JPH083646B2 - Photoreceptive member for electrophotography - Google Patents

Description

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

[Description of Prior Art]

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

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

However, the conventional electrophotographic light-receiving member having a light-receiving layer composed of A-Si has the following problems in terms of electro-optical and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness and operating environment characteristics. Moreover, in terms of stability over time and durability, each has been individually improved in characteristics, but there is room for further improvement in measuring overall characteristics. .

For example, when applied to a photoreceptive member for electrophotography,
When trying to measure high photosensitivity and high dark resistance at the same time, it is often observed in the past that residual potential remains during use, and if this type of light receiving member is used repeatedly for a long time, fatigue due to repeated use may occur. There were a few inconveniences such as accumulation, which caused a so-called ghost phenomenon in which an afterimage was generated.

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

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

Therefore, while improving the characteristics of the A-Si material itself, when designing the light-receiving member, the chemical composition creation method of each layer structure was devised so as to solve all of the above problems. Need to

[Object of the Invention]

It is an object of the present invention to solve various problems in a photoreceptive member for electrophotography having a conventional photoreceptive layer composed of a material having a silicon atom as a base as described above.

That is, the main object of the present invention is that electrical and photoconductive properties are substantially always stable with little dependence on the use environment, excellent light fatigue resistance, and deterioration phenomenon occurs even after repeated use. Another object of the present invention is to provide a photoreceptive member for electrophotography having a photoreceptive layer composed of a material having a silicon atom as a base material, which has excellent durability and moisture resistance and has no or almost no residual potential observed.

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

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

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

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

[Structure of Invention]

The electrophotographic light-receiving member of the present invention comprises a support, a long-wavelength light absorption layer (hereinafter sometimes abbreviated as “IR absorption layer”), and a charge transport layer (hereinafter referred to as “CTL”) on the support. A light receiving layer having a layer structure in which a charge generation layer (hereinafter sometimes abbreviated as “CGL”) is laminated in this order from the support side, and the long wavelength A non-single-crystal material in which the light absorption layer has a silicon atom as a base material and contains at least one of a germanium atom and a tin atom and at least one of a hydrogen atom and a halogen atom (hereinafter referred to as “Non-Si (H, X ) ”), And the charge generation layer and the charge transport layer are non-single-crystal materials having a silicon atom as a matrix and containing at least one of a hydrogen atom and a halogen atom. And said charge transfer The layer contains at least one of carbon atom, nitrogen atom and oxygen atom, and the concentration of the atom belonging to Group III or V of the periodic table (a substance that controls conductivity) in the layer thickness direction. In addition, it has at least a portion containing in an uneven distribution state having a portion increasing or decreasing from the support side.

[Action]

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

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

Furthermore, the electrophotographic light-receiving member of the present invention has high photosensitivity and fast photoresponse in the entire visible light range. Therefore,
It is suitable for forming 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, a charge separation layer (hereinafter abbreviated as “CTL”) and a charge generation layer (hereinafter abbreviated as “CGL”) are used as a light-receiving layer to form a function-separated type structure, whereby charges (Fotokyaria) are formed. By providing each of the separate layers with the important functions for the electrophotographic light-receiving member, that is, the generation of the charge and the transport of the generated charge, the degree of freedom in the layer design is greater than that in which the single layer has both the functions, Can have excellent characteristics. In addition, since the CTL contains at least one of carbon atom, nitrogen atom and oxygen atom, it is possible to reduce the relative dielectric constant of CTL, so that the capacity per layer thickness can be reduced and the electrostatic charge can be reduced. It is possible to improve the performance and sensitivity, further improve the withstand voltage against high voltage, and improve the durability. In addition, by containing a substance that controls conductivity in the CTL in a non-uniform distribution state in the layer thickness direction, it is possible to design a CTL having an optimum charge transporting ability as desired.

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

[Specific Description of the Invention]

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

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

An electrophotographic light-receiving member 100 shown in FIG. 1 comprises a support 101 for an electrophotographic light-receiving member and a light-receiving layer 102 formed on the support 101.
The light-receiving layer 102 has an IR absorption layer 103 and a non-Si (H,
X), containing at least one of carbon atom, nitrogen atom and oxygen atom, and containing a substance (M) controlling conductivity in a non-uniform distribution state in the layer thickness direction. CTL104 and Non-Si (H,
X) and the CGL105 composed of X). CGL
105 has a free surface 106.

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

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

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

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

The unevenness provided on the surface of the support is such that a cutting tool having a V-shaped cutting edge is fixed at a predetermined position of a cutting machine such as a milling machine or a lathe, and a cylindrical support is rotated according to a program designed in advance as desired. While moving regularly in a predetermined direction, the surface of the support is accurately cut to obtain the desired uneven shape, pitch,
Formed in depth. The inverted V-shaped linear protrusions created by the irregularities formed by such a cutting method have a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped projection may be a double or triple multiple spiral structure or a cross spiral structure.

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

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

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

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

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

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

As a result of 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 support surface is preferably 500 μm.
~ 0.3μm, more preferably 200μm ~ 1μm, optimally 50μ
It is preferably m to 5 μm.

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

Further, the maximum layer thickness difference due to non-uniform layer pressure of each layer deposited on such a support is preferably 0.1 μm to 2 μm, more preferably 0.1 μm to 1.5 μm, within the same pitch.
Optimally, 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 finer than the resolving power required for the light receiving member for electrophotography, and the irregularities are caused by a plurality of spherical trace depressions.

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

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

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

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

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

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

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

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

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

In the example of FIG. 4, a rigid true sphere having substantially the same radius Ro is used, but the support in the present invention is not limited to this, and the object of the present invention is achieved. A plurality of types of rigid true spheres having different radii Ro may be used in a state where the number and types are controlled within the range.

Fig. 5 shows IR on the support 501 prepared by the above method.
An example is shown in which a light receiving layer 500 formed of the absorption layer 502, CTL 503, and CGL 504 is formed. CGL 504 has a free surface 505.

IR Absorption Layer The IR absorption layer in the present invention has at least one of a germanium atom (Ge) and a tin atom (Sn) and at least one of a hydrogen atom (H) and a halogen atom (X) as constituent elements. One or the other, preferably a non-single crystal material that also contains silicon atoms (Si) (hereinafter "No
n-Si (Ge, Sn) (H, X) ").

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

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

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

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

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

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

In the example shown in Fig. 6, IR containing atoms (GS)
From the interface position t _B at which the surface where the absorption layer is formed and the surface of the IR absorption layer are in contact to the position t ₁ , the distribution concentration C of the atom (GS) has a constant value C ₁ and the atom ( GS) is formed
It is contained in the IR absorption layer, and the interface position is based on concentration C ₂ rather than position t _1.
It is gradually and continuously reduced until reaching t _T. Interface position
At t _T , the distribution concentration C of atoms (GS) is C ₃ .

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

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

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

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

In the example shown in FIG. 11, from the position t _B to the position t _T , the distribution concentration C of the atom (GS) decreases linearly so as to reach substantially zero from the position C ₁ of the concentration. .

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

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

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

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

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

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

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

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

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

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

As a substance that can be used as a raw material gas for supplying Si used in the present invention, a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or a gasifiable silicon hydride ( Silanes) can be used effectively. Especially, SiH ₄ and Si ₂ H ₆ are easy to handle during layer formation work and Si supply efficiency is good.
Are preferred.

As a substance that can be used as a source gas for Ge supply, GeH ₄ , G
e ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H
It is mentioned that germanium hydride in a gas state such as ₂₀ or which can be gasified is effectively used. Especially, in terms of ease of handling during layer formation work, good Ge supply efficiency, etc.
H ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ are preferred.

As a substance that can be used as a source gas for Sn supply, SnH ₄ , S
n ₂ H ₆ , Sn ₃ H ₈ , Sn ₄ H ₁₀ , Sn ₅ H ₁₂ , Sn ₆ H ₁₄ , Sn ₇ H ₁₆ , Sn ₈ H ₁₈ , Sn ₉ H
It is mentioned that tin hydride in a gas state such as ₂₀ or which can be gasified is effectively used, and in particular SnH ₄ , Sn ₂ H in terms of ease of handling during layer formation work, good Sn supply efficiency, etc. ₆ , S
n ₃ H ₈ is preferred.

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

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

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

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

When forming the characteristic electrophotographic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, it is necessary to supply Ge and / or Sn.
Consisting of non-Si (Ge, Sn) (H, X) containing halogen atoms on a desired support without using silicon hydride gas as a source gas capable of supplying Si together with the source gas for supply. IR
An absorption layer can be formed.

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

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

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

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

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

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

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms contained in the IR absorbing layer of the electrophotographic light-receiving member to be formed. (H + X) is preferably 0.01 to 40 atom%, more preferably 0.05 to 30 atom%, most preferably 0.1 to 2
It is preferably set to 5 atom%.

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

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

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

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

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

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

To form the IR absorption layer by glow discharge method, HRCVD method, FOCVD method As a starting material for introducing carbon atoms, at least a gaseous substance containing carbon atoms as constituent atoms or a gasified substance that can be gasified is used. Most of the can be used.

For example, a source gas containing silicon atoms (Si) as constituent atoms, a source gas containing carbon atoms (C) as constituent atoms, and optionally hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. Or a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing carbon atoms (C) and hydrogen atoms (H) as constituent atoms. Are mixed with each other at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) as constituent atoms, and three atoms of silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H). It can be used by mixing with a raw material gas containing as a constituent atom.

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

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

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

Specifically, methane (C
H ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (nC ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene-based hydrocarbons include ethylene (C ₂ H 6). _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), acetylenic hydrocarbons As hydrogen, acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₂
H ₄ ), butyne (C ₄ H ₆ ) and the like.

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

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

In order to form an IR absorption layer by glow discharge method, HRCVD method, FOCVD method, as a starting material for introducing oxygen atoms, a gaseous substance containing at least oxygen atoms as a constituent atom or a gasifiable substance is gasified. Most of the things can be used.

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

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

A starting material effectively used as a raw material gas for introducing oxygen atoms (O) is, for example, oxygen (O ₂ ),
Ozone (O ₃ ), Nitric oxide (NO), Nitrogen dioxide (N
O ₂ ), nitrogen monoxide (N ₂ O), nitrogen trioxide (N ₂ O ₃ ),
Trinitrous oxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitric oxide (NO ₂ ), silicon atom (Si), oxygen atom (O), hydrogen atom (H), and constituent atoms For example, disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSi
And lower siloxanes such as H ₃ ).

To form the IR absorption layer by the sputtering method,
When forming the IR absorption layer, a monocrystalline or polycrystalline Si wafer or Si ₃ N ₄ wafer, or a wafer containing Si and Si ₃ N ₄ mixed and / or a SiO ₂ wafer, or Si and SiO ₂ A wafer containing a mixture of and / or a SiC wafer or a wafer containing a mixture of Si and SiC as a target,
These may be performed by spattering in various gas atmospheres.

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

Alternatively, Si and Si ₃ N ₄ may be used as separate targets or by using a single target mixed with Si and Si ₃ N _{4 in} a diluting gas atmosphere as a gas for spatula or At least hydrogen atom (H) or /
And sputtering in a gas atmosphere containing a halogen atom (X) as a constituent atom.

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

In the present invention, when the IR absorption layer is formed, the distribution concentration C (N) and / or C (C) and / or C (of nitrogen atom and / or carbon atom and / or oxygen atom contained in the layer is formed. O) in the layer thickness direction to form a layer having a desired depth profile in the layer thickness direction, in the case of glow discharge method, HRCVD method, FOCVD method, the distribution concentration C ( N) and / or C (C) and /
Alternatively, the gas of the starting material for introducing the nitrogen atom and / or the carbon atom and / or the oxygen atom whose C (O) should be changed is appropriately changed in accordance with the desired rate-of-change curve, and the gas is placed in the deposition chamber. Made by introducing.

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

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

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

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

Amount of nitrogen atom (N), amount of oxygen atom (O), amount of carbon atom (C), or sum of amount of nitrogen atom and oxygen atom (N + O), or nitrogen contained in the IR absorption layer The sum of the amounts of atoms and carbon atoms (N + C), the sum of the amounts of carbon atoms and oxygen atoms (C + O), or the sum of the amounts of nitrogen atoms, carbon atoms and oxygen atoms (N + C + O) is preferably 0.
It is desirable that the content is 01 to 40 atomic%, more preferably 0.05 to 30 atomic%, and most preferably 0.1 to 25 atomic%.

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

A starting material for introducing a Group V atom is effectively used in the present invention as PH ₃ , P ₂ for introducing a phosphorus atom.
H _4, etc. of hydrogen phosphorus _{halides, PH 4 I, PF 3,} PF 5, PCl 3, PCl 5, PBr 3, PBr 5, P
Halogenated phosphorus such as I ₃ and the like. In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , B
iCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group V atom.

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

CTL The CTL of the present invention contains, as constituent elements, a silicon atom, at least one of a carbon atom, a nitrogen atom and an oxygen atom, and a substance (M) that controls conductivity.
It is composed of Non-Si (H, X) (hereinafter abbreviated as "Non-SiM (C, N, O) (H, X)") and has a charge transport characteristic that satisfies desired electrophotographic characteristics. The carbon atoms, nitrogen atoms or oxygen atoms contained in the CTL may be contained in the CTL in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. It may be contained so that there may be a part. 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 the CTL. The substance (M) is contained in the CTL so that the distribution concentration of the substance (M) controlling the conductivity in the layer thickness direction of the CTL becomes non-uniform in at least a part of the layer region of the CTL.

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

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

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

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

In the example shown in FIG. 12, the distribution concentration C of the substance (M) is C from the interface position t _B where CTL and CGL are in contact to the position t _11.
CTL that forms a substance (M) with a certain value of ₃₇
The concentration is gradually increased continuously from the concentration C ₃₈ from the position t ₁₁ to the interface position t _T. At the interface position t _T , the distribution concentration C of the substance (M) is C ₃₉ .

In the example shown in FIG. 13, the distribution concentration C of the contained substance (M) is from the position t _B to the position t _T.
Concentration C _{41 at} position t _T gradually decreases continuously from C ₄₀
A distribution state as follows is formed.

In the case of FIG. 14, the distribution concentration C of the position t _B to the position t ₁₂ to the material (M) is the concentration C ₄₂ a constant value, the position t ₁₂
And between the position t _T, is reduced gradually continuously from C _43, at the position t _T, the distribution concentration C is substantially zero (where substantially less than the detection limit amount is zero In the case of FIG. 15, the distribution concentration C of the substance (M) is at the position t _B.
Up to more position t _T, is reduced continuously and gradually from the concentration C _44, it is substantially zero at the position t _T.

In the example shown in FIG. 16, the distribution concentration C of the substance (M)
Is a constant value of the concentration C ₄₅ between the position t _B and the position t ₁₃ , and is a concentration 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. 17, from the position t _B to the position t _T , the distribution concentration C of the substance (M) is linearly decreased from the concentration C ₄₇ to substantially zero.

In the example shown in FIG. 18, the distribution concentration C of the contained substance (M) is C ₄₈ from the position t _B to the position t _T.
The distribution state is gradually reduced from C to C ₄₉ at the position t _T.

In the example shown in FIG. 19, the distribution concentration C of the substance (M) takes a constant value of C ₅₀ from the position t _B to the position t ₁₄ and the position t
_{From 14} to the position t _T, the distribution state is a linear function decreasing from C ₇₁ to C ₅₂ .

In the example shown in FIG. 20, the distribution concentration C of the substance (M) gradually and continuously increases from C ₄₅ to C ₄₄ from the position t _B to the position t _15, and from the position t ₁₅ to C _43. A distribution state is formed such that a constant value of is taken to reach the position t _T.

In the example shown in FIG. 21, the distribution concentration C of the substance (M) forms a distribution state in which it gradually increases continuously from C ₄₇ to C ₄₆ from the position t _B to the position t _T. .

In the example shown in FIG. 22, the distribution concentration C of the substance (M) is substantially zero to C ₄₉ from the position t _B to the position t _16.
Gradually increases continuously until a constant value of C ₄₈ is obtained from the position t ₁₆ to reach the position t _T.

In the example shown in FIG. 23, the distribution concentration C of the substance (M) is substantially zero to C ₅₀ from the position t _B to the position t _T.
It forms a distribution state that gradually increases continuously until.

In the example shown in FIG. 24, material distribution concentration C (M) is increased from C ₅₂ up to the position t ₁₇ from the position t _B C ₈₁ to a linear function manner, the C ₅₁ is the position t ₁₇ The distribution is formed such that it takes a constant value and reaches the position t _T.

In the example shown in FIG. 25, the distribution concentration C of the substance (M) is substantially zero to C ₅₃ from the position t _B to the position t _T.
Up to a linear function.

In the example shown in FIG. 26, the distribution concentration C of the substance (M) forms a distribution state in which it gradually increases continuously from C ₅₅ to C ₅₄ from the position t _B to the position t _T. There is.

In the example shown in FIG. 27, material distribution concentration C (M) is increased by the position t _B to the position from C ₅₈ up to t ₁₈ C ₅₇ to the primary function manner, the C ₅₆ is the position t ₁₈ The distribution is formed such that it takes a constant value and reaches the position t _T.

28 to 37 show typical examples of the distribution of carbon atoms (C), nitrogen atoms (N) and oxygen atoms (O) contained in CTL in the layer thickness direction. In the following description, for convenience, a carbon atom (C), a nitrogen atom (N) and an oxygen atom (O) are collectively referred to as “atom (Y)”.

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

FIG. 28 shows a first typical example of the distribution state of atoms (Y) contained in CTL in the layer thickness direction.

In the example shown in FIG. 28, from the interface position t _B to the position t ₂₄ , the layer in which the atom (Y) is formed while the distribution concentration C of the atom (Y) has a constant value C ₆₉ . It is contained in the region (Y) and gradually and continuously decreases from the distribution concentration value C ₇₀ from the position t ₁₉ to the interface position t _T. At the interface position t _T , the distribution concentration C of atoms (Y) has a value C ₇₁ .

In the example shown in FIG. 29, the distribution concentration C of the contained atom (Y) gradually decreases continuously from the distribution concentration value C ₇₂ from the position t _B to the position t _T , and at the position t _T. The distribution state is such that the distribution density value is C ₇₃ .

In the case of FIG. 30, atoms (Y) are present from t _B to position t _20.
The distribution density C of is set to a constant value with the distribution density value C _74, and the position t ₂₀
And between the position t _T, is gradually reduced continuously, at position t _T, the distribution concentration C is substantially zero (in the case of less than the detection limit amount substantially zero here is there,
The same applies to the meaning of "substantially zero" hereafter).

In the case of FIG. 31, the distribution concentration C of the atom (Y) is at the position t _B.
Up to more position t _T, is reduced continuously and gradually from the density value C _76, it is substantially zero at the position t _T.

In the example shown in FIG. 32, the distribution concentration C of atoms (Y)
Is in between position t _B and position t _21, is constant and the distribution density values C _77, at position t _T is the distribution density values C _78. Between the position t ₂₁ and the position t _T , the distribution density C is linearly reduced from the position t ₂₁ to the position t _T.

In the example shown in FIG. 33, from the position t _B to the position t _T , the distribution concentration C of the atom (Y) decreases linearly from the distribution concentration value C ₇₉ to substantially zero. ing.

In the example shown in FIG. 34, the distribution concentration C of the contained atom (Y) is a value C from the position t _B to the position t _T.
A distribution state is formed in which the value gradually decreases from ₈₀ and becomes the value C ₈₁ at the position t _T.

In the example shown in FIG. 35, the distribution concentration C of the atom (Y) has a constant value of C ₈₂ from the position t _B to the position t ₂₂ ,
From the position t ₂₂ to the position t _T , the distribution state is a linear function decreasing from the value C ₈₃ to the value C ₈₄ .

In the example shown in FIG. 36, the distribution concentration C of atoms (Y) has a constant value of C ₈₅ from the position t _B to the position t _T.

28 example shown in FIG. To FIG. 35, although both towards the t _B side of the t _T side is an example distribution concentration C is large atomic (Y), t _T side and t _B side exact opposite Then, the distribution concentration C of atoms (Y) may be higher on the t _T side than on the t _B side. For example, in the example shown in FIG. 37, in FIG. 28, and t _T side
When the t _B side is reversed, the distribution concentration C of the atom (Y) is constant at the value C ₈₈ from the interface position t _B to the position t ₂₃ , and t ₂₈
From t ₈₈ to t _24, gradually increasing continuously from position C to C at position t _24
87 , which is a constant value C ₈₆ from the position t ₂₄ to the interface position t _T.

Examples of the substance (M) that controls the conductivity include Group III atoms among the substances (M _R ) that control the conductivity mentioned in the description of the IR absorption layer.

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

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

The hydrogen atoms and / or halogen atoms contained in the CTL of the present invention can compensate the dangling bonds of silicon atoms to improve the layer quality.

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

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

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

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

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

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

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

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

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

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

When formed by the sputtering method, the atom (Y)
Of the atom (Y) in the layer thickness direction by changing the distribution concentration C (Y) in the layer thickness direction in the layer thickness direction.
First, as in the case of the glow discharge method, the starting material for introducing the atom (Y) is used in a gas state, and the gas flow rate when the gas is introduced into the deposition chamber is formed. Is appropriately changed as desired.

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

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

In order to structurally introduce a substance (M) that controls the conduction characteristics into CTL, for example, a group III atom or a group V atom, the starting material or the group V atom can be used as in the case of forming the IR absorption layer. Introduce the starting material for introduction into the deposition chamber in the form of gas,
May be introduced together with other starting materials for forming

No CGL or CTL with properties that can achieve the object of the present invention
A-Si containing a hydrogen atom and / or a halogen atom as n-Si (H, X) (hereinafter referred to as "A-Si (H, X)")
In order to select and configure the above, it is necessary to appropriately set the temperature and gas pressure of the support 1 as desired.

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

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

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

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

One method is to raise the substrate temperature to a high temperature,
This is a method in which the temperature is set to 0 to 600 ° C. 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, to form a film on the support at a support temperature of, for example, about 250 ° C. by a plasma CVD method, and then subject the amorphous film to an annealing treatment. This is a method to make it poly. The annealing treatment was carried out by adding 400 to the support.
It is carried out by heating to 600600 ° C. for about 5 to 30 minutes, or by irradiating with laser light for about 5 to 30 minutes.

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

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

FIG. 38 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the RF glow discharge decomposition method.

In the gas cylinders 1011, 1012, 1013, 1014, 1015, 1016 in the figure, the raw material gas for forming the respective layers of the present invention is sealed, and as an example, for example, 1011 SiH ₄ gas ( Purity 99.999%) cylinder, 1012 H ₂ gas (purity 99.9%)
99%) cylinder, 1013 is B ₂ H ₆ gas diluted with H ₂ gas (purity 99.999% or less abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 1014 is NO
Gas (purity 99.5%) cylinder, 1015 is GeH ₄ gas (purity 99.9%)
99%) cylinder, 1016 is CH ₄ gas (purity 99.999%) cylinder.

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

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

To allow these gases to flow into the reaction chamber 1001, confirm that the valves 1051 to 1057 of the gas cylinders 1011-1017 and the leak valve 1003 of the reaction chamber 1011 are closed, and that the inflow valves 1031-1037 and the outflow valve 1041 are closed. ~ 1047, auxiliary valve 10
Make sure that 70 is open, then first, main valve 1002
To evacuate the inside of the reaction chamber 1001 and the gas pipe.

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

After that, from the gas cylinder 1011, SiH ₄ gas, gas cylinder 10
12 from H ₂ gas, gas cylinder 1013 from B ₂ H ₆ / H ₂ gas, gas cylinder 1014 from NO gas, gas cylinder 1015 from GeH ₄ gas,
NH ₃ gas from gas cylinder 1016 and CH ₄ gas from gas cylinder 1017 are introduced by opening valves 1051 to 1054, 1056, 1057, and each gas pressure is adjusted to 2 Kg by pressure regulators 1061 to 1065, 1066, 1067.
Adjust to / cm ² .

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

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

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

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

CTLs are formed on the IR absorption layer formed as described above.

To form the CTL, gradually open the outflow valves 1041, 1043, 1045 and the auxiliary valve 1070 to obtain SiH ₄ gas B ₂ H ₆ gas NH
₃ Gas is allowed to flow into the reaction chamber 1001. At this time, the SiH ₄ gas flow rate B ₂ H ₆ gas flow rate NH ₃ gas flow rate is adjusted to a desired value, the outflow valves 1041, 1043, 1045 are adjusted, and the reaction chamber pressure is adjusted to a desired value. While watching the vacuum gauge 1004, adjust the opening of the main valve 1002. After that, the power source 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber, and the formation of CTL on the substrate cylinder is started. After the desired film thickness is formed, the RF glow discharge is stopped, the outflow valves 1041, 1043, 1045 are closed to stop the gas flow into the reaction chamber, and the CTL formation is completed.

 CGL is formed on the CTL formed as described above.

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

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and each gas is in the reaction chamber 1001 and the pipes from the outflow valves 1041 to 1046 to the reaction chamber 1001. In order to avoid remaining in the inside, the outflow valves 1041 to 1046 are closed, the auxiliary valve 1070 is opened, the main valve 1002 is fully opened, and the operation of temporarily exhausting the system to a high vacuum is performed.

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

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

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

FIG. 39 shows an apparatus for producing a light receiving member for electrophotography by the μW glow discharge decomposition method.

In the gas cylinders 2011, 2012, 2013, 2014, 2015, 2016, 2017 in the figure, the raw material gas for forming each layer of the present invention is sealed, and as an example, SiH ₄
Gas (purity 99.999%) cylinder, H ₂ gas (purity 9
9.999%) cylinder, 2013 is a B ₂ H ₆ gas (purity 99.999%, abbreviated as “B ₂ H ₆ / H ₂ ” hereinafter) cylinder diluted with H ₂ gas,
2014 is a NO gas (purity 99.5%) cylinder, 2015 is a GeH ₄ gas (purity 99.999%), 2016 is an NH ₃ gas (purity 99.999%) cylinder, and 2017 is a CH ₄ gas (purity 99.999%) cylinder.

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

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

To allow these gases to flow into the reaction chamber 2001, make sure that the valves 2051 to 2057 of the gas cylinders 2011 to 2017 and the leak valve 2003 of the reaction chamber 2011 are closed, and that the inflow valves 2031 to 2037 and the outflow valve 2041 are closed. ~ 2047, auxiliary valve 20
After confirming that 70 is open, the main valve 2002 is first opened to evacuate the reaction chamber 2001 and the gas pipe.

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

After that, from gas cylinder 2011, SiH ₄ gas, gas cylinder 20
12 from H ₂ gas, gas cylinder 2013 from B ₂ H ₆ / H ₂ gas, gas cylinder 2014 from NO gas, gas cylinder 2015 from GeH ₄ gas,
NH ₃ gas from gas cylinder 2016, CH ₄ from gas cylinder 2017
Gas is introduced by opening valves 2051 to 2057 and pressure regulator 20
Each gas pressure is adjusted to ² Kg / cm ² by 61 to 2067.

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

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

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

Outflow valves 2041,2043,204 to form the IR absorption layer
4,2045 and auxiliary valve 2070 are gradually opened to SiH ₄ gas,
B ₂ H ₆ / H ₂ gas NO gas GeH ₄ gas is flown into the reaction chamber 2001. At this time, the outflow valves 2041, 2043, 2044, 2045 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ / H ₂ gas flow rate, the NO gas flow rate, and the GeH ₄ gas flow rate have desired values, and The opening of the main valve 2002 is adjusted while observing the vacuum gauge 2004 so that the pressure in the reaction chamber becomes a desired value. Then microwave power
Set 2008 to desired power, waveguide 2009 and dielectric window
Through 2010, a μW glow discharge is generated in the reaction chamber to start forming a charge injection blocking layer on the substrate cylinder. After forming the desired film thickness, stop the μW glow discharge,
Further, the outflow valves 2041, 2043, 2044, 2045 are closed to stop the inflow of gas into the reaction chamber, and the formation of the charge injection blocking layer is completed.

CTLs are formed on the IR absorption layer formed as described above.

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

 CGL is formed on the CTL formed as described above.

To form CGL, the outflow valves 2041 and 2042 and the auxiliary valve 2070 are gradually opened to supply SiH ₄ gas and H ₂ gas to the reaction chamber 2001.
Let it flow in. At this time, the outflow valves 2041 and 2042 are adjusted so that the SiH ₄ gas flow rate and the H ₂ gas flow rate have desired values, and while watching the vacuum gauge 2004 so that the pressure in the reaction chamber has 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, the outflow valves 2041 and 2042 are closed to stop the gas flow into the reaction chamber, and the CGL formation is completed.

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

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

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

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

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

In FIG. 40, 3001 is a film forming chamber, 3002 is an activation chamber (A), 3003 and 3018 are microwave plasma generators, and 300
4 is a raw material gas introduction pipe of active species (A), 3005 is an active species (A) introduction pipe, 3006 is a motor, 3007 is a heater for heating a cylindrical substrate, 3008 and 3009 are blowing pipes, 301
Reference numeral 0 indicates a cylindrical substrate, and 3011 indicates a main exhaust valve. Further, reference numerals 3012 to 3016 are cylinders for supplying a source gas, 3017 is an activation chamber (B), 3019 is a source gas introduction pipe, and 3020 is an activated species introduction pipe generated from the activation chamber (B). A method for producing an electrophotographic light-receiving member having a layer structure according to the present invention on a cylindrical substrate using this apparatus will be specifically described.

As an example, Al is used as the cylindrical substrate, and SiH ₄ , GeH ₄ , B ₂ H ₆ , NOH is used as the IR absorption layer forming gas.
₂ , SiH ₄ H ₂ was used as the CGL forming gas, and SiH ₄ , SiF ₄ , CH ₄ H ₂ , and B ₂ H ₆ were used as the CTL forming gas.

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

To form the IR absorption layer, H ₂ gas is introduced from the cylinder 3012 into the activation chamber (A) through the introduction pipe 3004, activated by the microwave plasma generator 3003, and active hydrogen is blown out through the introduction pipe 3005. A tube 3008 led to a film forming chamber 3001. On the other hand, SiH ₄ gas from a cylinder 3013, B ₂ H ₆ gas from 3014, NO gas from 3015, CH ₄ gas from 3016, GeH ₄ gas and SiF ₄ gas from a cylinder not shown in an activation chamber (B ) 3017, microwave plasma generator 3018
After the activation treatment by, the gas was introduced into the film forming chamber 3001 through the introduction pipe 3020 and the blowing pipe 3009. At this time, the gas flow rate,
The internal pressure and the microwave power are set to desired values.

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

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

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

Gas cylinders 4011, 4012, 4013, 4014, 4015, 4016, 4017 in the figure, the source gas for forming each layer of the present invention is sealed, as an example, for example 4011 Si
H ₄ gas (purity 99.999%) cylinder, _{40 12} 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 is GeH ₄ gas (purity 99.5%)
Cylinder 4016 is CH ₄ gas (purity 99.99%)
Cylinder 4017 is F ₂ gas (10% He diluted, purity 99.99%).

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

As an example of forming a light receiving member for electrophotography,
SiH ₄ gas, B ₂ H ₆ H ₂ gas, NO gas, G for IR absorption layer forming gas
eH ₄ gas, F ₂ gas, SiH ₄ gas, H ₂ as CGL formation gas
Gas, SiH _{4 gas,} F ₂ gas as a gas for CTL formation, CH ₄ gas, B ₂ H ₆ gas, a case of using the F ₂ gas pick.

The raw material gas filled in the cylinders 4011 to 4016 is 40
It introduces into the vacuum chamber of 4020 to 4001 through each valve of 31 to 4036 and the mass flow controller of 4053 to 4058.

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

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

4061 heats the substrate 4060 to an appropriate temperature during film formation,
Alternatively, it is a heater for heating the substrate, which 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).

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

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

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

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

To form the IR absorption layer, the valves 4046 to 4049 are opened, and the outflow valves 4031, 4033, 4034, 4035 and the auxiliary valve 4060 are gradually opened to SiH ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, GeH. ₄ Gas is allowed to flow into the reaction chamber 4001. At this time, the outflow valves 4031, 4032, 4033, 4034, 40 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ / H ₂ gas flow rate, the NO gas flow rate, and the GeH ₄ gas flow rate have desired values.
35 is adjusted, and the opening of the main valve 4002 is adjusted while observing a vacuum gauge (not shown) at which the pressure in the reaction chamber reaches a desired value.

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

CTL and CGL are formed in this order on the IR absorption layer formed as described above by the same operation as above. For each layer, flow the required gas,
The valve may be operated in the same manner as the IR absorption layer.

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

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

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

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

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

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

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. When the sputtering method is used, for example, a target made of Si is used in an atmosphere of an inert gas such as Ar or He or a mixed gas containing these gases as a base. , A hydrogen atom (H) or / and a halogen atom (X) is introduced into the deposition chamber for sputtering, and a plasma atmosphere of a desired gas is formed.

In the case of the ion plating method, for example, polycrystal silicon or single crystal silicon is accommodated in a vapor deposition board as an evaporation source, and this evaporation source is heated and vaporized by a resistance heating method or an electron beam method (EB method). ,
It can be carried out in the same manner as in the sputtering method except that the flying evaporate is passed through a desired gas plasma atmosphere. In order to form CGL composed of Non-Si (H, X) by the HRCVD method, for example, the raw material gas for supplying Si can be a desired gas in the activation space provided in the previous stage in the deposition chamber where the pressure inside can be reduced. It is introduced under pressure to generate glow discharge or overheat in the activation space to generate active species (A), and a raw material gas for introducing hydrogen atom (H) and / or halogen. Similarly, the raw material gas for introducing the atom (X) is introduced into another activation space to generate the active species (B), and the active species (A) and the active species (B) are separately introduced into the deposition chamber. After introduction, a layer made of Non-Si (H, X) may be formed on the surface of a predetermined support which is installed at a predetermined position in advance. Non-Si by FOCVD method
In order to form CGL composed of (H, X), for example, a raw material gas for supplying Si is introduced into a deposition chamber in which the inside pressure can be reduced at a desired gas pressure state, and a halogen atom (X) gas is further used as a raw material. Separately from the gas, the gas is introduced into the deposition chamber in a desired gas pressure state, and these gases are chemically reacted in the deposition chamber to form a gas on the surface of a predetermined support previously installed at a predetermined position.
A layer made of Non-Si (H, X) may be formed.

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

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

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

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

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

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

In the present invention, the halogen compound described above as a raw material gas for introducing a halogen atom, or a silicon compound containing a halogen is used as an effective one, in addition, HF, HCl, HBr, such as HI Hydrogen halide, SiH
₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₂ , SiH ₂ Br ₂ , SiHBr ₂ , etc.Halogen-substituted silicon hydride, etc. Can be listed as a substance. Among these substances, the halides containing hydrogen atoms are introduced because, at the same time as the introduction of halogen atoms into the layer during the formation of CGL, hydrogen atoms that are extremely effective in controlling the electrical or photoelectric properties are also introduced. In the invention, it is used as a preferable raw material for introducing halogen.

To structurally introduce during CGL hydrogen atom, addition of H ₂ above or _{SiH 4, Si 2 H 6,} Si 3 H 8, Si 4 H 10 , etc. for supplying silicon hydride and Si, It can also be carried out by causing the above-mentioned silicon or silicon compound to coexist in the deposition chamber to cause discharge.

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

〔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 had been mirror-finished according to the preparation conditions shown in Tables, Tables 2, 3, and 4.

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

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

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

<Example 2> Using the manufacturing apparatus shown in FIG. 38, a drum was prepared in the same manner as in Example 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 6, and 7. Similar evaluation was performed.

 The results are shown in Table 8.

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

<Embodiment 3> Using the manufacturing apparatus shown in FIG. 38, a drum was prepared in the same manner as in Embodiment 1 by RF glow discharge under the preparation conditions shown in Tables 1, 2, 9, and 10. Similar evaluation was performed.

 The results are shown in Table 11.

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

<Embodiment 4> Using the manufacturing apparatus shown in FIG.
Photoreceptive members for electrophotography were formed on aluminum cylinders that had been mirror-finished according to the preparation conditions shown in Tables 13, 13 and 14.

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

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 16 shows the comprehensive evaluation results.

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

<Example 5> Using the manufacturing apparatus shown in FIG. 40, a photoreceptive member for electrophotography was formed on an aluminum cylinder that was mirror-finished by the HRCVD method according to the conditions shown in Tables 17 to 20. The prepared electrophotographic light-receiving member was set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging ability was set under various conditions. , The electrophotographic characteristics such as sensitivity, residual potential, and ghost were checked, and the deterioration of charging ability, surface scraping, increase of image defects, etc. were examined after the endurance of 2 million sheets of accelerated real machine.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Furthermore, the scratch resistance was examined by applying a constant load to a needle having a spherical tip to scratch the drum surface. Table 21 shows the comprehensive evaluation results.

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

<Embodiment 6> Using the manufacturing apparatus shown in FIG.
Photoreceptive members for electrophotography were formed on aluminum cylinders that were mirror-finished according to the preparation conditions shown in Table 3, Table 24, and Table 25.

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

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 26 shows the comprehensive evaluation results.

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

<Embodiment 7> Mirror-finished cylinders are further subjected to lathe processing with a sword bite having various angles to obtain cylinders having various sectional patterns as shown in Table 28 with a sectional shape as shown in FIG. 46. I prepared multiple books. The cylinder was sequentially set in the manufacturing apparatus shown in FIG. 38 and subjected to drum making under the making conditions shown in Table 27. The drums thus prepared were subjected to various evaluations by an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 29 were obtained.

<Embodiment 8> The surface of a cylinder that has been mirror-finished is continuously exposed to the dropping of a large number of bearing balls, and a so-called surface dimple forming treatment that causes innumerable dents on the cylinder surface is performed. A plurality of cylinders having the cross-sectional shape shown in the figure and various cross-sectional patterns as shown in Table 31 were prepared. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 38 and subjected to drum making under the making conditions shown in Table 30. The drums thus prepared were subjected to various evaluations using an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus having a digital exposure function using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 32 were obtained.

<Example 9> Using the manufacturing apparatus of FIG. 38, Table 33, Table 34, Table 35,
Drums were prepared in the same manner as in Example 1 under the preparation conditions shown in Table 36, and the same evaluation was performed.

 The results are shown in Table 37.

As shown in Table 37, good results were obtained for all items.

[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 extremely excellent initial charging ability, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability and the like. Further, its electrical characteristics are stable, and an image obtained by using it has a high density and a clear halftone, and is very excellent.

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

[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 views for explaining the distribution state of atoms (GS) contained in the IR absorption layer, and FIGS. 12 to 27 are respectively Substances contained in CTL (M)
28 to 37 are explanatory views for explaining the distribution state of carbon atoms and / or oxygen atoms and / or nitrogen atoms contained in CTL, respectively, and FIG. 38 is An example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention, a schematic explanatory view of a manufacturing apparatus by a glow discharge method using RF, FIG. 39 is an electrophotographic light of the present invention An example of an apparatus for forming a light receiving layer of a receiving member, which is a schematic explanatory view of a manufacturing apparatus by a glow discharge method using microwaves, FIG. 40 is a light receiving layer of a light receiving member for electrophotography of the present invention FIG. 41 is an example of an apparatus for forming a light-receiving layer of an electrophotographic light-receiving member of the present invention, which is an FOCVD method. 42 is a schematic explanatory view of a manufacturing apparatus according to FIG. FIG. 43 is a view showing flow rate changes during film formation of an impurity gas and a doping gas when the CTL of FIG. 4 is formed by RF glow discharge, and FIG. 43 is a microwave glow discharge of the CTL of the electrophotographic light-receiving member of the present invention. FIG. 44 is a diagram showing flow rate changes during film formation of an impurity gas and a doping gas in the case of using HRCVD. FIG. 44 shows CTL of the photoreceptive member for electrophotography of the present invention by HRCVD.
Showing changes in the flow rate of the impurity gas and the doping gas during the film formation when the CTL of the light-receiving member for electrophotography of the present invention is FOCVD
Showing changes in the flow rates of the impurity gas and the doping gas at the time of film formation in the case where the electrophotographic light receiving member of the present invention is formed. An enlarged view of the cylinder cross section in the case of a letter shape, FIG. 47 is an enlarged view of the cylinder cross section when the surface of the cylinder substrate when forming the electrophotographic light-receiving member of the present invention is subjected to so-called dimple processing, 48 The figure is a diagram showing flow rate changes at the time of film formation of an impurity gas and a doping gas in the case of an embodiment in which the CTL of the electrophotographic light-receiving member of the present invention is formed by using RF glow discharge. About Fig. 1, 100 ... Photoreceptive layer 101 ... Support 102 ... IR absorption layer 103 ... CTL 104 ... CGL 105 ... Free surface About Fig. 3, Fig. 4, 301401 ... Support 302402 ... … Support surface 303403 …… Rigid spherical sphere 304404 …… Spherical trace depression About Fig. 5, 500… Photoreceptive layer 501 …… Support 502 …… IR absorption layer 503 …… CTL 504 …… CGL 505 …… Free Surface In Fig. 38, 1001 ... reaction chamber 1002 ... main exhaust valve 1003 ... reaction chamber leak valve 1004 ... vacuum gauge 1007 ... cylinder substrate 1008 ... substrate heating heater 1009 ... cylinder substrate rotation motor 1010 …… RF power supply 1011-1017 …… Raw gas cylinder 1021 ～ 1027 …… Mass flow controller 1031 ～ 1037 …… Gas inlet valve 1041 ～ 1047 …… Gas outlet valve 1051 ～ 1057 …… For raw material gas cylinder Valves 1061 to 1067 ...... Pressure regulator Regarding Fig. 39, 2001 ...... Reaction 2002 …… Main exhaust valve 2003 …… Reaction chamber leak valve 2004 …… Vacuum gauge 2005 …… Base heating heater 2006 …… Cylinder base 2007 …… Base rotation motor 2008 …… Microwave power supply 2009 …… Waveguide Tube 2010 …… Dielectric window 2011 ～ 2017 …… Raw material gas cylinder 2021 ～ 2027 …… Mass flow controller 2031 ～ 2037 …… Gas inflow valve 2041 ～ 2047 …… Gas outflow valve 2051 ～ 2057 …… Raw material gas ・Cylinder valve 2061 to 1267 …… Pressure regulator About Fig. 40, 3001 …… Deposition chamber 3002 …… Activation chamber (A) 30033018 …… Microwave plasma generator 30043019 …… Raw material gas inlet pipe 30053020 …… Activity Seed introduction pipe 3006 …… Motor 3007 …… Cylinder substrate heating heater 30083009 …… Blowout pipe 3010 …… Cylinder substrate 3011 …… Main exhaust valve 3012-3016 …… Source gas cylinder 3017 …… Activation chamber (B ) Regarding Fig. 41, 4001 ...... Reaction chamber 4002 ...... Main exhaust valve 4011-4017 …… Raw material gas cylinder 40204021 …… Raw material gas inlet pipe 4031 -4037 …… Outflow valve 4046 〜 4052 …… Inflow valve 4053 -4059 …… Mass flow Controller 4060 …… Cylinder substrate 4061 …… Cylinder substrate heater 4062 …… Cylinder substrate rotation motor

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

Claims (1)

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