JPH0797230B2 - Photoreceptive member for electrophotography - Google Patents

Description

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

[Description of Prior Art]

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

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

However, the conventional photoreceptive member for electrophotography having a light-receiving layer composed of A-Si has the following electrical, optical and photoconductive characteristics such as dark resistance, photosensitivity, and photoresponsiveness and operating environment characteristics. With respect to the points, and further with respect to the stability over time and the durability, the characteristics have been individually improved, but there is room for further improvement in the overall improvement of the characteristics.

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

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

That is, for example, the life of the photo-carriers formed in the formed photoconductive layer by light irradiation is not sufficient, or the image transferred onto the transfer paper is generally called "white blank". Image defects that are considered to be caused by a local discharge breakdown phenomenon, and when a blade is used as a cleaning means, image defects commonly called "white streaks" that are thought to be caused by the rubbing have occurred. Further, when used in a humid atmosphere, or when used immediately after being left in a humid atmosphere for a long period of time, it is not uncommon for blurry images to occur.

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

[Object of the Invention]

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

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

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

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

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

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

[Structure of Invention]

The light-receiving member for electrophotography of the present invention has a support and a light-receiving member having a layer structure in which a charge generation layer, a charge transport layer and a surface layer are laminated in this order from the support side. A surface layer made of a non-single-crystal material containing a silicon atom, at least one of a carbon atom, a nitrogen atom and an oxygen atom, and at least one of a hydrogen atom and a halogen atom. , The charge generation layer (hereinafter abbreviated as “CGL”) and the charge transport layer (hereinafter abbreviated as “CTL”) have silicon atoms as a matrix,
A non-single crystal material containing at least one of a hydrogen atom and a halogen atom (hereinafter abbreviated as "Non-Si (H, X)"), and the charge transport layer is a carbon atom or a nitrogen atom. And a non-uniform distribution containing at least one of oxygen atoms and having a portion in which the concentration of atoms belonging to Group III or V of the periodic table increases or decreases in the layer thickness direction from the support side. At least a portion contained in the state is included, and the layer thickness of the charge generation layer is smaller than the layer thickness of the charge transport layer.

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

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

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

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

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

[Specific Description of the Invention]

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

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

The electrophotographic light-receiving member 100 shown in FIG. 1 includes a CGL 102 composed of Non-Si (H, X) on a support 101 and a non-Si (H, X) for the electrophotographic light-receiving member. ) And 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. And a light receiving layer having a layer structure including a surface layer 104. The CTL 105 has a free surface 106.

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

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

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

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

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

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

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

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

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

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

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

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

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

Further, the maximum layer thickness difference based on the non-uniformity of the layer thickness of each layer deposited on such a support is preferably within the same pitch.
The thickness is preferably 0.1 μm to 2 μm, more preferably 0.1 μm to 1.5 μm, and most preferably 0.2 μm to 1 μm.

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

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

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

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

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

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

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

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

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

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

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

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

FIG. 5 shows the CGL502, on the support 501 prepared by the above method.
An example in which a light receiving layer 500 including a CTL 503 and a surface layer 504 is formed is shown. The surface layer 504 has a free surface 505.

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, any of the substance (M), the carbon atom (C), the nitrogen atom (N), and the oxygen atom (D) that control conductivity are substantially contained. Not contained in.

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

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

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

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

In addition to these, the active species (A) generated by decomposing the raw material gas for forming the non-single crystal material and the active species (A)
And the active species (B) generated from the chemical substance for film formation that chemically interacts with each other are introduced separately into the film formation space for forming the deposited film and chemically reacted with each other. A method for forming a crystalline material (hereinafter abbreviated as “HRCVD method”), a source gas for forming a non-single-crystal material, and a halogen-based oxidant gas having a property of oxidizing the source gas are separately deposited. Examples thereof include a thin film deposition method such as a method of forming a non-single crystal material by introducing it into a film formation space for forming a film and chemically reacting these (hereinafter abbreviated as “FOCVD method”). These thin film deposition methods are
It is appropriately selected and adopted depending on factors such as manufacturing conditions, load level of capital investment, manufacturing scale, and desired characteristics of the light receiving member to be produced. Since it is relatively easy to control the conditions for manufacturing, and halogen atoms and hydrogen atoms can be easily introduced together with silicon atoms, the glow discharge method, the sputtering method, the ion plating method, ECR-CVD method, HRCVD method and FOCVD method are suitable. In some cases, these methods may be used together in the same device system. For example, by the glow discharge method, Mon-Si (H,
In order to form CGL composed of X), basically, a raw material gas for supplying Si and a raw material gas for introducing hydrogen atom (H) or / and a halogen atom (X ) A raw material gas for introduction is introduced into a deposition chamber in which the inside can be decompressed under a desired gas pressure state to cause glow discharge in the deposition chamber, and on a predetermined support surface installed in advance at a predetermined position. A layer made of Non-Si (H, X) may be formed on. In the case of forming by the sputtering method, for example, using a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas in which these gases are used as a space, and if necessary. , A hydrogen atom (H) or / and a halogen atom (X) is introduced into the deposition chamber for sputtering, and a plasma atmosphere of a desired gas is formed.

In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon is housed in a vapor deposition board as an evaporation source, and this evaporation source is heated and evaporated by a resistance heating method, an electron beam method (EB method), or the like. In the same manner as in the sputtering method, except that the flying evaporated material is allowed to pass through a desired gas plasma atmosphere. Composed of Non-Si (H, X) by HRCVD method
To form CGL, for example, a raw material gas for supplying Si is introduced in a desired gas pressure state into an activation space provided in the preceding stage in the deposition chamber where the inside pressure can be reduced, and glow discharge is performed in the activation space. Is generated or is heated to generate an active species (A), and a raw material gas for introducing a hydrogen atom (H) and / or a raw material gas for introducing a halogen atom (X) is similarly activated. To generate an active species (B) by introducing the active species (A) and the active species (B) into the deposition chamber separately, and a predetermined support previously installed at a predetermined position. A layer made of Non-Si (H, X) may be formed on the surface. In order to form CGL composed of Non-Si (H, X) by the FOCVD method, for example, a raw material gas for supplying Si is introduced into a deposition chamber where the inside can be depressurized at a desired gas pressure state, and halogen (X ) A gas is introduced into the deposition chamber in a desired gas pressure state separately from the source gas, and these gases are chemically reacted in the deposition chamber to form a non-deposited gas on the surface of a predetermined support previously installed at a predetermined position. It suffices to form a layer other than Si (H, X).

Examples of the substance that can be used as the raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H _{10 in} a gas state or a gasifiable silicon hydride (silane). Are used effectively, and in particular, SiH ₄ , Si ₂ H in terms of ease of handling during layer formation work, good Si supply efficiency, etc.
₆ is mentioned as a preferable one.

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

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

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

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

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

According to the glow discharge method, when producing CGL containing a halogen atom, basically, for example, in a deposition chamber for forming CGL by adjusting the silicon halide, which is the raw material gas for Si supply, to a predetermined gas flow rate. Introduced, by generating a glow discharge to form a plasma atmosphere of these gases, it is possible to form CGL on the desired support,
In order to make it easier to control the introduction ratio of hydrogen atoms, hydrogen gas or a gas of a silicon compound containing hydrogen atoms may be mixed in a desired amount with these gases to form a layer.

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

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

Further, in the case of introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or the gases of the above-mentioned silanes are introduced into the deposition chamber for sputtering and the plasma atmosphere of the gases is changed. Just form it.

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

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

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

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

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

FIGS. 6 to 21 show typical examples of the distribution state of the substance (M) contained in CTL in the layer thickness direction, which controls the conductivity.

In FIGS. 6 to 21, the horizontal axis represents the distribution concentration C of the contained substance (M), the vertical axis represents the layer thickness of CGL, t _B represents the position of the end surface of CGL on the support side, and t _T represents 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. 6 shows a first typical example of the state of distribution of the substance (M) contained in CGL in the layer thickness direction.

In the example shown in FIG. 6, from the interface position t _B to the position t ₁₆ , the layer region in which the substance (M) is formed while the distribution concentration C of the substance (M) has a constant value C _57. It is contained in (M) and gradually and continuously decreases from the distribution concentration value C ₅₈ from the position t ₁₆ to the interface position t _T. At the interface position t _T , the distribution concentration C of the substance (M) has a value C ₅₉ .

In the example shown in FIG. 7, the substance contained (M)
Distribution density C of the distribution density value from position t _B to position t _T
A distribution state is formed in which the distribution concentration value C ₆₁ gradually decreases continuously from C ₆₀ and reaches the distribution concentration value C ₆₁ at the position t _T.

In the case of FIG. 8, the distribution concentration C of the substance (M) is a constant value with the distribution concentration value C ₆₂ from the position t _B to the position t ₁₇ .
Between the position t ₇ and position t _T, is gradually reduced continuously, at position t _T, the distribution concentration C is substantially zero (where substantially less than the detection limit amount is zero The same applies to the meaning of "substantially zero" hereafter).

In the case of FIG. 9, the distribution concentration C of the substance (M) is continuously and gradually decreased from the concentration value C ₆₄ from the position t _B to the position t _T , and becomes substantially zero at the position t _T. Has been done.

In the example shown in FIG. 10, the distribution concentration C of atoms (M)
Is a constant value with the distribution density value C ₆₅ between the position t _B and the position t ₁₈ , and is a distribution density value C _{66 at} the position t _T. Between the position t ₁₈ and the position t _T , the distribution concentration C is linearly reduced from the position t ₁₈ to the position t _T.

In the example shown in FIG. 11, from the position t _B to the position t _T , the distribution concentration C of the substance (M) decreases linearly as the distribution concentration value C ₆₆ reaches substantially zero. ing.

In the example shown in FIG. 12, substances contained (M)
The distribution density C is gradually reduced from the value C ₆₈ to the value t _T from the position t _B to the value C ₆₉ at the position t _T , thus forming a distribution state.

In the example shown in FIG. 13, the distribution concentration C of the substance (M) has a constant value C ₇₀ from the position t _B to the position t _19, and the value C ₇₁ from the position t ₁₉ to the position t _T. It is assumed that the distribution state decreases linearly up to the value C ₇₂ .

In the example shown in FIG. 14, the distribution concentration C of the substance (M) has a constant value C ₇₃ from the position t _B to the position t _T.

The example shown in Figure 6 to Figure 13, although both towards the t _B side of the t _T side is an example distribution concentration C is larger substances (M), t _T side and t _B side exact opposite Then, the distribution concentration C of the substance (M) may be higher on the t _T side than on the t _B side.

For example, in the example shown in FIG. 15, when t _T side and t _B are reversed in FIG. 6, the distribution concentration C of the substance (M) is a value C ₇₆ from the interface position t _B to the position t _20. interface position from C ₇₅ next position t ₂₀ gradually increases continuously to position t ₂₀ from t _T
It becomes a constant value up to the value C ₇₄ .

FIGS. 22 to 31 show the carbon atoms and / or nitrogen atoms and / or oxygen atoms (hereinafter collectively referred to as “atoms (Y)”) contained in CTL in the layer thickness direction. A typical example of distribution is shown.

22 to 31, 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. 22 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. 22, the interface position where CGL and CTL contact
From t _B to the position of t ₂₄ , the distribution concentration C of the atom (Y) is C _89.
The atom (Y) is contained in the CTL in which the atom (Y) is formed with a certain constant value, and is gradually and continuously reduced from the concentration C ₉₀ to the interface position t _T from the position t ₂₄ . At the interface position t _T , the distribution concentration C of atoms (Y) is C ₉₁ .

In the example shown in FIG. 23, the contained atom (Y)
The distribution concentration C of C is gradually and continuously decreased from the concentration C ₉₂ to the position t _T from the position t _B, and becomes the concentration C ₉₃ at the position t _T.

In the case of FIG. 24, from the position t _B to the position t ₂₅ , the distribution concentration C of the atom (Y) is set to a constant value as the concentration C _94, and the position t ₂₅
And between the position t _T, gradually reduced continuously from C _95, at the position t _T, the distribution concentration C is substantially zero (where substantially less than the detection limit amount is zero Is the case).

In the case of FIG. 25, the distribution concentration C of the atom (Y) is continuously and gradually decreased from the concentration C ₉₆ until it reaches the position t _T from the position t _B , and becomes substantially zero at the position t _T. ing.

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

In the example shown in FIG. 27, from the position t _B to the position t _T , the distribution concentration C of the atom (Y) is linearly decreased from the concentration C ₉₉ to substantially zero.

In the example shown in FIG. 28, the contained atom (Y)
The distribution density C of C gradually decreases continuously from C ₁₀₀ from position t _B to position t _T , and forms a distribution state of C _{101 at} position t _T.

In the example shown in FIG. 29, the distribution concentration C of atoms (Y) takes a constant value of C ₁₀₂ from the position t _B to the position t _27, and from the C ₁₀₃ to C ₁₀₄ from the position t ₂₇ to the position t _T. It is assumed that the distribution state decreases linearly until.

In the example shown in FIG. 30, the distribution concentration C of atoms (Y) takes a constant value of C ₁₀₅ from the position t _B to the position t.

The example shown in Figure 22 to Figure 29 are all but towards the t _B side of the t _T side is an example distribution concentration C is large atomic (Y) to reverse the t _T side and t _B side at all The distribution concentration C of atoms (Y) may be higher on the t _T side than on the t _B side. For example, in the example shown in FIG. 31, when the t _T and t _B sides are reversed in FIG. in the distribution concentration C of the atoms (Y) up to the interface position t _B to the position t ₂₈ is gradually increased continuously from C _108, the C ₁₀₇ next position t ₂₈ to the interface position t _T at the position t ₂₈ C
_{It is} a constant value of ₁₀₆ .

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

In the present invention, by containing a group III atom or a group V atom as the substance (M) for controlling conductivity in the entire layer region of CTL, the effect of mainly controlling the conductivity type and / or the conductivity and / or Alternatively, the effect of improving the charge injection property between CGL and CTL can be obtained, but the content thereof is set to a relatively small amount. The content of the substance (M) is preferably 1 × 10 ⁻³ to 1 × 10 ³ ppm, more preferably 5 × 1.
It is desirable that the content is 0 ³ to 1 × 10 ² atomic ppm, optimally 1 × 10 ⁻² to 50 atomic ppm.

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

Further, the hydrogen atom contained in the CTL of the present invention or /
And the halogen atom can compensate the dangling bond of the silicon atom to improve the layer quality.

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

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

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

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

To form a CTL by glow discharge method, HRCVD method, FOCVD method As a starting material for introducing nitrogen atoms, at least a substance on a gas containing nitrogen atoms as a constituent atom or a gasified substance that can be gasified is selected. Most can be used.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing 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 3 and a raw material gas having three constituent atoms of a silicon atom (Si), a nitrogen atom (N) and a hydrogen atom (H).

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

A starting material effectively used as a raw material gas for introducing a nitrogen atom (N) includes N as a constituent atom or N and H as a constituent atom, such as nitrogen (N ₂ ), ammonia ( NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ) and other gaseous or gasifiable nitrogen compounds, nitrogen compounds such as nitrides and azides. Can be mentioned. In addition to this, in addition to the introduction of nitrogen atoms (N), the introduction of halogen atoms (X) is also possible, so nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F)
₄ N ₂ ) and other halogenated nitrogen compounds.

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

For example, a source gas containing silicon atoms (Si) as constituent atoms, a source gas containing carbon atoms (C) as constituent atoms, and optionally hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. Or a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing carbon atoms (C) and hydrogen atoms (H). Is also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) as constituent atoms and three gases of silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H). It is possible to mix and use a raw material gas that is a constituent atom.

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

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

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

As a source gas containing Si, C and H as constituent atoms, Si (C
Mention may be made of alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

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

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

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (O) as constituent atoms, and, if necessary, hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. A raw material gas is mixed at a desired mixing ratio and used, or a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) as constituent atoms. And, also in the desired mixing ratio, or silicon atoms (Si)
It is possible to mix and use a raw material gas having a constituent atom of 3 and a raw material gas having three constituent atoms of a silicon atom (Si), an oxygen atom (O) and a 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.

Starting materials that are effectively used as raw material gases for introducing oxygen atoms (O) include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), and nitrogen dioxide (NO ₂ ). , Nitric oxide (N ₂ O), Nitric oxide (N ₂ O ₃ ), Nitric oxide (N ₂ O ₄ ), Nitric oxide (N ₂ O ₅ ), Nitric oxide (NO
₂ ), silicon atoms (Si), oxygen atoms (O), hydrogen atoms (H) and constituent atoms, such as disiloxane (H ₃ SiOS
Examples thereof include lower siloxanes such as iH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ).

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

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

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

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

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

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

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

Second, a target for sputtering, such as Si
If you are using the mixed Tagetsuto the top of the Si ₃ N ₄ and a mixing ratio of Si and Si ₃ N _4, in the layer thickness direction of Tagetsuto, made by allowed to advance changed.

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

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

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

CGL102, CTL103 having properties capable of achieving the object of the present invention
In order to select and configure A-Si containing hydrogen atoms and / or halogen atoms as Non-Si (H, X) (hereinafter referred to as "A-Si (H, X)"), 101 temperature,
It is necessary to set the gas pressure appropriately as desired.

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

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

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

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

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

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

Surface Layer The surface layer 104 in the present invention is a non-Si (containing at least one of a silicon atom, a carbon atom, a nitrogen atom and an oxygen atom, and at least one of a hydrogen atom and a halogen atom) as a constituent element. C, N, O) (H, X)
Composed of. The surface layer contains no or substantially no substance (M) that controls conductivity as contained in CTL.

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

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

32 to 41 show carbon atoms and / or nitrogen atoms and / or oxygen atoms (hereinafter,
These are collectively referred to as “atoms (Y)”), and typical examples of the state of distribution in the layer thickness direction are shown.

32 to 41, the horizontal axis represents the distribution concentration C of contained atoms (Y), the vertical axis represents the layer thickness of the surface layer, and t _B
Indicates the position of the end surface of the surface layer on the side opposite to the support side, and t _T indicates the position of the end surface of the surface layer on the side opposite to the support side. That is, the surface layer containing atoms (Y) is formed from the t _B side toward the t _T side.

FIG. 32 shows a first typical example of the distribution state of atoms (Y) contained in the surface layer in the layer thickness direction.

In the example shown in FIG. 32, the distribution concentration C of atoms (Y) is
Forms a distribution state in which it gradually increases continuously from C ₁₁₁ to C ₁₁₀ from position t _B to position t ₂₉ , and takes a constant value of C ₁₀₉ from position t ₂₉ to reach position t _T. There is.

In the example shown in FIG. 33, the distribution concentration C of the atom (Y) forms a distribution state in which it gradually increases continuously from C ₁₁₃ to C ₁₁₂ from the position t _B to the position t _T. There is.

In the example shown in FIG. 34, the distribution concentration C of the atom (Y) is substantially zero to C ₁₁₅ from the position t _B to the position t _30.
The distribution state is such that it gradually increases continuously up to and takes a constant value of C ₁₁₄ from the position t ₃₀ and reaches the position t _T.

In the example shown in FIG. 35, the distribution concentration C of atoms (Y) forms a distribution state in which the distribution concentration C of the atom (Y) gradually increases continuously from zero to C ₁₁₆ from the position t _B to the position t _T. is doing.

In the example shown in FIG. 36, atomic distribution concentration C (Y) is increased from C ₁₁₈ up to the position t ₃₁ from the position t _B C ₁₁₇ to a linear function manner, the C ₁₁₇ is the position t ₃₁ The distribution is formed such that it takes a constant value and reaches the position t _T.

In the example shown in FIG. 37, the distribution concentration C of the atom (Y) is substantially zero to C ₁₁₉ from the position t _B to the position t _T.
Up to a linear function.

In the example shown in FIG. 38, the distribution concentration C of the atom (Y) forms a distribution state in which it gradually increases continuously from C ₁₂₅ to C ₁₂₀ from the position t _B to the position t _T. There is.

In the example shown in FIG. 39, the distribution concentration C of atoms (Y)
Form a distribution that increases linearly from C ₁₂₄ to C ₁₂₃ from position t _B to position t ₃₂ and takes a constant value of C ₁₂₂ from position t ₃₂ to position t _T. There is.

In the example shown in FIG. 40, the distribution concentration C of atoms (Y) takes a constant value of C ₁₂₅ from the position t _B to t _T.

In the example shown in FIG. 41, the distribution concentration C of atoms (Y) has a constant value of C ₁₂₈ from the position t _B to t _{33, and} has a constant value of C ₁₂₇ from the position t ₃₃ to the position t _34. Take a value, position
From t _34, a constant value of C ₁₂₆ is taken and a distribution state is formed such that it reaches the position t _T.

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

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

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

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

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

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

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

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

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

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

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

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

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

FIG. 42 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 each layer 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 NH ₃ gas (purity 99.99%)
9%) cylinder and 1016 are CH ₄ gas (purity 99.999%) cylinders.

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

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

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

Next, when the reading of the vacuum gauge 1004 reaches about 5 × 10 ₋₆ Torr, the auxiliary valve 1070 and the outflow valves 1041 to 1046 are closed.

After that, SiH ₄ gas from gas bobbin 1011, gas cylinder 1012
H ₂ gas, gas cylinder 1013 to B ₂ H ₆ / H ₂ gas, gas cylinder 1014 to NO gas, gas cylinder 1015 to NH ₃ gas, gas cylinder 1016 to CH ₄ gas by introducing valves 1051 to 1056 and adjusting the pressure. Gas pressure of 2K
Adjust to g / cm ² .

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

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

After the preparation for film formation is completed as described above, film formation of each of CGL, CTL, and the surface layer is performed on the base cylinder 1007.

To form CGL, the outflow valves 1041 and 1042 and the auxiliary valve 1070 are gradually opened to allow SiH ₄ gas and H ₂ gas to flow into the reaction chamber 1001. At this time, the outflow 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 vacuum gauge 1004 adjusts the pressure inside the reaction chamber to a desired value.
While watching, adjust the opening of the main valve 1002. After that, the power source 1010 is set to a desired power to generate an RF glow discharge in the reaction chamber, and the formation of CGL on the substrate cylinder is started. After the desired film thickness is formed, the RF glow discharge is stopped, and the outflow valves 1041 and 1042 are closed to stop the inflow of gas into the reaction chamber to complete the formation of CGL.

CTLs are formed on CGLs formed as above. CT
To form L, the outflow valves 1041, 1043, 1045 and the auxiliary valve 1070 are gradually opened to allow SiH ₄ gas, B ₂ H ₆ gas, and NH ₃ gas to flow into the reaction chamber 1001. At this time, the outflow valves 1041, 1043, 1045 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ gas flow rate, and the NH ₃ gas flow rate have the desired values, and the pressure in the reaction chamber reaches the desired value. Adjust the opening of the main valve 1002 while watching the vacuum gauge 1004. 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.

A surface layer is formed on the CTL formed as described above. To form the surface layer, the outflow valves 1041 and 1046 and the auxiliary valve 1070 are gradually opened to allow SiH ₄ gas and CH ₄ gas to flow into the reaction chamber 1001. At this time, SiH ₄ gas flow rate,
CH ₄ effluent such that the gas flow rate becomes a desired value the valve 1041,10
46 is adjusted, and the opening of the main valve 1002 is adjusted while observing the vacuum gauge 1004 so that the pressure in the reaction chamber becomes a desired value. After that, the power source 1010 is set to a desired electric power to cause RF glow discharge in the reaction chamber, and the formation of the surface layer on the substrate cylinder is started. After the desired film thickness is formed, the RF glow discharge is stopped, the outflow valves 1041 and 1046 are closed to stop the inflow of gas into the reaction chamber, and the formation of the surface layer is completed.

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

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

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

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

FIG. 43 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 in the figure, the raw material gas for forming each layer of the present invention is sealed, and as an example, for example, in 2011 SiH ₄ gas (purity 99.999%) cylinder, H ₂ gas (purity 99.9% in 2012)
99%) cylinder, 2013 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, 2014 is NO
Gas (purity 99.5%) cylinder, 2015 is NH ₃ gas (purity 99.99%)
9%) cylinder, 2016 is CH ₄ gas (purity 99.999%) cylinder.

As an example of a gas used when forming a light receiving member for electrophotography in the apparatus shown in FIG. 43, SiH is used as a gas for forming CGL.
₄ gas, H ₂ gas, SiH ₄ gas, NH ₃ as CTL forming gas
Gas, B ₂ H ₆ gas, SH ₄ gas, C as surface layer forming gas
Take the case of using H ₄ gas.

A gas cylinder is required to allow these gases to flow into the reaction chamber 2001.
Check that valves 2051 to 2056 of 2011-2016, leak valve 2003 of reaction chamber 2011 are closed, and also inflow valves 2031 to 2036, outflow valves 2041 to 2046, auxiliary valve 20.
Make sure 70 is open, then first open main valve 20
Open 02 to evacuate the reaction chamber 2001 and the gas pipe.

Next, when the reading of the vacuum gauge 2004 becomes about 5 × 10 ⁻⁶ Torr, the auxiliary valve 2070 and the outflow valves 2041 to 2046 are closed.

After that, from gas cylinder 2011 SiH ₄ gas, gas cylinder 2012
H ₂ gas, B ₂ H ₆ / H ₂ gas from gas cylinder 2013, NO gas from gas cylinder 2014, NH ₃ gas from gas cylinder 2015, CH ₄ gas from gas cylinder 2016 by introducing valves 2051 to 2056 and adjusting the pressure Gas pressure of 2K
Adjust to g / cm ² .

Next, the inflow valves 2031 to 2036 are gradually opened to introduce the above gases into the mass flow controllers 2021 to 2026.

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

After the preparation for film formation is completed as described above, film formation of each of CGL, CTL, and the surface layer is performed on the base cylinder 1007.

To form CGL, the outflow valves 2041 and 2042 and the auxiliary valve 2070 are gradually opened to allow SiH ₄ gas and H ₂ gas to flow into the reaction chamber 2001. At this time, the outflow valves 2041 and 2042 are adjusted so that the SiH ₄ gas flow rate and the H ₂ gas flow rate are at desired values, and the vacuum gauge 2004 is set so that the pressure in the reaction chamber is at a desired value.
Adjust the opening of the main valve 2002 while watching. Then, set the microwave power supply 2008 to the desired power and
A μW glow discharge is generated in the reaction chamber through 2009 and the dielectric window 2010 to initiate the formation of CGL on the substrate cylinder. After the desired film thickness is formed, the μW glow discharge is stopped, and the outflow valves 2041 and 2042 are closed to stop the inflow of gas into the reaction chamber to complete the formation of CGL.

CTLs are formed on CGLs formed as above. CT
To form L, the outflow valves 2041, 2043, 2045 and the auxiliary valve 2070 are gradually opened to allow SiH ₄ gas, B ₂ H ₆ gas, and NH ₃ gas to flow into the reaction chamber 2001. At this time, the outflow valves 2041, 2043, 2045 are adjusted so that the SiH ₄ gas flow rate, the B ₂ H ₆ gas flow rate, and the NH ₃ gas flow rate have the desired values, and the pressure in the reaction chamber reaches the desired value. Adjust the opening of main valve 2002 while watching 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 formation of CTL is completed.

A surface layer is formed on the CTL formed as described above. To form the surface layer, the outflow valves 2041 and 2046 and the auxiliary valve 2070 are gradually opened to allow SiH ₄ gas and CH ₄ gas to flow into the reaction chamber 2001. At this time, SiH ₄ gas flow rate, CH ₄
Outflow valves 2041, 2046 so that the gas flow rate is the desired value
Further, the opening of the main valve 2002 is adjusted while observing the vacuum gauge 2004 so that the pressure in the reaction chamber becomes a desired value. After that, the micro power source 2008 is set to a desired power, a μw glow discharge is generated in the reaction chamber through the waveguide 2009 and the dielectric window 2010, and the formation of the surface layer on the substrate cylinder is started. After forming the desired film thickness, μ
w The glow discharge is stopped, the outflow valves 2041 and 2046 are closed to stop the inflow of gas into the reaction chamber, and the formation of the surface layer is completed.

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

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

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

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

FIG. 44 shows an apparatus for manufacturing an electrophotographic light-receiving member by the HRCVD method.

In FIG. 44, 3001 is a film forming chamber, 3002 is an activation chamber (A),
3003 and 3018 are microwave plasma generators, 3004 is a raw material gas introduction pipe for activated species (A), 3005 is an activated species (A) introduction pipe, 3006 is a motor, 3007 is a heater for heating a cylindrical substrate, 3008, Reference numeral 3009 indicates a blowing pipe, 3010 indicates a cylindrical base body, and 3011 indicates a main exhaust valve.
Further, 3012 to 3016 are cylinders for supplying raw material gas,
Reference numeral 17 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 a cylindrical substrate, SiH ₄ , H ₂ is used as a CGL forming gas, and SiH ₄ , SiF ₄ , CH ₄ , H ₂ , B ₂ H ₆ are used as CTL forming gases. Using.

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

In order to form CGL, H ₂ gas is introduced from the cylinder 3012 into the inlet pipe 3004.
To the activation chamber (A) through the microwave plasma generator 3003, and activated hydrogen is introduced into the activation chamber (A).
It was led to the film formation chamber 3001 through the blowing pipe 3008 through 05. On the other hand, SiH ₄ gas was introduced from a cylinder 3013 into an activation chamber (B) 3017 through an introduction pipe 3019, and a microwave plasma generator 3018 was used.
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, internal pressure, and microwave power are set to desired values.

The Al cylindrical substrate 3010 was heated and maintained at a desired temperature by the heater 3007, and the exhaust gas was exhausted by appropriately adjusting the opening of the main exhaust valve 3011. CGL was thus formed. In the same way on the above CGL, from the cylinder 3012 H ₂
Gas, from 3013 SiH ₄ gas, from 3014 B ₂ H ₆ gas, from 3016
Supply CH ₄ gas and SiF ₄ gas from a cylinder (not shown) to CTL
And on the CTL, thereby forming a H ₂ gas, SiH ₄ gas from the gas cylinder 3013, not from the illustration of the cylinder by supplying CH ₄ gas surface layer Wori sequentially formed electrophotographic light-receiving member from a cylinder 3012.

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

FIG. 45 shows an apparatus for manufacturing a photoreceptive member for electrophotography by the FOCVD method.

Gas cylinders 4011, 4012, 4013, 4014, 4015, 4016, 4017 in the figure, the source gas for forming the respective layers of the present invention is sealed, as an example, for example, 4011
SiH ₄ gas (purity 99.999%) cylinder, 4012 H ₂ gas (purity 99.999%) cylinder, 4013 B ₂ H ₆ gas diluted with H ₂ (purity 99.999% or less B ₂ H ₆ / H ₂ (Abbreviated) cylinder, 4014 is NO
Gas (purity 99.5%) cylinder, 4015 is CH ₄ gas (purity 99.99%)
9%) cylinder, 4016 is F ₂ gas (10% He diluted, purity 99.99
%).

SiH ₄ gas, H ₂ gas, F ₂ gas as CTL formation gas
SiH ₄ gas, CH ₄ gas, B ₂ H ₆ gas, F ₂ gas as forming gas, SiH ₄ gas, CH ₄ gas, F ₂ as surface layer forming gas
Take up the case of using gas.

The source gas filled in the 4011-4015 cylinders is 4031-
Each valve of 4035 and the mask low controller of 4053-4057 are introduced to the vacuum chamber of 4020-4001.

F ₂ gas filled in the cylinder of 4016 is the same as above.
Introduce to vacuum chamber 4001 through 4021.

The vacuum chamber 4001 is exhausted by a vacuum exhaust device (not shown) via the main vacuum valve 4002. Reference numeral 4061 denotes a heater for heating the substrate, which heats the substrate cylinder 4060 to an appropriate temperature during film formation, preheats the substrate cylinder 4060 before film formation, or heats the film after film formation to anneal the film. .

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

Also, the base cylinder 4060 is used to form a uniform film.
It is rotating by the rotating mechanism of 4062. In order to introduce 4011-4016 gas into 4001, the chamber inside 4001 has about 5 x 10
^{When -6} Torr is reached, it must be slowly introduced by various valve operations.

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

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

To form CGL, open valves 4046-4050 and gradually open outflow valves 4031 and 4032 and auxiliary valve 4060 to SiH ₄
Gas and H ₂ gas are caused to flow into the reaction chamber 4001. At this time, Si
The outflow valves 4031 and 4032 are adjusted so that the H ₄ gas flow rate and the H ₂ gas flow rate reach desired values, and 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.
Adjust the opening of.

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

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

〔Example〕

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

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

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

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

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

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

The results are shown in Table 8.

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

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

The results are shown in Table 11.

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

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

The results are shown in Table 14.

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

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

The results are shown in Table 17.

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

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

The results are shown in Table 20.

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

<Embodiment 7> Using the manufacturing apparatus shown in FIG.
Photoreceptive members for electrophotography were formed on aluminum cylinders that had been mirror-finished according to the preparation conditions shown in Tables 22, 22, 23, and 24.

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

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 25 shows the comprehensive evaluation results.

As shown in Table 25, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Embodiment 8> Using the manufacturing apparatus shown in FIG.
An electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the conditions shown in the table. The prepared electrophotographic light-receiving member is set in an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and under various conditions, an initial charging ability, The electrophotographic characteristics such as sensitivity, residual potential and ghost were checked, and the deterioration of charging ability, surface scraping and increase of image defects after 2 million sheets of accelerated real machine durability were examined.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 30 shows the comprehensive evaluation results.

As shown in Table 30, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 9> Tables 31 to 34 were prepared by the FOCVD method using the manufacturing apparatus shown in FIG.
An electrophotographic light-receiving member was prepared on an aluminum cylinder that was mirror-finished according to the preparation conditions shown in the table.

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

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 35 shows the comprehensive evaluation results.

As shown in Table 35, good results were obtained for all items. In particular, remarkable superiority was observed in the initial chargeability and durability.

<Example 10> Mirror-processed cylinders were further subjected to lathe processing with a sword bite having various angles to obtain cylinders having various cross-sectional patterns as shown in Table 37 with a cross-sectional shape as shown in FIG. 50. I prepared multiple books. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 42 and subjected to the drum manufacturing under the manufacturing conditions shown in Table 36. Various evaluations were performed on the produced drum with an electrophotographic apparatus using a halogen lamp as a light source and an electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the results shown in Table 38 were obtained.

<Example 11> The surface of the mirror-finished cylinder was exposed to a large number of bearing balls to be dropped, and the surface of the cylinder was subjected to so-called surface dimple forming treatment to produce innumerable dents. A plurality of cylinders having a cross-sectional shape as shown in the figure and various cross-sectional patterns as shown in Table 41 were prepared.
The cylinders are sequentially set in the manufacturing apparatus shown in FIG.
The drum was produced under the production conditions shown in Table 40. The drum thus prepared was 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 42 were obtained.

<Example 12> Using the manufacturing apparatus shown in Fig. 42, a drum was prepared in the same manner as in Example 1 under the preparation conditions shown in Tables 43, 44 and 45, and the same evaluation was performed.

The results are shown in Table 46.

As shown in Table 46, good results were obtained for all items.

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

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

[Brief description of drawings]

FIG. 1 is a schematic layer structure diagram for explaining a layer structure of a light-receiving member for electrophotography of the present invention, and FIGS. 2 to 5 are respectively an uneven shape of a surface of a support and a method for producing the uneven shape. 6 to 21 are schematic diagrams for explaining the above, respectively, and FIGS. 22 to 31 are carbon atoms and / or oxygen atoms or / and 32 is an explanatory view for explaining the distribution state of nitrogen atoms, FIGS. 32 to 41 are explanatory views for explaining the distribution state of carbon atoms or / and oxygen atoms or / and nitrogen atoms constituting the surface layer, respectively. FIG. 42 is an example of a device for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention, which is a schematic explanatory view of a manufacturing device by a glow discharge method using RF, and FIG. 43 is an electron of the present invention. To form the light-receiving layer of the light-receiving member for photography FIG. 44 is a schematic explanatory view of a manufacturing device by a glow discharge method using microwave in an example of the device of FIG. 44, and FIG. 44 is an example of the device for forming the light receiving layer of the light receiving member for electrophotography of the present invention. FIG. 45 is a schematic explanatory view of a manufacturing apparatus by the FOCVD method, FIG. 45 is an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography of the present invention, and FIG. FIG. 47 is a diagram showing flow rate changes during film formation of an impurity gas and a doping gas when the CTL of the electrophotographic light-receiving member of the present invention is formed by using an RF glow discharge, and FIG. 47 is an electrophotographic light of the present invention. FIG. 48 shows changes in the flow rates of the impurity gas and the doping gas during film formation when the CTL of the receiving member is formed by using microwave glow discharge. FIG. 48 shows the CTL of the light receiving member for electrophotography of the present invention by HRCVD.
FIG. 49 is a diagram showing flow rate changes during film formation of an impurity gas and a doping gas when the film is formed by using the method, and FIG. 49 shows the CTL of the electrophotographic light-receiving member of the present invention in 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. 51 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, 52 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. In FIG. 1, 101 ... Support 102 ... CGL 103 ... CTL 104 ... Surface layer 105 ... Free surface About FIGS. 3 and 4, 301, 401 ... Support 302, 402 ... Support surface 303, 403 ... … Rigid spherical sphere 304,404 …… Spherical trace dents About Fig. 5, 500 …… Photoreceptive layer 501 …… Support 502 …… CGL 503 …… CTL 504 …… Surface layer 505 …… Free surface In Fig. 42, 1001 …… Reaction chamber 1002 …… Main exhaust valve 1003 …… Reaction chamber leak valve 1004 …… Vacuum gauge 1007 …… Cylinder substrate 1008 …… Heater for substrate heating 1009 …… Cylinder substrate rotation motor 1010 …… RF power supply 1011〜 1017 …… Raw material gas cylinder 1021 to 1027 …… Mass flow controller 1031 to 1037 …… Gas inflow valve 1041 to 1047 …… Gas outflow valve 1051 to 1057 …… Raw material gas cylinder valve 1061 to 1067 …… Pressure Controller Fig. 43, 2001 ... Reaction chamber 2002 ... May Exhaust valve 2003 …… Reaction chamber leak valve 2004 …… Vacuum gauge 2005 …… Heater for substrate heating 2006 …… Cylindrical substrate 2007 …… Motor for rotating substrate 2008 …… Microwave power supply 2009 …… Waveguide 2010… … Dielectric window 2011 ～ 2017 …… Gas gas cylinder 2021 ～ 2027 …… Mass flow controller 2031 ～ 2037 …… Gas inflow valve 2041 ～ 2047 …… Gas outflow valve 2051 ～ 2057 …… Gas gas cylinder valve 2061 to 1267 ...... Pressure regulator Regarding Fig. 44, 3001 ...... Film formation chamber 3002 ...... Activation chamber (A) 3003, 3018 ...... Microwave plasma generator 3004, 3019 ...... Source gas introduction pipe 3005, 3020 ...... Activated species introduction pipe 3006 ...... Motor 3007 …… Heater for heating the cylinder substrate 3008, 3009 …… Blow-off pipe 3010 …… Cylindrical substrate 3011 …… Main exhaust valve 3012 to 3016 …… Raw material gas cylinder 3017 …… Activation room (B) Figure 45 4001 …… Reaction chamber 4002 …… Main exhaust valve 4011-4017 …… Raw material gas cylinder 4020,4021 …… Raw material gas inlet pipe 4031 -4037 …… Outflow valve 4046 〜 4052 …… Inflow valve 4053 -4059 …… Mass ・Flow controller 4060 …… Cylinder substrate 4061 …… Cylinder substrate heater 4062 …… Cylinder substrate rotation motor.

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

Claims (1)

[Claims] 1. A support, and a photoreceptive layer having a layer structure in which a charge generation layer, a charge transport layer, and a surface layer are laminated on the support in this order from the support side. The surface layer is composed of a silicon atom, at least one of a carbon atom, a nitrogen atom and an oxygen atom, and a non-single crystal material containing at least one of a hydrogen atom and a halogen atom, the charge generation layer and the The charge transport layer is composed of a non-single crystal material containing a silicon atom as a base material and at least one of a hydrogen atom and a halogen atom, and the charge transport layer comprises a carbon atom, a nitrogen atom and an oxygen atom. In addition to containing at least one of the
At least a portion containing atoms belonging to Group III or Group V of the periodic table in a non-uniform distribution state having a concentration increasing or decreasing from the support side in the layer thickness direction, and the charge generation The light-receiving member for electrophotography, wherein the layer thickness of the layer is smaller than that of the charge transport layer.