Group III or V of the periodic table whose concentration increases or decreases in the layer thickness direction from the support side. A photoreceptive member for electrophotography, comprising at least a portion contained in a distributed state, and having a layer thickness of the charge generation layer smaller than that of the charge transport layer.