JPH0785176B2 - Photoreceptive member for electrophotography - Google Patents

Description

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

[Description of conventional technology]

In the field of image formation, as a photoconductive material for forming a light receiving layer in a light receiving member for electrophotography, it has high sensitivity and high SN ratio [photocurrent (Ip) / dark current (Id)], It is required to have characteristics such as absorption spectrum characteristics adapted to the spectrum characteristics, fast photoresponsiveness, a desired dark resistance value, and no pollution to the 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 silicon (hereinafter referred to as A-Si) is one of the photoconductive materials that has recently received attention based on such a point. For example, German Patent Publication Nos. 2746967 and 2855718 disclose electronic materials. The application as a photographic light-receiving member is described.

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

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

When the light-receiving layer is made of an A-Si material, in order to improve its electrical and photoconductive properties, a hydrogen atom or a halogen atom such as a fluorine atom or a chlorine atom, and an electrically conductive type are used. The boron atom, the phosphorus atom, etc. are contained in the photoconductive layer as constituent atoms, respectively, for the purpose of controlling the above, or for improving other characteristics. Depending on how these constituent atoms are contained, In some cases, problems may occur in the electrical or photoconductive characteristics or pressure resistance of the formed layer.

That is, for example, the life of a photo-carrier generated in the formed photoconductive layer by light irradiation in the layer is not sufficient, or commonly referred to as "white blank" in the image transferred to the transfer paper, Image defects that are considered to be caused by a local discharge breakdown phenomenon, and when a blade is used for cleaning, image defects commonly called "white stripes" 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 time, blurring of a so-called image often occurs.

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

[Object of the Invention]

An object of the present invention is to solve various problems in the electrophotographic light receiving member having the conventional light receiving layer composed of A-Si as described above.

That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially always stable with little dependence on the operating environment, excellent light resistance, and deterioration phenomenon even after repeated use. To provide a photoreceptive member for electrophotography having a photoreceptive layer composed of A-Si and polycrystalline silicon, which does not cause deterioration, has excellent durability and 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,
A-, which is dense and stable in terms of structural arrangement and has high layer quality
Another object of the present invention is to provide a photoreceptive member for electrophotography having a photoreceptive layer composed of Si and polycrystalline silicon.

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

Another object of the present invention is to easily obtain a high-quality image with high density, high density, clear halftone, and no image defects or image blurring in long-term use. Another object of the present invention is to provide a light receiving member having a light receiving layer composed of A-Si and polycrystalline silicon for photography.

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

[Structure of Invention]

The light-receiving member for electrophotography of the present invention comprises a support and at least one of a nitrogen atom, an oxygen atom and a carbon atom having a content of 0.0005 to 70 atom% and a hydrogen atom having a content of 0.1 to 70 atom% on the support. An adhesion layer composed of a polycrystalline material containing halogen atoms and silicon atoms as constituent elements, and an amorphous material containing silicon atoms as a matrix and at least one of hydrogen atoms and halogen atoms as constituent elements (hereinafter referred to as “A −
Si (H, X) ”) and has a photoconductive layer exhibiting photoconductivity, and a polycrystalline material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent elements. A surface layer containing 1 × 10 ⁻³ to 70 atomic% and a light-receiving layer having the surface layer.

Further, the surface layer may contain a halogen atom,
Further, the photoconductive layer may contain at least one kind of atom selected from carbon atom, oxygen atom and nitrogen atom.

Further, between the photoconductive layer and the adhesion layer, at least one of an oxygen atom, a nitrogen atom and an atom (a substance that controls conductivity) belonging to Group III or Group V of the periodic table, a hydrogen atom and a halogen atom. A charge injection blocking layer, which is made of an amorphous material or a polycrystalline material containing at least one of the above and silicon atoms as constituent elements and blocks injection of charges from the support, may be provided. As a result, the charging characteristics are improved, and the photoelectric conversion characteristics are better, but the resistance A is relatively high.
It is also possible to use a photoconductive layer composed of −Si (H, X).

Further, it is composed of an amorphous material containing silicon atoms and germanium atoms between the photoconductive layer or the charge injection blocking layer and the support, and is sensitive to long wavelength light, or long wavelength light is effective. A long-wavelength light-sensitive layer (long-wavelength light-absorption layer) that is an amorphous layer that absorbs light may be provided. As a result, particularly when a long-wavelength photosensitive layer is provided between the photoconductive layer and the support, a photoreceptive member for electrophotography having excellent photosensitivity to a semiconductor laser and fast photoresponse can be obtained. .

Hereinafter, in the present invention, the amorphous layer containing silicon atoms and germanium atoms is referred to as a long wavelength light sensitive layer.

Further, at least one of oxygen atoms, nitrogen atoms and a substance for controlling conductivity contained in the charge injection blocking layer and the long wavelength light-sensitive layer and germanium atom contained in the long wavelength light-sensitive layer are If necessary, it may be uniformly distributed in the layer thickness direction, or may be non-uniformly distributed.

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 extremely excellent electrical, optical and photoconductive properties. , Shows pressure resistance and operating environment characteristics.

In particular, it has no influence of residual potential on image formation, its electrical characteristics are stable, and it has high sensitivity and high SN ratio, and it has excellent light resistance, repeated use characteristics, humidity resistance, and pressure resistance. Because it is long, the density is high and the halftone is clear,
In addition, it is possible to stably repeat high-quality images with high resolution.

Hereinafter, the photoconductive member of the present invention will be described in detail with reference to the drawings.

FIGS. 1-1 and 1-2 are schematic configuration diagrams shown for explaining the layer configuration of the electrophotographic light-receiving member of the present invention.

Photoreceptive member for electrophotography shown in FIGS. 1-1 and 1-2.
100 is a support 101 used for a light receiving member, and a light receiving layer 102 is provided on the support 101. The light receiving layer 102 is a nitrogen atom,
A photoconductive layer 103 having photoconductivity, which comprises an adhesion layer made of a polycrystalline material containing at least one of oxygen atoms and carbon atoms and a silicon atom, and A-Si (H, X), a silicon atom, and carbon. It has a layer structure including a surface layer 104 composed of a polycrystalline material having atoms and hydrogen atoms as constituent elements.

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,
Examples include metals such as V, Ti, Pt, and Pb or alloys thereof.

As the electrically insulating support, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, or polyamide, glass, ceramic, paper or the like is usually used. . It is desirable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is provided on the surface side subjected to the conductive treatment.

For example, glass is Ni, Cr, Al, C on the surface.
r, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , Sn
Conductivity is imparted by providing a thin film made of O ₂ , ITO (In ₂ O ₃ + SnO ₂ ) or the like, or NiCr, Al, Ag, Pb, Z if it is a synthetic resin film such as a polyester film.
A thin film of a metal such as n, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt is provided on the surface by vacuum vapor deposition, electron beam vapor deposition, sputtering, etc., or the surface is laminated with the metal. By processing, the surface is made conductive. The shape of the support may be any shape such as a cylindrical shape, a belt shape, a plate shape, and the shape is determined as desired. For example, in the case of continuous high-speed copying, an endless belt shape or a cylindrical shape is used. It is desirable to do. The thickness of the support is appropriately determined so that a desired electrophotographic light-receiving member is formed,
When flexibility is required as the light receiving member for electrophotography, the thickness is made as thin as possible within a range in which the function as a support is sufficiently exhibited. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is usually 10 μm or more.

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

FIG. 3 shows a light receiving member in which a light receiving layer 1500 is provided on a support 1501 having an uneven shape along the inclined surface of the unevenness. In FIG. 3, 1502-1 is an adhesion layer, 1502-2 is a photoconductive layer, and 1503 is a surface layer. At this time, since the degree of inclination at the interface formed between the free surface 1504 and the light receiving layer 1500 is different, the reflection angles of the reflected light at the interfaces formed in the free surface 1504 and the light receiving layer 1500 are different.

Therefore, shearing interference corresponding to a so-called Newton's ring phenomenon occurs, and the interference fringes are dispersed in the depression. As a result, even if microscopic interference fringes appear, the images appearing through such a light receiving member are such that they are not visually recognizable. That is, the use of a support having a surface shape that makes it hard is to use a light-receiving member having a multi-layered light-receiving layer formed thereon, in which light passing through the light-receiving layer has a layer interface and a support. It is possible to effectively prevent the formed image from having a striped pattern due to the reflection on the surface and the interference therebetween.

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 precisely cut to form a desired uneven shape, pitch, and depth. The inverted V-shaped linear protrusions created by the irregularities formed by such a cutting method have a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped projection may be a double or triple multiple spiral structure or a cross spiral structure.

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

The vertical cross-sectional shape of the convex and concave portions provided on the surface of the support is such that the layer thickness is controlled to be nonuniform in the microcolumns of each layer to be formed, and the support and the layer directly provided on the support. In order to ensure good adhesion between the two and the desired electrical contact, they are formed into inverted V shapes, but are preferably substantially an isosceles triangle, a right triangle or an isosceles triangle as shown in FIG. Is desirable. Among these shapes, isosceles triangles and right triangles are preferable.

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

That is, the first is the A-Si (H, X) layer constituting the light receiving layer,
It is structurally sensitive to the state of the layered surface, and the layer quality greatly changes depending on the surface state.

Therefore, it is necessary to set the dimension of the unevenness provided on the surface of the support so as not to deteriorate the layer quality of the A-Si (H, X) layer.

Secondly, if the free surface of the light-receiving layer has extreme irregularities, it becomes impossible to completely perform cleaning after 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, problems in the process of electrophotography, and conditions for preventing interference fringe patterns,
The pitch of the recesses on the surface of the support is preferably 500 μm to 0.3.
μm, more preferably 200 μm to 1 μm, optimally 50 μm
It is preferably m to 5 μm.

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

In addition, the maximum layer thickness difference based on the nonuniformity of the layer thickness of each layer deposited on such a support is preferably 0.1 within the same pitch.
It is desirable that the thickness is from 2 μm to 2 μm, more preferably from 0.1 μm to 1.5 μm, and most preferably from 0.2 μm to 1 μm.

In addition, as another method of eliminating the image defect due to the interference fringe pattern when using coherent light such as laser light, the support surface 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 due to a plurality of spherical trace depressions.

Hereinafter, the shape of the surface of the support in the electrophotographic light-receiving member of the present invention and a preferred production example thereof will be described with reference to FIGS. 4 and 5, and the shape of the support in the light-receiving member of the present invention and The manufacturing method is not limited to this.

FIG. 4 schematically shows a typical example of the shape of the surface of the support in the light-receiving member for electrophotography of the present invention by partially enlarging a part of the uneven shape.

In FIG. 4, 1601 is a support, 1602 is the surface of the support, 1603
Is a rigid spherical body, and 1604 is a spherical dent.

Further, FIG. 4 also shows an example of a preferred manufacturing method for obtaining the surface shape of the support. That is, a rigid spherical body 1603
The spherical depressions by allowing them to naturally fall from a position at a predetermined height above the support surface 1602 and colliding with the support surface 1602.
1604 can be formed. Then, by using a plurality of rigid true spheres 1603 having substantially the same diameter R'and dropping them from the same height h at the same time or at a time,
The support surface 1602 can be formed with a plurality of spherical dent recesses 1604 having approximately the same radius of curvature R and the same width D.

As described above, FIG. 5 shows a typical example of a support having an uneven shape formed by a plurality of spherical trace depressions on the surface. 17
Reference numeral 01 denotes a support, 1702 denotes a convex surface of an uneven portion, 1703 denotes a rigid spherical body, and 1704 denotes a concave surface.

By the way, the radius of curvature R and the width D of the uneven shape due to the spherical dents on the surface of the support of the light receiving member for electrophotography of the present invention.
Is an important cause in order to efficiently achieve the effect of preventing the occurrence of interference fringes in the light receiving member of the present invention. The present inventors have made the following discoveries as a result of various experiments. That is, when the radius of curvature R and the width D satisfy the following equation: D / R ≧ 0.035, there are 0.5 or more Newton rings due to shear ring interference in each of the trace depressions. Furthermore, when the following formula: D / R ≧ 0.055 is satisfied, there will be one or more Newton rings due to shear ring interference in each of the dent depressions.

From these things, to disperse the interference fringes generated in the entire light receiving member in each trace dent, in order to prevent the occurrence of interference fringes in the light receiving member, the D / R is 0.035, preferably 0.055 or more. It is preferable that

In addition, the width D of the unevenness due to the trace depression is at most 500 μm
Degree, preferably less than 200 μm, more preferably 100 μm
The following is preferable.

Adhesion Layer The adhesion layer in the present invention is composed of a polycrystalline material containing at least one of a nitrogen atom, an oxygen atom and a carbon atom, a silicon atom and, if necessary, at least one of a hydrogen atom and a halogen atom. Further, the adhesion layer may contain a substance that controls conductivity as a constituent atom.

That is, the main purpose of the layer is to improve the adhesion between the support and the charge injection blocking layer. In addition, by including a substance that controls conductivity in the layer, it becomes possible to more efficiently transport charges between the support and the charge injection blocking layer.

At least one of a nitrogen atom, an oxygen atom and a carbon atom contained in the layer, and a hydrogen atom contained in the layer if necessary,
At least one of the halogen atoms and the substance that controls the conductivity may be evenly distributed in the layer, or may be distributed in a non-uniform distribution state in the layer thickness direction.

In the present invention, the amount of carbon, oxygen or nitrogen contained in the adhesion layer to be formed must be appropriately determined as desired, but is preferably 0.0005 to 70 atom%, more preferably 0.001 to 50 atom%. Optimally, 0.002 to 30 atomic% is desirable.

The thickness of the adhesive layer is appropriately determined in consideration of adhesiveness, charge transport efficiency, and production efficiency, but is preferably 0.01 to 10 μm, and more preferably 0.02 to 5 μm.

The amount of hydrogen atoms or the amount of halogen atoms or the sum of the amount of hydrogen atoms and halogen atoms contained in the adhesive layer is preferably 0.
1 to 70 atom%, more preferably 0.5 to 50 atom%, optimally
It is desirable to be 1.0 to 30 atom%.

Since the adhesion layer of the present invention is composed of a polycrystalline material, it is structurally dense and stable, and the adhesion with the photoconductive layer or the long-wavelength photosensitive layer formed on the layer is dramatically improved. Was done. As a result, the durability, especially the increase in image defects during the durability, was hardly recognized.

Photoconductive layer In the present invention, in order to effectively achieve the object, the photoconductive layer which is formed on the support and constitutes a part of the light receiving layer has the following semiconductor characteristics, It is composed of A-Si (H, X) that exhibits photoconductivity with respect to the generated light.

p-type A-Si (H, X) ......... including only acceptors. Alternatively, a substance containing both a donor and an acceptor and having a high relative concentration of the acceptor.

A p ^- type A-Si (H, X) type with a low acceptor concentration (Na) or a low relative donor concentration.

n-type A-Si (H, X) ... Includes only donors.
Alternatively, a substance containing both a donor and an acceptor and having a high relative concentration of the donor.

n ^- type A-Si (H, X) ......... with low donor concentration (Nd) or low relative acceptor concentration.

i-type A-Si (H, X) ………… NaNdO or N
aNd's.

In the present invention, the halogen atom (X) contained in the photoconductive layer is preferably F, Cl, Br, I, and particularly preferably F, Cl.

In the present invention, in order to form the adhesion layer, the photoconductive layer and, if necessary, the charge injection blocking layer, a discharge phenomenon such as a glow discharge method, a microwave discharge method, a sputtering method, or an ion plating method is used. It is made by the vacuum deposition method used. For example, in order to form a layer by the glow discharge method, it is basically possible to supply silicon atoms (Si) to Si.
A raw material gas for introducing a hydrogen atom (H) and / or a halogen atom (X) is introduced together with the supply raw material gas into a deposition chamber whose inside can be decompressed to cause a glow discharge in the deposition chamber. Then, a layer made of A-Si (H, X) or polycrystalline silicon may be formed on the surface of a predetermined support which is installed at a predetermined position in advance. Further, in the case of forming by the sputtering method, when the target composed of Si is sputtered in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms (H ) Or / and a gas for introducing a halogen atom (X) may be introduced into the deposition chamber for sputtering.

As the raw material gas for supplying Si used in the present invention, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc. in a gas state or gasifiable silicon hydride (silanes) Can be used effectively, and in particular, the ease of handling layer formation work, Si
SiH ₄ and Si ₂ H ₆ are preferable as they have good supply efficiency.

Effective 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 other gases. Preference is given to halogenated compounds in the state or gasifiable.

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

Halogen compounds that can be preferably used in the present invention are specifically halogen gas of fluorine, chlorine, bromine, iodine, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , IF ₇ , Interhalogen compounds such as ICl and IBr can be mentioned.

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

When forming a characteristic photoconductive member of the present invention by the glow discharge method using a silicon compound containing such a halogen atom, without using a hydrogenated silicon gas as a source gas capable of supplying Si In both cases, a layer made of A-Si: H or polycrystalline silicon containing a halogen atom as a constituent element can be formed on a predetermined support.

When a layer containing halogen atoms is manufactured according to the glow discharge method, basically, a halogen gas, which is a raw material gas for supplying Si, and a gas such as Ar, H ₂ and He, etc., have a predetermined mixing ratio and gas flow rate. It is introduced into the deposition chamber in which the adhesion layer, the photoconductive layer and the charge injection blocking layer are formed as described above, and a glow discharge is generated to form a plasma atmosphere of these gases. Adhesive layer, photoconductive layer and charge injection blocking layer can be formed, but in order to measure the introduction of hydrogen atoms, a predetermined amount of a silicon compound gas containing hydrogen atoms is mixed with these gases to form a layer. You may.

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.

In order to form a layer of A-Si (H, X) or polycrystalline silicon by the reaction sputtering method or the ion plating method, for example, in the case of the sputtering method, a target made of Si is used. In the case of the ion plating method, sputtering is performed in a predetermined gas plasma atmosphere, and in the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a vapor deposition boat as an evaporation source, and the silicon evaporation source is subjected to a resistance heating method or an electron beam method ( It can be performed by heating and evaporating by the EB method, etc. and passing the flying evaporate in a predetermined gas plasma atmosphere.

At this time, in order to introduce a halogen atom into the layer formed by either the sputtering method or the ion plating method, the gas of the halogen compound or the silicon compound containing the halogen atom is introduced into the deposition chamber. What is necessary is just to introduce and form a plasma atmosphere of the gas.

When introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or a gas such as the above-mentioned silanes is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. You can do it.

In the present invention, the halogen compound or the halogen-containing silicon compound described above is used as an effective one as a raw material gas for introducing a halogen atom, but in addition, HF, HCl, HBr, HI, etc. Hydrogen halide, SiH ₂ F ₂ , S
Halogen-substituted silicon hydrides such as iH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr _{3 and the} like, as well as halides having a hydrogen atom as one of the constituent elements in a gas state or capable of being gasified. It can be mentioned as a starting material for forming an effective adhesion layer, photoconductive layer and charge injection blocking layer.

Halides containing these hydrogen atoms, at the same time as the introduction of halogen atoms into the layer during the formation of the layer, hydrogen atoms that are extremely effective in controlling the electrical or photoelectric properties are also introduced,
In the present invention, it is used as a preferable material for introducing halogen.

In order to structurally introduce hydrogen atoms into the layer, in addition to the above,
H _2, or _{SiH 4, Si 2 H 6,} Si 3 H 8, Si 4 the silicon hydride gas H ₁₀ such that to generate discharge coexist in the silicon compound in the deposition chamber for supplying Si But you can do it.

For example, in the case of the reaction sputtering method, a Si target is used, and a gas for introducing a halogen atom and H ₂ gas are introduced into the deposition chamber together with an inert gas such as He and Ar as needed, and a plasma atmosphere is introduced. And then sputtering the Si target to form A-Si (H, X) on the substrate.
Alternatively, a layer made of polycrystalline silicon is formed.

Furthermore, a gas such as B ₂ H ₆ can be introduced while also serving as impurity doping.

In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or hydrogen atoms contained in the adhesion layer, photoconductive layer and charge injection blocking layer of the electrophotographic light-receiving member to be formed. And the total amount of halogen atoms are preferably 1 to 40 atom%,
It is more preferable that the amount is 5 to 30 atomic%.

The amount of hydrogen atoms (H) and / or halogen atoms (X) contained in the layer can be controlled by, for example, the support temperature or /
It is sufficient to control the amount of the starting material used to contain the hydrogen atom (H) or the halogen atom (X) into the deposition apparatus system, the discharge power, and the like.

In the present invention, the dilution gas used when forming the adhesion layer, the photoconductive layer or the charge injection blocking layer by the glow discharge method or the sputtering method is a so-called rare gas such as He, Ne, Ar.
And the like can be mentioned as preferable ones.

In order to make the semiconductor characteristics of the photoconductive layer a desired property among, or in the case of containing a substance that controls conductivity in the adhesion layer or the charge injection blocking layer, when forming the layer, The n-type impurity, the p-type impurity, or both impurities are doped in the layer to be formed while controlling the amount thereof. Examples of such impurities include atoms belonging to Group III of the periodic table as p-type impurities, such as B, Al, Ga, In and Tl.
And the like, and the n-type impurities include
Atoms belonging to Group V of the periodic table, for example, N, P, As, Sb, Bi and the like can be mentioned as preferable ones, but B, Ga, P, Sb and the like are particularly preferable.

In the present invention, the amount of impurities doped into the photoconductive layer to have a desired conductivity type is appropriately determined according to desired electrical and optical characteristics. In the case of impurities, the doping should be done in an amount range of 3 × 10 ^-3 atomic% or less, and in the case of Group V of the periodic table, 5 × 10 ^-3
It suffices to dope in the amount range of atomic% or less.

In the present invention, the content of the group III atom or the group V atom contained in the adhesion layer and the charge injection blocking layer is appropriately determined according to the desire so that the object of the present invention can be effectively achieved. It is preferably 3 × 10 ^{−3 to} 5 atom%, more preferably 5 × 10 ⁻³ to 1 atom%, and most preferably 1 × 10 ^{−2 to} 0.5 atom%.

In order to dope impurities into the adhesion layer, the photoconductive layer and the charge injection blocking layer, a raw material for introducing impurities in a gaseous state during formation of the layer is placed in the deposition chamber in the adhesion layer, the photoconductive layer and the charge injection blocking layer. It may be introduced together with the main raw material forming the. As such a raw material for introducing impurities, it is desirable to employ a material that is gaseous at room temperature and atmospheric pressure or that can be easily gasified under at least the layer forming conditions.

As a starting material for introducing such impurities, specifically, PH
₃ , P ₂ H ₄ , PF ₃ , PF ₅ , PCl ₃ , AsH ₃ , AsF ₃ , AsF ₅ , AsCl ₃ ,
SbH ₃ , SbF ₃ , SbF ₅ , BiH ₃ , BF ₃ , BCl ₃ , BBr ₃ , B ₂ H ₆ , B ₄ H
₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , AlCl ₃ , GaC
l ₃ , InCl ₃ , TlCl _3, etc. can be mentioned.

In order to make the adhesion layer, the photoconductive layer and the charge injection blocking layer contain at least one kind of carbon atom, oxygen atom and nitrogen atom, for example, in the case of forming by the glow discharge method,
A compound containing at least one element selected from carbon atom, oxygen atom and nitrogen atom is introduced into a deposition chamber capable of reducing the pressure inside together with a material gas for forming an adhesion layer, a photoconductive layer and a charge injection blocking layer, Glow discharge may be generated in the deposition chamber to form the adhesion layer, the photoconductive layer and the charge injection blocking layer.

Examples of such a carbon atom-containing compound as a raw material for introducing carbon atoms include saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and acetylene hydrocarbons having 2 to 3 carbon atoms. Etc.

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 .

Examples of the oxygen atom-containing compound as a raw material for introducing oxygen atoms include oxygen (O ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), nitric oxide, and nitrogen dioxide.

Examples of the nitrogen atom-containing compound which is a raw material for introducing nitrogen atoms include nitrogen (N ₂ ), carbon monoxide, carbon dioxide, ammonia and the like.

In addition, for example, when the adhesion layer, the photoconductive layer and the charge injection blocking layer are formed by the sputtering method, the desired mixing ratio is
For example, (Si + Si ₃ N ₄ ), (Si + SiC) or (Si + SiO ₂ )
Use a target for sputter that is mixed and molded with the following components, or use two targets of Si wafer and Si ₃ N ₄ wafer, two of Si wafer and SiC wafer, or two of Si wafer and SiO ₂ wafer. Then, the sputtering is performed, or the gas of the compound containing carbon, the gas of the compound containing nitrogen, or the gas of the compound containing oxygen is introduced into the deposition chamber together with the gas for the sputtering such as Ar gas. Then, the adhesion layer, the photoconductive layer, and the charge injection blocking layer may be formed by performing sputtering using Si or a target.

In the present invention, the amount of carbon, oxygen or nitrogen contained in the photoconductive layer to be formed has a great influence on the characteristics of the electrophotographic light-receiving member to be formed. It must be decided appropriately, but preferably 0.0005 ~
30 atomic%, more preferably 0.001 to 20 atomic%, optimally 0.0
It is desirable that the amount is 02 to 15 atom%.

In the present invention, the content of oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer, or the sum of the two, is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably It is desirable that the content is 0.001 to 50 atom%, more preferably 0.002 to 40 atom%, and most preferably 0.003 to 30 atom%.

In forming the adhesion layer, the photoconductive layer and the charge injection blocking layer, the temperature of the support during formation of the layer is an important factor that influences the structure and characteristics of the formed layer, and in the present invention, It is desirable to strictly control the temperature of the support during the formation of the layers so that the adhesion layer, the photoconductive layer and the charge injection blocking layer having the desired characteristics can be formed as desired.

As the temperature of the support when forming the adhesion layer for effectively achieving the object of the present invention, an optimum range is appropriately selected according to the method of forming the adhesion layer, and the formation of the adhesion layer is performed. However, preferably 200 ℃ ~ 700 ℃, more preferably 250 ℃
It is desirable to set the temperature to ~ 600 ° C.

Further, the support temperature in forming the photoconductive layer 103 and the charge injection blocking layer for effectively achieving the object of the present invention is appropriately set in accordance with the method for forming the photoconductive layer 103 and the charge injection blocking layer. The optimum range is selected to carry out the formation of the photoconductive layer 103 and the charge injection blocking layer, but preferably 50 ° C to 35 ° C.
It is desirable that the temperature is 0 ° C, more preferably 100 ° C to 300 ° C. In forming the adhesion layer, the photoconductive layer 103 and the charge injection blocking layer, it is relatively easy to control the composition ratio of atoms constituting the layer and control the layer thickness, as compared with other methods. It is advantageous to adopt the glow discharge method or the sputtering method, but when the adhesion layer, the photoconductive layer and the charge injection blocking layer are formed by these layer forming methods, the layer temperature is the same as the above-mentioned support temperature. The discharge power and gas pressure during formation are one of the important factors that influence the characteristics of the adhesion layer, photoconductive layer and charge injection blocking layer.

The discharge power condition for the charge injection blocking layer composed of the adhesion layer and the polycrystalline silicon having the characteristics for achieving the object in the present invention to be effectively produced with good productivity is preferably 100 to 500 W. , More preferably 200-2000
W is preferred. The gas pressure in the deposition chamber is preferably 10 ^{−3 to} 0.8 Torr, more preferably 5 × 10 ^{−3 to} 0.5 Torr.

The discharge power condition for the photoconductive layer 103 having the characteristics for achieving the object of the present invention and the charge injection blocking layer composed of amorphous silicon to be effectively produced with good productivity is preferably 10-1000W, more preferably 20-500
W is preferred. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr, and more preferably 0.1 to 0.5 Torr.

In the present invention, the values in the above-mentioned ranges are mentioned as desirable numerical ranges of the support temperature and the discharge power for forming the adhesion layer, the photoconductive layer and the charge injection blocking layer. Is not decided independently, but the optimum value of each layer forming factor is decided based on mutual organic relation so that the adhesion layer photoconductive layer and charge injection blocking layer having desired characteristics are formed. It is desirable to be able to.

The layer thickness of the photoconductive layer is appropriately determined as desired so that the photocarriers generated by irradiation with light having desired spectral characteristics are efficiently transported, and preferably 1 to
It is desirable that the thickness is 100 μ, more preferably 2 to 50 μ.

The layer thickness of the charge injection blocking layer provided as necessary is preferably 0.01 to 10 μ, and more preferably 0.1 to 5 μ.

In the present invention, between the charge injection blocking layer and the adhesion layer, a long-wavelength photosensitive layer containing a silicon atom and a germanium atom and made of an amorphous material sensitive to long-wavelength light is provided. May be.

Further, the long-wavelength photosensitive layer may contain at least one of oxygen atoms, nitrogen atoms and a substance for controlling conductivity in a uniform or non-uniform distribution state in the layer thickness direction.

By providing the layer, the electrophotographic light-receiving member of the present invention has high photosensitivity in the entire visible range, particularly excellent matching with a semiconductor laser, and improved photoresponsiveness.

Further, by containing either one of an oxygen atom and a nitrogen atom in the layer, the adhesion between the layer and the adhesion layer and / or the layer and the charge injection blocking layer and the band gap of the layer can be adjusted. .

Furthermore, by containing a substance that controls conductivity in the layer, it is possible to prevent charge injection from the support or improve the transport efficiency of photoexcited charges.

In order to form a long-wavelength photosensitive layer composed of an amorphous material containing silicon atoms and germanium atoms by the glow discharge method, basically, a silicon source gas for supplying silicon atoms (Si) can be supplied. With the germanium atom (Ge)
A source gas for supplying Ge and a source gas for introducing hydrogen atoms (H) and / or for introducing halogen atoms (X), if necessary, are introduced into a deposition chamber where the inside pressure can be reduced. A glow discharge may be generated in the deposition chamber to form a layer on the surface of a predetermined support which is installed at a predetermined position in advance. Further, when formed by the sputtering method, for example, a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases,
Alternatively, it was diluted with a diluting gas such as He or Ar, if necessary, using two sheets of the target composed of the target and Ge or using a target composed of Si and Ge. As a raw material gas for Ge supply, a gas for introducing hydrogen atoms (H) and / or halogen atoms (X) is introduced into a deposition chamber for spattering, if necessary, to form a plasma atmosphere of the desired gas. Made by

As the raw material gas for supplying Si used in the present invention, silicon hydride (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or capable of being gasified is effective. It is used especially for the ease of handling layer formation work, Si
SiH ₄ and Si ₂ H ₆ are preferable as they have good supply efficiency.

Materials that can be used as the source gas for Ge supply include GeH ₄ , Ge
₂ H ₆ , Ge ₃ H ₅ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , GeH ₁₄ , Ge ₇ H ₁₆ , Ge
Germanium hydride in a gas state or gasifiable such as ₈ H ₁₈ or Ge ₈ H ₂₀ is mentioned as being effectively used. Particularly, it is easy to handle during the layer formation work, and the Ge supply efficiency is good. In this respect, GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ are preferable.

As a raw material gas for introducing a halogen atom used in the present invention, many halogen compounds can be cited, for example, halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Alternatively, a halogen compound that can be gasified is preferable.

When forming a long-wavelength photosensitive layer, a halogen compound or a halogen-containing silicon compound is effectively used as a raw material gas for introducing a halogen atom. In addition, GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂
Cl ₂ , GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂ I
₂ , germanium hydride such as GeH ₃ I, halides such as GeF ₄ , GeCl, which have one hydrogen atom as a constituent element
GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI _{2, and} other germanium halides, and other substances in the gas state or capable of being gasified are also listed as effective starting materials for forming the long-wavelength photosensitive layer. Can be done.

The content of the germanium atom contained in the long-wavelength photosensitive layer in the present invention is appropriately determined as desired so that the object of the present invention can be effectively achieved, but with respect to the sum with the silicon atom, Preferably 1 to 10 × 10 ⁵ atomic pp
m, preferably 100-9.5 x 10 ⁵ atomic ppm, optimally 500
It is desirable that it is set to 8 × 10 ⁵ atomic ppm.

The long-wavelength photosensitive layer is a substance that further controls conductivity,
It may contain at least one of oxygen atom and nitrogen atom.

In the present invention, the content of the substance for controlling the conductive properties contained in the long-wavelength photosensitive layer is preferably 0.01 to
5 × 10 ⁵ atomic ppm, more preferably 0.5 to 1 × 10 ⁴ atomi
c ppm, optimally 1 to 5 × 10 ³ atomic ppm is desirable.

The amount of nitrogen atoms (N) or the amount of oxygen atoms (O) or the sum of the amounts of nitrogen atoms and oxygen atoms (N + O) contained in the long-wavelength photosensitive layer is preferably 0.01 to 40 atom%, more preferably Is preferably 0.05 to 30 atom%, and optimally 0.1 to 25 atom%.

The support temperature for effectively achieving the object of the present invention is appropriately selected from the optimum range, but when forming a long-wavelength photosensitive layer composed of an amorphous material, preferably 50 ° C to 35 ° C.
The temperature is preferably 0 ° C, more preferably 100 ° C to 300 ° C.
In the formation of the long-wavelength photosensitive layer in the present invention, the delicate control of the composition ratio of the atoms constituting the layer and the control of the layer thickness are easy as compared with other methods, so that the glow discharge method or the sputtering method is used. However, when forming a long-wavelength photosensitive layer by these layer forming methods, the long-wavelength at which the discharge power and the gas pressure at the time of forming the layer are created in the same manner as the above-mentioned support temperature. This is an important factor that influences the characteristics of the photosensitive layer.

A long wavelength photosensitive layer having characteristics capable of achieving the object of the present invention,
In producing efficiently with high productivity, discharge power conditions, when forming a long-wavelength photosensitive layer composed of an amorphous material, preferably 10 ~ 1000W, more preferably 2
It is desirable to set it to 0 to 500 W, and the gas pressure in the deposition chamber is preferably 0.01 to 1 Torr, more preferably, when forming a long wavelength photosensitive layer composed of an amorphous material.
It is desirable to set it to about 0.1 to 0.5 Torr.

In the present invention, the support temperature for forming the long wavelength light-sensitive layer, the range described above as a desirable numerical value range of the discharge power is mentioned, these layer forming factors,
It is usually not independently determined separately, but it is desirable to determine the optimum value of each layer forming factor based on mutual and organic relations so as to form a long-wavelength photosensitive layer having desired characteristics. .

In the present invention, the layer thickness of the long wavelength photosensitive layer is preferably
30Å ~ 50μ, more preferably 40Å ~ 40μm, optimally 50
Å ~ 30μm is desirable.

Surface layer The surface layer formed on the photoconductive layer has a free surface, and achieves the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance use environment characteristics, and durability. It is provided for this purpose.

The surface layer is made of a polycrystalline material composed of silicon atoms, carbon atoms and hydrogen atoms.

The surface layer 104 is formed by a glow discharge method, a sputtering method,
Ion implantation method, ion plating method, electron beam method, etc. are used. These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, a load level of capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be produced. From the advantages that it is relatively easy to control the production conditions for producing the electrophotographic light-receiving member having, and that it is possible to easily introduce carbon atoms and hydrogen atoms together with silicon atoms into the surface layer. The glow discharge method or the sputtering method is preferably adopted.

Further, in the present invention, the surface layer may be formed by using the glow discharge method and the sputtering method together in the same apparatus system.

To form the surface layer by the glow discharge method, the raw material gas is mixed with a diluting gas at a predetermined mixing ratio as necessary, and introduced into a deposition chamber for vacuum deposition in which a support is installed, The introduced gas may be turned into gas plasma by causing glow discharge to deposit a surface layer on the photoconductive layer already formed on the support.

In the present invention, as the raw material gas for forming the surface layer, Si,
A gaseous substance having at least one of C and H as a constituent atom or a gasified substance capable of being gasified may be used.

When a source gas containing Si as a constituent atom is used as one of Si, C, and H, for example, a source gas containing Si as a constituent atom, a source gas containing C as a constituent atom, and a constituent atom of H as a constituent atom. Or a raw material gas having Si as a constituent atom and a raw material gas having C and H as a constituent atom are mixed at a desired mixing ratio. Or a raw material gas containing Si as a constituent atom, and Si, C and H.
Can be used as a mixture with a raw material gas having three of the constituent atoms.

Alternatively, a raw material gas containing Si and H as constituent atoms and a raw material gas containing C as constituent atoms may be mixed and used.

In the present invention, SiH ₄ and Si ₂ H containing Si and H as constituent atoms are effectively used as the source gas for forming the surface layer.
₆ , Si ₃ H ₃ , Si ₄ H _{10 and} other silanes, such as silanes, silicon hydride gas, C and H as constituent atoms, for example, carbon number 1 ~
4 saturated hydrocarbon, C2-C4 ethylene hydrocarbon, C2-C3 acetylene hydrocarbon, etc. are mentioned.

Specifically, saturated hydrocarbons include methane (CH ₄ ),
Ethane (C ₂ H _6), propane (C ₃ H _8), n- butane (n-C ₄
H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene-based hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-
1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C
₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene hydrocarbons 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 these raw material gases, H ₂ is of course also used as an effective raw material gas for introducing H.

To form the surface layer 104 by the sputtering method,
Single crystal or polycrystalline Si wafer or C wafer or
A wafer containing a mixture of Si and C as a target may be used as a target and sputtered in various gas atmospheres.

For example, if you use a Si wafer as a target,
The raw material gas for introducing C and H is diluted with a diluting gas, if necessary, and introduced into the deposition chamber for the sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. Good.

Also, separately, Si and C are used as separate targets or Si
By using a single target of mixed C and C, the sputtering is performed in a gas atmosphere containing at least hydrogen atoms.

As the raw material gas for introducing C or H, the raw material gas shown in the example of the glow discharge described above can be used as an effective gas even in the case of sputtering.

In the present invention, as the diluting gas used when forming the surface layer 104 by the glow discharge method or the sputtering method, so-called rare gas, for example, He, Ne, Ar and the like can be mentioned as preferable ones. .

The surface layer in the present invention is carefully formed so that its required properties are provided as desired.

That is, a substance having Si, C and H as constituent atoms structurally takes a form from crystalline to amorphous depending on its preparation condition, and has an electrical property ranging from conductive to semiconducting to insulating. In addition, since each of the properties from the photoconductive property to the non-photoconductive property is exhibited, in the present invention, a surface layer having desired properties according to the purpose is formed as desired so that the surface layer is formed. Strict selection of creation conditions is made.

That is, by forming a surface layer composed of a polycrystalline material containing silicon atoms, carbon atoms and hydrogen atoms as constituent elements, the defect concentration in the surface layer is reduced, and the structure is dense and stable. Therefore, the ability to prevent the injection of electric charges from the free surface is improved, and the residual potential and ghost due to the trap of electric charges due to defects are reduced, and the electrophotographic characteristics are improved. Furthermore, the hardness of the surface layer increases,
Durability has improved dramatically.

When the surface layer is formed on the surface of the photoconductive layer, the temperature of the support during formation of the layer is an important factor that influences the structure and characteristics of the layer formed, and is an object of the present invention. It is desirable that the support temperature during layer formation be strictly controlled so that a surface layer having characteristics can be formed as desired.

In order to effectively achieve the object of the present invention, the support temperature at the time of forming the surface layer is appropriately selected in accordance with the method of forming the surface layer, and the formation of the surface layer is carried out. However, preferably 50 ℃ ~ 350 ℃, more preferably 100 ℃ ~ 300
It is desirable that the temperature is set to ° C. In forming the surface layer, delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy as compared with other methods.
It is advantageous to use the glow discharge method or the sputtering method, but when forming the surface layer by these layer forming methods, the discharge power and the gas pressure at the time of layer formation are created in the same manner as the above-mentioned support temperature. One of the important factors that influence the characteristics of the surface layer
Is one.

The discharge power condition for the surface layer having the characteristics for achieving the object of the present invention to be effectively and effectively produced is preferably 100 to 5000 W, and preferably 200 to 2 W.
000W is desirable. The gas pressure in the deposition chamber is preferably 1 × 10 ^{−3 to} 0.8, preferably 5 × 10 ^{−3 to} 0.5 Torr.

In the present invention, the support temperature for forming the surface layer,
Although the values in the above-mentioned range are mentioned as the desirable numerical value range of the discharge power, these layer forming factors are not independently determined and a surface layer made of a polycrystalline material having desired characteristics is formed. Thus, it is desirable that the final value of each layer forming factor be determined based on the mutual organic relationship.

The amount of carbon atoms and hydrogen atoms contained in the surface layer of the electrophotographic light-receiving member of the present invention is the same as the conditions for producing the surface layer, so that the surface layer is formed with desired properties for achieving the object of the present invention. Is an important factor.

The amount of carbon atoms contained in the surface layer in the present invention is preferably 1 × 10 ^{−3 with} respect to the total amount of silicon atoms and carbon atoms.
It is desirable that the content be ˜90 atom%, and more preferably 10-80 atom%. The content of hydrogen atoms is preferably 1 × 10 ⁻³ to 70 atom%, more preferably 1 × 10 ^{−2 to} 60 atom% with respect to the total amount of constituent atoms,
The light-receiving member formed when the hydrogen content is in these ranges can be sufficiently applied as a remarkably excellent one which has not been heretofore in actual use.

That is, defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer composed of a polycrystalline material containing silicon atoms, hydrogen atoms and carbon atoms have a characteristic as a photoreceptive member for electrophotography. It is known to have an adverse effect, for example, deterioration of charging characteristics due to injection of electric charges from a free surface, fluctuation of charging characteristics due to change of surface structure under use environment, for example, high humidity, and further during corona charging or light exposure. Charge retention is injected into the surface layer from the photoconductive layer at the time of irradiation and trapped by defects in the surface layer, which may be an afterimage phenomenon upon repeated use.

However, by using a polycrystalline material containing silicon atoms, carbon atoms, and hydrogen atoms for the surface layer, the defects in the surface layer are significantly reduced, and as a result, all of the above problems are eliminated, and in particular In comparison, it is possible to make dramatic improvements in electrical characteristics and high-speed continuous usability.

The hydrogen content in the surface layer depends on the flow rate of H ₂ gas, the support temperature,
It can be controlled by discharge power, gas pressure and the like.

Further, a halogen atom may be contained in the surface layer. As a method of containing a halogen atom in the surface layer,
For example, if the source gas is SiF ₄ , SiFH ₃ , Si ₂ F ₆ , SiF ₃ SiH ₃ , SiCl
Mixing a halogenated silicon gas such as ₄ or
It may be formed by mixing a halogenated carbon gas such as CF ₄ , CCl ₄ , or CH ₃ CF ₃ with the glow discharge decomposition method or the sputtering method.

The numerical range of the layer thickness in the present invention is one of the important factors for effectively achieving the object of the present invention.

The numerical range of the layer thickness of the surface layer in the present invention is appropriately determined according to the intended purpose in order to effectively achieve the object of the present invention.

Also, the layer thickness of the surface layer, in relation to the layer thickness of the photoconductive layer, must be appropriately determined as desired under the organic relationship according to the characteristics required for each layer region. There is. In addition, it is desirable to consider in terms of economical efficiency in consideration of productivity and mass productivity.

The thickness of the surface layer in the present invention is preferably 0.003
~ 30μ, more preferably 0.004-20μ, optimally 0.005-10
It is desirable that it be μ.

The layer thickness of the light-receiving layer of the light-receiving member for electrophotography according to the present invention is appropriately determined according to the purpose according to the purpose.

In the present invention, as the layer thickness of the light receiving layer, the characteristics imparted to the photoconductive layer and the surface layer constituting the light receiving layer are effectively utilized, respectively, and the object of the present invention is effectively achieved. The layer thickness of the photoconductive layer and the surface layer is appropriately determined according to the desire, and preferably the layer thickness of the photoconductive layer is several hundred to several thousand times the layer thickness of the surface layer. The above is preferable.

The specific value is preferably 3 to 100 μ, more preferably 5 to 70 μ, and most preferably 5 to 50 μ.

Next, a method for manufacturing a photoconductive member formed by the glow discharge decomposition method will be described.

FIG. 6 shows an apparatus for manufacturing a light receiving member for electrophotography by the glow discharge decomposition method.

In the gas cylinders 1102, 1103, 1104, 1105, 1106 in the figure, the raw material gas for forming each layer of the present invention is sealed. For example, 1102 is SiH ₄ gas (purity
99.999%) cylinder, 1103 is B ₂ H ₆ gas diluted with H ₂ (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 1104 is Si
₂ H ₆ gas (purity 99.99%) cylinder, 1105 is H ₂ gas (purity 99.99%)
9.999%) cylinder, 1106 is a CH ₄ gas cylinder.

A gas cylinder is required to allow these gases to flow into the reaction chamber 1101.
Check that valves 1122 to 1126 and leak valve 1135 of 1102 to 1106 are closed, and check that the inflow valves 1112 to 111
6. After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 to 1133 are opened, the main valve 1134 is first opened to exhaust the reaction chamber 1101 and the gas pipe. Next vacuum gauge 1136
When the reading of about 5 × 10 ^-6 Torr is reached, the auxiliary valve 11
32 to 1133 and the outflow valves 1117 to 1112 are closed.

As an example of forming the light receiving layer on the base cylinder 1137, SiH ₄ gas from the gas cylinder 1102, gas cylinder
B ₂ H ₆ / H ₂ gas from 1103, to adjust the pressure of the outlet pressure gauge 1127,1128 to 1 kg / cm ² by opening the valve 1122, 1123, inlet valve
Gradually open 1112, 1113, mass flow controller 1107,
Inflow into 1108. Then the outflow valve 1117, 1118,
Auxiliary valve 1132 is gradually opened to let each gas flow into reaction chamber 1101.
Flow into. At this time, the outflow valves 1117 and 1118 are adjusted so that the ratio of the SiH ₄ gas flow rate and the B ₂ H ₆ / H ₂ gas flow rate becomes a desired value.
Is adjusted, or the opening of the main valve 1134 is adjusted while observing the reading of the vacuum gauge 1136 so that the pressure in the reaction chamber becomes a desired value. Then, after confirming that the temperature of the basic cylinder 1137 is set to a temperature of 50 to 350 ° C. by the heater 1138, the power source 1140 is set to a desired electric power and a glow discharge is generated in the reaction chamber 1101 to cause a basic discharge. Form the photoconductive layer on the cylinder.

When a halogen atom is contained in the photoconductive layer, for example, SiF ₄ gas is further added to the above gas and sent into the reaction chamber 1101.

When forming each layer, the layer formation rate can be further increased depending on the selection of gas species. For example, instead of SiH ₄ gas, Si
_If a layer is formed using ₂ H ₆ gas, it can be increased several times and productivity is improved.

To form a surface layer on the photoconductive layer formed as described above, the same valve operation as in the formation of the photoconductive layer is performed, for example, SiH ₄ gas, CH ₄ gas, and optionally H Diluted gas such as _{2 is} caused to flow into the reaction chamber 1101 at a desired flow rate ratio to cause glow discharge according to desired conditions.

The amount of carbon atoms contained in the surface layer can be controlled as desired, for example, by arbitrarily changing the flow rate ratio of SiH ₄ gas and CH ₄ gas introduced into the reaction chamber 1101 as desired. I can.

The amount of hydrogen atoms contained in the surface layer can be controlled as desired by, for example, arbitrarily changing the flow rate of the H ₂ gas introduced into the reaction chamber 1101 as desired.

It goes without saying that all of the outflow valves other than the gas required for forming each layer are closed, and when forming each layer, the gas used for forming the previous layer flows out into the reaction chamber 1101. In order to avoid remaining in the piping from the valves 1117 to 1121 to the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valve 1132 is opened, the main valve 1134 is fully opened, and the system is temporarily evacuated to a high vacuum. Perform the operation as required.

Further, during the layer formation, in order to make the layer formation uniform, the base cylinder 1137 is rotated at a constant speed by the motor 1139.

Example 1 Using the manufacturing apparatus shown in FIG. 6, an electrophotographic light-receiving member was formed on an aluminum cylinder that was mirror-finished according to the manufacturing conditions shown in Table 1. Further, by using the same apparatus as that shown in FIG. 6, a cylinder having the same specifications, on which only the surface layer was formed and a case where only the adhesion layer was formed, were separately prepared as analysis samples. The light receiving member (hereinafter referred to as a drum) is set in an electrophotographic apparatus, and under various conditions,
We checked the electrophotographic characteristics such as the initial chargeability, residual potential, and ghost, and examined the decrease of chargeability, deterioration of sensitivity, and increase of image defects after the endurance of 1.5 million sheets. Furthermore, the image deletion of the drum in a high temperature and high humidity atmosphere of 35 ° C and 85% was also evaluated. Then, the drums that had been evaluated were cut out at portions corresponding to the upper, middle, and lower portions of the image portion, and subjected to quantitative analysis of hydrogen contained in the surface layer using SIMS. For samples with only the surface layer and adhesion layer, cut out the upper, middle, and lower parts of the sample in the generatrix direction, and use an X-ray diffractometer to measure Si (111) near a diffraction angle of 27 °. The diffraction pattern was calculated and the presence or absence of crystallinity was examined. Table 2 shows the above evaluation results, the hydrogen content in the surface layer, and the presence / absence of crystallinity in the surface layer and the adhesion layer. As can be seen in Table 2, initial chargeability, image deletion, residual potential, ghost,
A remarkable superiority was recognized for each item of image defects and increase of image defects.

<Comparative Example 1> A drum and a sample were prepared by the same apparatus and method as in Example 1 except that the manufacturing conditions were changed as shown in Table 3, and the same evaluation and analysis were performed. The results are shown in Table 4.

As shown in Table 4, it was confirmed that various items were inferior to those of Example 1.

Example 2 Using the manufacturing apparatus shown in FIG. 6, an electrophotographic light-receiving member was formed on an aluminum cylinder that was mirror-finished according to the manufacturing conditions shown in Table 5. Further, using a device of the same type as in FIG. 6, a cylinder having the same specifications and having only a surface layer formed thereon and a layer having only an adhesion layer formed thereon were separately prepared as analysis samples. Light receiving member (hereinafter referred to as drum)
Those who checked the electrophotographic characteristics such as initial charging ability, residual potential, ghost, etc. under various conditions after set in the electrophotographic device, and also reduced charging ability after the endurance of 1.5 million actual machines,
We investigated the deterioration of sensitivity and the increase of image defects. Furthermore, 35 ℃, 85%
The image deletion of the drum in the high temperature and high humidity atmosphere was also evaluated. Then, for the drum that has been evaluated, the portions corresponding to the upper, middle, and lower portions of the image portion are cut out and subjected to quantitative analysis of hydrogen contained in the surface layer by using SIMS. The component profiles of boron (B) and oxygen (O) in the layer thickness direction were examined. On the other hand, for the sample with only the surface layer and the adhesion layer, after cutting out the parts corresponding to the upper, middle, and lower directions of the generatrix of the sample, use an X-ray diffractometer to measure Si (111) near the diffraction angle of 27 °. The corresponding diffraction pattern was determined and examined for crystallinity. Table 6 shows the above evaluation results, the hydrogen content in the surface layer, and the presence or absence of crystallinity in the surface layer and the adhesion layer. FIG. 9 shows the component profile of the element in the charge injection blocking layer. As can be seen from Table 6, a remarkable superiority was observed particularly in the items of initial chargeability, residual potential, ghost, image deletion, image defects, and increase in image defects.

<Example 3 (Comparative Example 2)> A plurality of drums and surface layers were formed under the same conditions as in Example 1 except that the preparation conditions of the surface layer were changed to several conditions shown in Table 7. A sample for analysis was prepared. These drums and samples were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 8 were obtained.

<Example 4> The production conditions of the photoconductive layer were changed to several conditions shown in Table 9,
Other than that, a plurality of drums were prepared under the same conditions as in Example 1. As a result of subjecting these drums to the same evaluation as in Example 1, the results shown in Table 10 were obtained.

Example 5 The conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 11, and only the plurality of drums and the charge injection blocking layer were formed under the same conditions as in Example 1 except for the above. A sample was prepared. These drums and the sample for analysis were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 12 were obtained.

Example 6 A plurality of drums and a charge injection blocking layer were formed under the same conditions as in Example 1 except that the conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 13. A sample was prepared. The drum and the analysis sample were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 14 were obtained.

<Example 7> The conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 15, and only the plurality of drums and the charge injection blocking layer were formed under the same conditions as in Example 1 except for the above. A sample was prepared. The drum and the analysis sample were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 16 were obtained.

<Example 8> The conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 17, and only the plurality of drums and the charge injection blocking layer were formed under the same conditions as in Example 1 except for the above. A sample was prepared. These drums and the sample for analysis were subjected to the same evaluation and analysis as in Example 1, and the results shown in Table 18 were obtained.

Example 9 A plurality of drums were prepared under the same conditions as in Example 1 except that the conditions for producing the long-wavelength photosensitive layer were changed to several conditions shown in Table 19. These drums were subjected to the same evaluations as in Example 1, and the results shown in Table 20 were obtained.

Example 10 A plurality of drums were prepared under the same conditions as in Example 1 except that the conditions for producing the long-wavelength photosensitive layer were changed to several conditions shown in Table 21. The drums were subjected to the same evaluations as in Example 1, and the results shown in Table 22 were obtained. And
From the No. 1002 drum that has been evaluated, cut out the parts corresponding to the top, middle, and bottom of the image part, and use SIMS to analyze the germanium (Ge) component profile in the layer thickness direction of the long-wavelength photosensitive layer. Examined. The results are shown in Fig. 10.

<Example 11> An adhesion layer was formed on a basic cylinder under several production conditions shown in Table 23, and a light-receiving member was further formed thereon under the same production conditions as in Example 1. Formed. Separately from this, a sample in which only the adhesion layer was formed was prepared. The light receiving member was subjected to the same evaluation as in Example 1, and a part of the sample was cut out and a diffraction pattern corresponding to Si (111) near a diffraction angle of 27 ° was obtained with an X-ray diffractometer. The presence or absence of crystallinity was investigated. The above results are shown in Table 24.

<Example 12> A mirror-finished cylinder is further subjected to lathe machining with a sword bite having various angles, and a plurality of cylinders each having a cross-sectional shape as shown in Fig. 7 and various cross-sectional patterns as shown in Table 25 are provided. I prepared a book. The cylinder was sequentially set in the manufacturing apparatus shown in FIG. 6 and subjected to the drum manufacturing under the same manufacturing conditions as in Example 1. The drum thus prepared was subjected to various evaluations with 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 26 were obtained.

<Example 13> The surface of a cylinder that has been mirror-finished is subjected to a so-called surface dimple forming process in which the cylinder surface is exposed to the dropping base of a large number of bearing balls to produce innumerable dents. A plurality of cylinders having a cross-sectional shape like this and various cross-sectional patterns as shown in Table 27 were prepared. The cylinder was sequentially set in the manufacturing apparatus shown in FIG. 6 and subjected to the drum manufacturing under the same manufacturing conditions as in Example 1. Various evaluations were performed on the produced drum with 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 28 were obtained.

<Comparative Example 3> A drum and a sample were produced by the same apparatus and method as in Example 1 except that the production conditions were changed as shown in Table 29, and subjected to the same evaluation and analysis. The results are shown in Table 30.

As seen in Table 30, it was recognized that various items were inferior to those of Example 1.

[Summary of Effects of the Invention] The light-receiving member of the present invention has the same layer structure as that of the above-described specific layer structure of the light-receiving member for electrophotography having a photoconductive layer composed of A-Si (H, X). By doing so, it is possible to solve all the problems in the conventional photoreceptive member for electrophotography composed of A-Si, and in particular, extremely excellent moisture resistance, continuous repeated use characteristics, electrical pressure resistance, and use environment characteristics. And durability and the like. In addition, there is no effect of residual potential, and its electrical characteristics are stable, and the image obtained by using it has high density and clear halftone, and is very excellent. .

Particularly, in the electrophotographic light-receiving member of the present invention, that is, by forming a surface layer composed of a polycrystalline material, which contains silicon atoms, carbon atoms and hydrogen atoms as constituent elements, the defect concentration in the surface layer And the structure is dense and stable, which improves the ability to prevent the injection of charges from the free surface, and also reduces the residual potential and ghost caused by the trap of charges due to defects. Has improved. Furthermore, the hardness of the surface layer has increased, and the durability has dramatically improved.

Further, particularly in the electrophotographic light-receiving member of the present invention, by providing an adhesion layer composed of a polycrystalline material, the layer is structurally dense and stable, and thus the light formed on the layer is formed. The adhesiveness with the conductive layer or the long-wavelength photosensitive layer was dramatically improved. As a result, durability is improved,
In particular, almost no increase in image defects was observed during durability.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic layer structure diagram for explaining a layer structure of a light-receiving member for electrophotography of the present invention, and FIGS. 2 to 5 are uneven shapes on a surface of a support and FIG. 6 is a schematic diagram for explaining a method for producing a concavo-convex shape, and FIG. 6 is an example of a device for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention. It is a figure. 7 and 8
Each of the drawings is an explanatory view showing a sectional shape of one embodiment of the present invention. 9 and 10 are explanatory views for explaining the distribution state of each molecule contained in the layer. About FIGS. 1-1 and 1-2, 100 ... Electrophotographic light-receiving member, 101 ... Support, 102 ...
… Photoreceptive layer, 103 …… Photoconductive layer, 104 …… Surface layer, 105…
… Free surface, 106 …… Adhesion layer, 107 …… Charge injection blocking layer. Regarding Fig. 3, 1500 ... Photoreceptive layer, 1501 ... Support, 1502 ... Photoconductive layer, 1503 ... Surface layer, 1504 ... Free surface. 4 and 5 1601,1701 …… Support, 1602, 1702 …… Support surface, 160
3,1703 …… Rigid sphere, 1604,1704 …… Spherical dent. About Fig. 6 1101 …… Reaction chamber, 1102-1106 …… Gas cylinder, 1107-11
11 …… mass flow controller, 1112 ～ 1116 …… inflow valve, 1117 ～ 1121 …… outflow valve, 1122 ～ 1126 …… valve, 1127 ～ 1131 …… pressure regulator, 1132,1133 …… auxiliary valve, 1134 …… Main valve, 1135 ... Leak valve,
1136 ... vacuum gauge, 1137 ... basic cylinder, 1138 ... heating heater, 1139 ... motor, 1140 ... high frequency power supply.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minor Kato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasushi Fujioka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Co., Ltd. (56) References JP-A-59-119360 (JP, A)

Claims (5)

[Claims] 1. A support, and at least one of a nitrogen atom, an oxygen atom and a carbon atom having a content of 0.0005 to 70 atomic% and a hydrogen atom or a halogen atom and a silicon atom having a content of 0.1 to 70 atomic% on the support. An adhesion layer composed of a polycrystalline material containing a constituent element, and a photoconductive material composed of an amorphous material containing silicon atoms as a base material and at least one of a hydrogen atom and a halogen atom as a constituent element. It has a conductive layer and a polycrystalline material containing silicon atoms, carbon atoms and hydrogen atoms as constituent elements, and the hydrogen atoms are 1 × 10 ^−3.
A light-receiving member for electrophotography, comprising: a surface layer containing 70 to 70 atomic% of the light-receiving layer. 2. The electrophotographic light-receiving member according to claim 1, wherein the surface layer contains a halogen atom. 3. The photoreceptive member for electrophotography according to claim 1, wherein the photoconductive layer contains at least one kind of carbon atom, oxygen atom and nitrogen atom. 4. A silicon atom and at least one of a carbon atom, an oxygen atom, a nitrogen atom and an atom belonging to Group III or Group V of the periodic table between the photoconductive layer and the support. 4. The photoreceptive member for electrophotography according to claim 1, further comprising a charge injection blocking layer composed of an amorphous material or a polycrystalline material containing as. 5. A silicon atom and a germanium atom are contained between the photoconductive layer or the charge injection blocking layer and a support,
Claim 1 having a long-wavelength photosensitive layer made of an amorphous material sensitive to long-wavelength light.
The light receiving member for electrophotography according to any one of items 1 to 4.