JPH0713747B2 - 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 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 silicon (hereinafter referred to as A-Si) is one of the photoconductive materials that has recently been attracting attention based on such a point. For example, German publications 2746967 and 2855718 disclose electrophotography. The application as a light receiving member for use is described.

However, the conventional photoreceptive member for electrophotography having a photoreceptive layer composed of A-Si has electrical, optical and photoconductive properties such as dark resistance value, photosensitivity and photoresponsiveness, and operating environment properties. In terms of the above, and further in terms of stability over time and durability, 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 photoconductive layer formed by photoconductive irradiation has a poor life in the photoconductive layer, or is commonly referred to as "white blank" in the image transferred to the transfer paper. , Image defects that are thought to be due to local discharge breakdown phenomenon, and when using a blade for cleaning,
Image defects commonly referred to as "white streaks" were thought to have been caused by the rubbing. 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 layer 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 electrophotographic light-receiving member of the present invention, a support, and a long-wavelength photosensitive layer having a sensitivity to long-wavelength light, which is composed of a polycrystalline material containing a silicon atom and a germanium atom, on the support, A charge injection blocking layer composed of an amorphous material containing a silicon atom as a base and an atom (a substance that controls conductivity) belonging to Group III or V of the periodic table, and a base of silicon atom, A photoconductive layer made of an amorphous material containing at least one of a hydrogen atom and a halogen atom as a constituent element (hereinafter abbreviated as “A-Si (H, X)”) and exhibiting photoconductivity, and silicon. A surface layer composed of an amorphous material containing atoms, carbon atoms and hydrogen atoms as constituent elements; and a light-receiving layer having a surface layer containing 41 to 70 atomic% of hydrogen atoms. It is characterized by

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

The charge injection blocking layer that blocks the injection of charges from the support contains a substance that controls the conductivity as constituent atoms in a distributed state in which the charge injection blocking layer is uniformly distributed in the layer thickness direction or largely distributed on the support side.

Furthermore, the charge injection blocking layer may contain oxygen atoms and / or nitrogen atoms as constituent atoms in a distribution state in which the charge injection blocking layer is evenly distributed in the layer thickness direction or is largely distributed on the support side. Oxygen atoms and / or nitrogen atoms in the charge injection blocking layer may be unevenly distributed on the support side.

Furthermore, a long-wavelength light-sensitive layer (long-wavelength light-absorbing layer), which is a polycrystalline layer having sensitivity to long-wavelength light or effectively absorbing long-wavelength light, is used, especially between the photoconductive layer and the support. In the case of being provided in the above, it is possible to obtain an electrophotographic light-receiving member having excellent photosensitivity to a semiconductor laser and having a fast photoresponse.

Hereinafter, in the present invention, the polycrystalline layer containing silicon atoms and germanium atoms is referred to as a long wavelength photosensitive layer. The long-wavelength light-sensitive layer is made of Group III or V of the periodic table.
At least one of an atom belonging to the group, an oxygen atom and a nitrogen atom may be contained.

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.

That is, when applied as a photoreceptive member for electrophotography, it has no influence of residual potential on image formation, has stable electrical characteristics, high sensitivity, and high SN ratio. It has excellent light fatigue resistance, repeated use characteristics, high density, clear halftone, and high resolution and high quality images can be stably and repeatedly obtained.

Furthermore, the electrophotographic light-receiving member of the present invention has a high photosensitivity in the entire visible light region, in particular, is excellent in matching with a semiconductor laser and has a fast photoresponse.

The electrophotographic light-receiving member of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a schematic configuration diagram schematically shown for explaining the light receiving member for electrophotography of the present invention.

In the electrophotographic light-receiving member shown in FIG. 1, a light-receiving layer 100 is provided on a support 101 for the light-receiving member, and the light-receiving layer 100 contains a silicon atom and a germanium atom. Long-wavelength photosensitive layer 10 composed of polycrystalline material
6, a charge injection blocking layer 102, A—Si (H, X), and a photoconductive photoconductive layer 103, and an amorphous material having silicon atoms, carbon atoms, and hydrogen atoms as constituent elements. And a surface layer containing 41 to 70 atomic% of the hydrogen atom.
The surface layer 104 has a free surface 105.

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,
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 evaporation, electron beam evaporation, spattering, 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.
In the case of continuous high speed copying, it is desirable to use an endless belt or a cylinder. The thickness of the support is appropriately determined so that a desired electrophotographic light-receiving member is formed. When flexibility is required as the electrophotographic light-receiving member,
It is made as thin as possible within the range where 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. 21 shows a light receiving member provided with a light receiving layer 1500 on a support 1501 having an uneven shape along the total slope of the unevenness. At this time, since the degrees of inclination at the interfaces formed in the free surface 1504 and the light receiving layer 1500 are 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.

In FIG. 21, 1505 is a long-wavelength photosensitive layer, 1502-1 is a charge injection blocking layer, 1502-2 is a photoconductive layer, and 1503 is a surface layer.

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 parallel 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 in an inverted V shape, but preferably they are substantially an isosceles triangle, a right triangle or an isosceles triangle as shown in FIG. Is desirable. Among these shapes, an isosceles triangle and a right triangle 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 studying the above-mentioned problems in layer deposition, problems in the process of electrophotography, and conditions for preventing interference fringe patterns, the pitch of recesses on the surface of the support is preferably 500 μm to 0.3 μm.
m, more preferably 200 μm to 1 μm, optimally 50 μm to 5
It is preferably μm.

The maximum depth of the recess is preferably 0.1 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm, optimally 0.6 μm to 2
It is desirable to be set to μm. When the pitch and the 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 pressure of each layer deposited on such a support is preferably 0 within the same pitch.
The thickness is preferably 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 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. 22 and 23, 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. 22 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. 22, 1601 is a support, 1602 is a support surface, 1603
Is a rigid spherical body, and 1604 is a spherical dent.

Further, FIG. 22 also shows an example of a preferred manufacturing method for obtaining the surface shape of the support. That is, 16
It is shown that the spherical depression 1604 can be formed by allowing 03 to spontaneously drop from a position at a predetermined height above the support surface 1602 and colliding with the support surface 1602. 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 has substantially the same curve radius R and the same width. A plurality of spherical trace dimples 1604 having D can be formed.

As described above, FIG. 23 shows a typical example of a support having an uneven shape formed by a plurality of spherical trace depressions on the surface. 23rd
In the figure, 1701 is the support, 1702 is the position of the convex portion, 1703
Is a rigid spherical body, and 1704 is the bottom position of the recess.

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 factor for efficiently achieving 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, the radius of curvature R and the width D are as follows: If the above condition is satisfied, there will be 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 interference fringes from occurring in the light receiving member by dispersing the interference fringes generated in the entire light receiving member in the respective trace depressions, Is 0.035, preferably 0.055 or more.

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.

Long-wavelength light-sensitive layer The long-wavelength light-sensitive layer in the present invention is composed of a polycrystalline material containing silicon atoms and germanium atoms, and the germanium atoms contained in the layer are evenly distributed in the layer. Alternatively, or even if it is contained evenly in the layer thickness direction, the distribution concentration may be non-uniform. However, in any case, in the in-plane direction parallel to the surface of the support, the content may be evenly distributed.
It is also necessary from the viewpoint of uniforming the characteristics in the in-plane direction. That is, the long wavelength light-sensitive layer is uniformly distributed in the layer thickness direction, and the side opposite to the side where the support is provided (the free surface side of the light-receiving layer) is described above. It is contained in the long-wavelength light-sensitive layer so that it is distributed more on the support side or in the opposite distribution.

In the light-receiving member of the present invention, as described above, the distribution state of the germanium atoms contained in the long-wavelength photosensitive layer is:
In the layer thickness direction, it is desirable to take the above-mentioned distribution state and to make a uniform distribution state in the in-plane direction parallel to the surface of the support.

Further, in one of the preferred embodiments, the distribution state of germanium atoms in the long-wavelength photosensitive layer is such that germanium atoms are continuously and evenly distributed in the whole layer region, and the germanium atom layer thickness is Since the distribution concentration C in the direction is changed from the support side toward the charge injection blocking layer, the affinity between the long wavelength light-sensitive layer and the charge injection blocking layer is excellent, and will be described later. As described above, by making the distribution concentration C of germanium atoms extremely large at the end portion on the side of the support, long-wavelength light, which is hardly absorbed by the photoconductive layer when a semiconductor laser or the like is used, can be obtained. The light-sensitive layer can absorb light substantially completely and can prevent interference due to reflection from the support surface.

2 to 7 show typical examples in which the distribution state of germanium contained in the long-wavelength photosensitive layer of the light-receiving member in the present invention is uneven in the layer thickness direction.

2 to 7, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the layer thickness of the long-wavelength photosensitive layer.
t _B represents the position of the end surface of the long wavelength photosensitive layer on the support side, and t _T represents the position of the end surface of the long wavelength photosensitive layer on the side opposite to the support side. That is, the long wavelength photosensitive layer containing germanium atoms is formed from the t _B side toward the t _T side.

FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the long-wavelength photosensitive layer in the layer thickness direction.

In the example shown in FIG. 2, from the interface position t _B where the surface on which the long-wavelength photosensitive layer containing germanium atoms is formed and the surface of the long-wavelength photosensitive layer contact to the position t _{1 to} germanium, distribution concentration C of the atoms contained in the long-wavelength light sensitive layer notwithstanding et germanium atoms taking a constant value C ₁ becomes is formed, gradually continuous than the concentration C ₂ is from the position t ₁ up to the interface position t _T Has been reduced. At the interface position t _T , the distribution concentration C of germanium atoms is C ₃ .

In the example shown in FIG. 3, the distribution concentration C of contained germanium atoms is from the position t _B to the position t _T.
A distribution state is formed in which the concentration gradually decreases continuously from C ₄ and the concentration becomes C ₅ at the position t _T.

In the case of FIG. 4, from the position t _B to the position t ₂ , the distribution concentration C of germanium atoms is set to a constant value of the concentration C ₆ , and gradually and continuously between the positions t ₂ and t _T. Reduced position
At t _T , the distribution concentration C is substantially zero (here, substantially zero is less than the detection limit amount).

In the case of FIG. 5, until the distribution concentration C of the germanium atoms reaches the position t _T to the position t _B, is reduced continuously and gradually than the concentration C _6, and is substantially zero at the position t _T .

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of the concentration C ₉ between the position t _B and the position t ₃ , and is the concentration C _{10 at the} position t _T. Between the position t ₃ and the position t _T , the distribution concentration C is linearly reduced from the position t ₃ to the position t _T.

In the example shown in FIG. 7, from the position t _B to the position t _T , the distribution concentration C of germanium atoms is linearly decreased from the concentration C ₁₁ to substantially zero.

As described above with reference to FIGS. 2 to 7, some typical examples of the distribution state of the germanium atoms contained in the long wavelength light-sensitive layer in the layer thickness direction are explained. , A portion having a high distribution concentration C of germanium atoms, and the distribution concentration C is considerably lower on the interface t _T side than on the support side. When it is provided in the above, it is mentioned as one of the suitable examples. As the distribution state of germanium atoms in the layer thickness direction, the maximum value Cmax of the distribution concentration of germanium atoms is preferably 1000 atom ppm or more, more preferably 5000 atom ppm or more, most preferably 1 ×, with respect to the sum with the silicon atom. It is desirable to form a layer so that a distribution state of 10 ⁴ atomic ppm or more can be obtained.

In the present invention, the content of the germanium atom contained in the long-wavelength photosensitive layer 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 atom pp
m, preferably 100-9.5 × 10 ⁵ atomic ppm, optimally 500-8
It is desirable that the concentration is × 10 ⁵ atom ppm.

The long-wavelength photosensitive layer is a substance that further controls conductivity,
You may contain at least 1 sort (s) among an oxygen atom and a nitrogen atom.

Further, examples of the above-mentioned substance that controls conductivity include so-called impurities in the semiconductor field, and in the present invention, an atom belonging to Group III of the periodic table (hereinafter referred to as “III Group atom ”) or an atom belonging to Group V of the periodic table (hereinafter referred to as“ Group V atom ”) that provides n-type conductivity. Specific examples of the group III atom include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium), and B and Ga are particularly preferable. Specific examples of the Group V atom include P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), and the like, with P and As being particularly preferable.

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 atom ppm, more preferably 0.5 to 1 × 10 ⁴ atom pp
m, optimally 1 to 5 × 10 ³ atomic ppm is desirable.

In the present invention, in order to form a long-wavelength photosensitive layer composed of a polycrystalline material containing silicon atoms and germanium atoms, a discharge phenomenon such as a glow 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 long-wavelength photosensitive layer by the glow discharge method, basically, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying Ge that can supply germanium atoms (Ge) can be used. Source gas of
If necessary, a raw material gas for introducing a hydrogen atom (H) or / and a raw material gas for introducing a halogen atom (X) is introduced into a deposition chamber whose inside can be decompressed in a desired gas pressure state, A glow discharge may be caused to occur and a layer may be formed on the surface of a predetermined support which is installed at a predetermined position in advance.
Further, in order to contain the germanium atoms in a non-uniform distribution state, the layer may be formed while controlling the distribution concentration of the germanium atoms according to a desired change rate curve. In the case of forming by the sputtering method, for example, a target composed of Si in the atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, or composed of the target and Ge. Using two of the target, or using a mixture of Si and Ge target, if necessary, the source gas for Ge supply diluted with a diluent gas such as He, Ar, If necessary, a gas for introducing hydrogen atoms (H) and / or halogen atoms (X) is introduced into the deposition chamber for sputtering, and a plasma atmosphere of the desired gas is formed. When the distribution of germanium atoms is made uniform, the gas flow rate of the source gas for Ge supply may be controlled according to a desired rate-of-change curve, and the target may be sputtered.

In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed as evaporation sources in a vapor deposition board, and the evaporation sources are subjected to resistance heating or electron beam. It can be carried out in the same manner as in the sputtering method, except that it is heated and evaporated by the method (EB method) and the flying evaporated material is passed through a desired gas plasma atmosphere.

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. (Silanes) are mentioned as being effectively used. Especially, SiH ₄ and Si ₂ H ₆ are easy to handle at the time of layer formation work and have good Si supply efficiency.
Are preferred.

GeH ₄ and Ge ₂ H are substances that can be used as the source gas for Ge supply.
₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ ,
Ge ₉ H ₂₀ or the like in a gas state or a gasifiable germanium hydride can be mentioned as being effectively used, and in particular, in terms of ease of handling during layer formation work, good Ge supply efficiency, and the like,
GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ are preferred.

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

Further, a silicon hydride compound containing a halogen atom, which is composed of silicon atoms and halogen atoms 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 and IF _7. , ICl, IBr
Interhalogen compounds such as

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

When forming a photoconductive member characteristic of the present invention by a glow discharge method using a silicon compound containing such a halogen atom, hydrogen as a source gas capable of supplying Si together with the source gas for supplying Ge It is possible to form a long-wavelength photosensitive layer containing a halogen atom on a desired support without using a silicon gas.

According to the glow discharge method, when manufacturing a long-wavelength photosensitive layer containing a halogen atom, basically, for example, silicon halide as a source gas for Si supply and germanium hydride and Ar as a source gas for Ge supply. , Gas such as H ₂ and He is introduced into the deposition chamber where the long wavelength photosensitive layer is formed at a predetermined mixing ratio and gas flow rate, and glow discharge is generated to generate a plasma atmosphere of these gases. By forming it, it is possible to form a long-wavelength photosensitive layer on a desired support. However, in order to make it easier to control the introduction ratio of hydrogen atoms, hydrogen gas is further added to these gases. Alternatively, a gas of a silicon compound containing a hydrogen atom may be mixed in a desired amount 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.

In order to introduce a halogen atom into the layer formed by either the sputtering method or the ion plating method,
It suffices to introduce the gas of the halogen compound or the silicon compound containing the halogen atom into the deposition chamber to form the plasma atmosphere of the gas.

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

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
iH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr _{3 and} other halogen-substituted hydrogen, and GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ ,
GeH ₂ Cl ₂ , GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ , G
eH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, and other halides containing hydrogen atoms as one of the constituent elements, GeF ₄ ,
GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI _{2, and} other germanium halides, etc. are also effective starting materials for forming the long-wavelength photosensitive layer in a gas state or a gasifiable substance. I can name it.

Among these substances, halogenated articles containing hydrogen atoms are
During the formation of the long-wavelength light-sensitive layer, a hydrogen atom, which is extremely effective for controlling the electrical or photoelectric properties, is introduced at the same time as the introduction of a halogen atom into the layer. Used as a raw material.

To structurally introduce hydrogen atoms into the long-wavelength photosensitive layer,
In addition to the above, H ₂ or germanium or germanium compound for supplying silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ or Si ₄ H ₁₀ to Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ ,
Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H _{20 and} other germanium hydride and silicon or a silicon compound for supplying Si are allowed to coexist in the deposition chamber. It can also be done by causing a discharge.

In a preferred embodiment of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the amount of hydrogen atoms and halogen atoms contained in the long-wavelength photosensitive layer of the formed light-receiving member is adjusted. The sum (H + X) is preferably 0.01 to 40 atom%, more preferably 0.05 to 30 atom%, and most preferably 0.1 to 25 atom%.

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

In the present invention, in order to make the long-wavelength photosensitive layer contain a nitrogen atom, the starting material for introducing a nitrogen atom at the time of forming the long-wavelength photosensitive layer is the starting material for forming the long-wavelength photosensitive layer described above. It may be used together with it to control the amount thereof to be contained in the layer to be formed.

In order to form a long-wavelength photosensitive layer by the glow discharge method, as a starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms as constituent atoms or those obtained by gasifying a gasifiable substance are used. Things 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 used by mixing it with 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. Are mixed with each other at a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms and a silicon atom (Si), a nitrogen atom (N) and a hydrogen atom (H) are mixed. It is possible to mix and use a raw material gas having one of the constituent atoms.

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

A starting material effectively used as a raw material gas for introducing a nitrogen atom (N) is, for example, nitrogen (N ₂ ), ammonia (NH ₂ ) having N as a constituent atom or N and H as a constituent atom. ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (H
N _3), gaseous or nitrogen can be gasified, such as ammonium azide (NH ₄ N _3), can be mentioned nitrogen compounds such as nitrides and azides. In addition to this, nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ) and the like can be introduced in addition to the introduction of the nitrogen atom (N) and the introduction of the halogen atom (X). Nitrogen halide compounds can be mentioned.

In the present invention, the long wavelength light-sensitive layer may contain nitrogen atoms and / or oxygen atoms. Examples of the raw material gas for introducing oxygen atoms into the long-wavelength photosensitive layer include oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), Nitrogen monoxide (N ₂ O),
Nitrogen trioxide (N ₂ O ₃ ), Tetranitrogen dioxide (N ₂ O ₄ ), Nitrogen pentaoxide (N ₂ O ₅ ), Nitric oxide (NO ₃ ), Silicon atom (S
i), an oxygen atom (O), and a hydrogen atom (H) as constituent atoms, and examples thereof include lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). I can.

To form a long-wavelength photosensitive layer by the sputtering method, when forming the long-wavelength photosensitive layer, a single crystal or polycrystalline Si wafer or Si ₃ N ₄ wafer, or Si and Si ₃ N ₄ are mixed and contained. It may be carried out by targeting a known wafer and spattering them in various gas atmospheres.

For example, if you use a Si wafer as a target,
A raw material gas for introducing a nitrogen atom and, if necessary, a hydrogen atom and / or a halogen atom is diluted with a diluting gas as needed, and then introduced into a deposition chamber for a spatula. It suffices to form plasma and sputter the Si wafer.

Separately, Si and Si ₃ N ₄ are used as 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 the sputtering. Is sputtered in a gas atmosphere containing as.

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

In the present invention, when the long-wavelength photosensitive layer is formed, the distribution concentration C (N) of nitrogen atoms contained in the layer is changed in the layer thickness direction to obtain a desired distribution state in the layer thickness direction ( depth profil
In order to form a layer having e), in the case of glow discharge, a gas of a starting material for introducing a nitrogen atom whose distribution concentration C (N) is to be changed, and its gas flow rate is appropriately adjusted according to a desired change rate curve. It is made by changing it and introducing it into the deposition chamber.

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

When forming by the sputtering method, the distribution concentration C (N) of nitrogen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state of nitrogen atoms in the layer thickness direction (depth profile).
First, as in the case of the glow discharge method, the starting material for introducing nitrogen atoms is used in a gas state, and the gas flow rate at the time of introducing the gas into the deposition chamber is set as desired. It is made by changing it appropriately.

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, at the thickness direction of the Tagetsuto, made by allowed to advance changed.

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 It is preferably 0.05 to 30 atom%, and most preferably 0.1 to 25 atom%.

In order to structurally introduce a substance that controls the conduction characteristics, for example, a group III atom or a group V atom, into the long-wavelength photosensitive layer, a starting material for introducing a group III atom during layer formation or The starting material for introducing the group V atom may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the long wavelength photosensitive layer. As such a starting material for introducing 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 such a starting material for introducing a Group III atom, specifically for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄
And boron hydrides such as BF ₃ , BCl ₃ , and BBr _{3 and the} like. In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , In
Other examples include Cl ₃ and TlCl ₃ .

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.

In order to effectively achieve the object of the present invention in forming the long-wavelength photosensitive layer, the temperature of the support is appropriately selected from an optimum range, but preferably 200 ° C to 700 ° C, more preferably 250
It is desirable to set the temperature between ℃ and 600 ℃.

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 the long-wavelength photosensitive layer is formed by these layer forming methods, the discharge power and the gas pressure at the time of forming the layer are created in the same manner as the above support temperature. It is an important factor that influences the characteristics of the wavelength light-sensitive layer.

In producing the long-wavelength photosensitive layer having properties capable of achieving the object of the present invention with good productivity and efficiency, the discharge power condition is preferably 100 to 5000 W, and more preferably 200 to The pressure is preferably 2000 W, and the gas pressure in the deposition chamber is preferably 10 ^{−3 to} 0.8 Torr, more preferably 10 ^{−2 to} 0.5 Torr.

In the present invention, the above-mentioned ranges are mentioned as the desirable numerical ranges of the support temperature and the discharge power for producing the long-wavelength photosensitive layer, but these layer-forming factors are usually independent and separate. However, it is desirable to determine the optimum value of each layer-forming factor based on mutual and organic relationships 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 to 50 μm, more preferably 40Å to 40 μm, optimally
It is desirable that the thickness is 50Å to 30 μm.

Charge Injection Blocking Layer The charge injection blocking layer in the present invention is composed of A-Si (H, X), and a substance for controlling conductivity is uniformly or preferably distributed in a large amount on the support side in the entire layer region of the layer. Thus, it is contained in a non-uniform state. Further, if necessary, oxygen atoms and / or nitrogen atoms may be uniformly or preferably contained in a non-uniform state so that a large number of oxygen atoms and / or nitrogen atoms are distributed on the support side in the entire layer region or a part of the layer region of the charge injection blocking layer. The adhesion between the charge injection blocking layer and the support can be improved, and the band gap can be adjusted.

Examples of the substance for controlling the conductivity contained in the charge injection blocking layer include so-called impurities in the field of semiconductors. In the present invention, the substance belongs to Group III of the periodic table, which imparts p-type conductivity. An atom (hereinafter referred to as “Group III atom”) or an atom belonging to Group V of the periodic table (hereinafter referred to as “Group V atom”) that provides N-type conductivity is used. As the group III atom, specifically, B (boron),
There are Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferable. As the group V atom, specifically, P (phosphorus), As
(Arsenic), Sb (antimony), Bi (bismuth), etc.
P and As are particularly preferable.

8 to 12 show that the charge injection blocking layer contains II.
A typical example of the state of distribution of group I atoms or group V atoms in the layer thickness direction is shown.

In the examples of FIGS. 8 to 12, the horizontal axis represents the distribution concentration C of group III atoms or group V atoms, the vertical axis represents the layer thickness t of the charge injection blocking layer, and t _B is the interface position on the support side. , _{T T} indicates the position of the interface on the side opposite to the support side. That is, the charge injection blocking layer is formed from the t _B side toward the t _T side.

FIG. 8 shows a first typical example in which the group III atoms or the group V atoms contained in the charge injection blocking layer are distributed in the layer thickness direction.

In the example shown in FIG. 8, up to the position t ₄ beyond the interface position t _B , the content concentration C of the group III atom or the group V atom is contained at a constant value of C _12, and is contained at the position t. _{As shown in FIG. 4} , the distribution concentration C is gradually and continuously decreased from C ₁₃ until reaching the interface position t _T. The distribution concentration C is C _{14 at the} interface position t _T.

In the example shown in FIG. 9, the distribution concentration C of the contained Group III atoms or Group V atoms gradually decreases continuously from C ₁₅ from the position t _B to the position t _T and the position t increases. C at _T
A distribution state of ₁₆ is formed.

In the example shown in FIG. 10, the distribution concentration C of the group III atom or the group V atom is C ₁₇ between the position t _B and the position t _5.
Is a constant value and is C _{18 at the} position t _T. Position t
_{Between 5} and the position t _T , the distribution concentration C is linearly functioning at the position t
It is reduced from ₅ to the position t _T.

In the example shown in FIG. 11, the distribution density C takes a constant value of C ₁₉ from the position t _B to the position t ₆ , and from the position t ₆ to the position t _T.
Up to C ₂₁ , the distribution state decreases linearly from C ₂₀ to C ₂₁ .

In the example shown in FIG. 12, the distribution density C takes a constant value of C ₂₂ from the position t _B to the position t _T.

In the present invention, the charge injection blocking layer is a group III atom or a group V atom.
When a large number of group atoms are contained on the support side, the maximum distribution concentration value of group III atoms or group V atoms is preferably 50 atom ppm or more, more preferably 80 atom ppm or more.
It is desirable that the layers are formed so that the distribution state may be at least atomic ppm or more, optimally at least 100 atomic ppm.

In the present invention, the content of the group III atom or the group V atom contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably 30 Up to 5 × 10 ⁴ atomic ppm, more preferably 50
~ 1 x 10 ⁴ atom ppm, optimally 1 x 10 ^{2 to} 5 x 10 ³ atom ppm
Is desirable.

The charge injection blocking layer, as described above, mainly contains oxygen atoms and / or nitrogen atoms to improve the adhesion between the long-wavelength photosensitive layer and the charge injection blocking layer, and the charge injection blocking layer and the photoconductive layer. And the band gap of the charge injection blocking layer can be adjusted.

FIGS. 13 to 19 show typical examples of the distribution state of oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer in the layer thickness direction.

In the examples of FIGS. 13 to 19, the horizontal axis represents the distribution concentration C of oxygen atoms and / or nitrogen atoms, the vertical axis represents the layer thickness t of the charge injection blocking layer, t _B represents the interface position on the support side, t _T indicates the position of the interface on the side opposite to the support side. That is, the charge injection blocking layer is formed from the t _B side toward the t _T side.

FIG. 13 shows a first typical example of the distribution state of oxygen atoms and / or nitrogen atoms contained in the charge injection blocking layer in the layer thickness direction.

In the example shown in FIG. 13, from the position t _B to the position t ₇ , the concentration C of oxygen atoms and / or nitrogen atoms has a constant value of C ₂₃ and is distributed from the position t _7. The concentration C is gradually and continuously decreased from C ₂₄ until reaching the interface position t _T. The distribution concentration C is C _{25 at the} interface position t _T.

In the example shown in FIG. 14, the distribution concentration C of contained oxygen atoms and / or nitrogen atoms gradually decreases continuously from C ₂₆ from the position t _B to the position t _T , and at the position t _T. C
A distribution state of ₂₇ is formed.

In the case of FIG. 15, the distribution concentration C of oxygen atoms and / or nitrogen atoms is constant at C ₂₈ from the position t _B to the position t ₈ .
It is gradually and continuously reduced between the position t ₈ and the position t _T, and is substantially zero at the position t _T.

In the case of FIG. 16, the oxygen atom and / or the nitrogen atom are located
The distribution concentration C is continuously and gradually reduced from C ₃₀ from t _B to the position t _T, and is substantially zero at the position t _T.

In the example shown in FIG. 17, the distribution concentration C of oxygen atoms or / and nitrogen atoms than the position t _B to the position t ₉ takes a constant value of C _31, from C ₃₁ up to the position t _T to the position t ₉ It is assumed that the distribution state decreases linearly up to C ₃₂ .

In the example shown in FIG. 18, the distribution concentration C of oxygen atoms and / or nitrogen atoms is C ₃₃ between the position t _B and the position t _10.
Is a constant value and is C _{35 at the} position t _T. Position t
_{Between 10} and the position t _T , the distribution concentration C is linearly positioned
It is decreased from t ₁₀ to the position t _T.

In the example shown in FIG. 19, the distribution density C takes a constant value of C ₃₆ from the position t _B to the position t _T.

In the present invention, when the charge injection blocking layer contains oxygen atoms and / or nitrogen atoms in a distributed state in which a large number of oxygen atoms and / or nitrogen atoms are distributed on the support side, the distribution concentration value of oxygen atoms and / or nitrogen atoms or the maximum value of the sum of both atoms is obtained. However, preferably 500 atomic ppm or more,
It is desirable to form a layer so that the distribution state can be more preferably 800 atom ppm or more, and most preferably 1000 atom ppm or more.

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

In the present invention, the thickness of the charge injection blocking layer is preferably 0.01 to 10 μm, more preferably 0.05 to 8 μm, and most preferably 0 to 10 μm in view of obtaining desired electrophotographic characteristics and economic effects.
It is desirable to set it to 1 to 5 μ.

Photoconductive Layer The photoconductive layer in the present invention is composed of A-Si (H, X) and has photoconductive characteristics satisfying desired electrophotographic characteristics.

A substance for controlling the conductivity may be contained in the entire area of the photoconductive layer as long as the characteristics required for the photoconductive layer are not impaired.

Further, at least one of a carbon atom, an oxygen atom and a nitrogen atom may be contained in the entire area of the photoconductive layer within a range not impairing the properties required for the photoconductive layer.

As the substance for controlling the conductivity, a group III atom or a group V atom can be used as in the charge injection blocking layer described above.

When the entire region of the photoconductive layer of the present invention contains a group III atom or a group V atom, it mainly exerts the effect of controlling the conductivity type and / or the conductivity, and the group III atom or the group V atom Content is relatively small, preferably 1 x 10
^{-3 to} 3 x 10 ² atom ppm, more preferably 5 x 10 ^-3 to 10 ² atom p
pm, optimally 1 × 10 ^-2 to 50 atomic ppm is desirable.

When the photoconductive layer of the present invention contains oxygen atoms or carbon atoms in the entire layer region, the effect is mainly to increase the dark resistance and improve the adhesion between the charge injection blocking layer and the photoconductive layer. However, it is desirable that the content of oxygen atoms is relatively small so that the photoconductive characteristics of the layer 103 are not deteriorated.

In the case of a nitrogen atom, in addition to the above points, the photosensitivity can be improved in the coexistence with, for example, a Group III atom, especially B. The content of oxygen atoms or nitrogen atoms contained in the photoconductive layer, or the sum of both is preferably 1 × 10 ⁻³ to 10
³ atomic ppm, more preferably 5 × 10 ^{−2 to} 5 × 10 ² atomic ppm, and most preferably 1 × 10 ⁻¹ to 2 × 10 ² atomic ppm.

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 and is irradiated with light. On the other hand, the photoconductive layer is made of A-Si (H, X).

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

The concentration (Na) of the acceptor is lower than that of the p-type A-Si (H, X) --- type,
Or, the relative concentration of the acceptor is low.

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

The concentration of the donor (Nd) is lower than that of the n-type A-Si (H, X)-type, or the relative concentration of the donor is low.

i-type A-Si (H, X) --- NaNd or NaN
d thing.

In the present invention, the halogen atom (X) contained in the charge injection blocking layer and / or the photoconductive layer is preferably F or C.
l, Br, I, especially F, Cl are desirable.

In the present invention, the charge injection blocking layer and / or the photoconductive layer composed of A-Si (H, X) is formed by, for example, a glow discharge method, a microwave discharge method, a sputtering method, or an ion plating method. It is formed by a vacuum deposition method utilizing a discharge phenomenon such as a towing method. For example, in order to form an amorphous layer composed of A-Si (H, X) by the glow discharge method, basically, together with a source gas for supplying Si capable of supplying silicon atoms (Si), hydrogen is used. A raw material gas for introducing an atom (H) and / or for introducing a halogen atom (X) is introduced into a deposition chamber whose inside can be decompressed to cause glow discharge in the deposition chamber, and A-Si (H, X) may be formed. 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.

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.

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
Preferable examples are silicon halides such as F ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ .

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 composed of A-Si: H 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. A desired layer can be formed on a predetermined support by introducing into a deposition chamber for forming a desired layer as described above, and causing a glow discharge to form a plasma atmosphere of these gases. However, in order to measure the introduction of hydrogen atoms, a predetermined amount of a silicon compound gas containing hydrogen atoms may be mixed 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.

In order to form a layer of A-Si (H, X) 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, and the target is made of a predetermined gas. In the case of the ion plating method, the sputtering is performed in a 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 this silicon evaporation source is a resistance heating method or an electron beam method (EB method). It can be carried out by heating and evaporating by means such as the above, and letting the flying evaporate pass through 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 an effective starting material for forming the charge injection blocking layer and the photoconductive layer.

The halide containing these hydrogen atoms is introduced into the layer formed at the time of layer formation at the same time as the introduction of the halogen atom into which a hydrogen atom extremely effective in controlling the electrical or photoelectric properties is also introduced. In this case, it is used as a preferable raw material for introducing halogen.

To introduce hydrogen atoms structurally into the layer to be formed,
Another of H ₂ above, or _{SiH 4, Si 2 H 6,} Si 3 H 8, Si 4 and the H ₁₀ such as silicon hydride gas coexist in the silicon compound in the deposition chamber for supplying a Si discharge It can also be done by causing.

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.
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 atom (H) or the amount of halogen atom (X), or the amount of hydrogen atom and halogen contained in the charge injection blocking layer and the photoconductive layer of the electrophotographic light-receiving member to be formed. The sum of atomic amounts is preferably 1 to 40 atomic%,
It is more preferable that the amount is 5 to 30 atomic%.

In order to control the amount of hydrogen atoms (H) or / and halogen atoms (X) contained in the formed layer, for example, the temperature of the support or / and the hydrogen atoms (H), or the halogen atom (X) may be adjusted. It suffices to control the amount of the starting material used for inclusion in the deposition apparatus system, the discharge power, and the like.

In order to make the charge injection blocking layer or the photoconductive layer contain a group III atom or a group V atom, and a carbon atom, an oxygen atom or a nitrogen atom, the charge injection blocking layer or the light is formed by a glow discharge method or a reaction sputtering method. When forming the conductive layer, a starting material for introducing a group III atom or a group V atom and starting materials for introducing an oxygen atom, a nitrogen, and a carbon are respectively provided as described above for the charge injection blocking layer and the photoconductive layer. It is made by using together with the starting material for forming a layer and controlling the amount thereof to be contained in the layer to be formed.

As such a starting material for introducing a carbon atom, for introducing an oxygen atom and / or for introducing a nitrogen atom, or a starting material for introducing a group III atom or a group V atom, at least a carbon atom, an oxygen atom and Most of the gasified substances having any of nitrogen atoms or group III atoms or group V atoms as constituent atoms or gasified substances can be used.

For example, a raw material gas containing silicon atoms (Si) as a constituent atom, a raw material gas containing oxygen atoms (O) as a constituent atom, and a hydrogen atom (H) or a halogen and / or a halogen as necessary if they contain oxygen atoms. A raw material gas containing atoms (X) as constituent atoms 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 are also mixed at a desired mixing ratio, or
It is possible to use a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing silicon atoms (Si), oxygen atoms (O) and hydrogen atoms (H) as constituent atoms. I can.

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 oxygen atoms (O) as constituent atoms.

Specific examples of starting materials for introducing oxygen atoms and nitrogen atoms include oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and Nitrogen dioxide (N ₂ O), Nitrogen trioxide (N ₂ O ₃ ), Nitrogen dioxide (N ₂ O ₄ ), Nitrogen dioxide (N ₂ O ₅ ), Nitric oxide (N
O ₃ ), nitrogen (N ₂ ), ammonia (NH ₃ ), hydrogen azide (H
N ₃ ), hydrazine (NH ₂ NH ₂ ), silicon atom (Si), oxygen atom (O) and hydrogen atom (H) as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ S
Lower siloxanes such as iOSiH ₂ OSiH ₃ ) can be mentioned.

Examples of the carbon atom-containing compound as a raw material for introducing carbon atoms include 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 (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 .

When glow discharge is used to form the charge injection blocking layer and the photoconductive layer containing a group III atom or a group V atom, the starting material used as a raw material gas for forming the layer is the above-mentioned A-Si. A material appropriately selected from the charge injection blocking layer composed of (H, X) and the starting material for forming the photoconductive layer is
A starting material for introducing a group I atom or a group V atom is added. As a starting material for introducing such a group III atom or a group V atom, a substance in a gas state having a group III atom or a group V atom as a constituent atom or a gasified substance capable of being gasified is used. , Any of them may be used.

What is effectively used as a starting material for introducing a Group III atom in the present invention is specifically B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H for introducing a boron atom. ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ ,
Examples thereof include boron hydrides such as B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ , and BBr ₃ , and AlCl ₃ and GaC.
l ₃ , InCl ₃ , TlCl ₃ etc. can also be mentioned.

In the present invention, what is effectively used as a starting material for introducing a Group V atom is, specifically, for introducing a phosphorus atom,
PH ₃ , P ₂ H ₄ etc. Phosphorus hydride, PH ₄ I, PF ₃ , PF ₅ , PCl ₃ , PC
Examples thereof include phosphorus halides such as l ₅ , PBr ₃ , PBr ₅ , and PI ₃ .
In addition, AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , Sb
_{F 3, SbF 5, SbCl 3} , SbCl 5, BiH 3, BiCl can also be mentioned _3, BiBr _3, etc..

The content of the group III atom or the group V atom introduced into the charge injection blocking layer and the photoconductive layer containing the group III atom or the group V atom depends on the group III atom introduced into the deposition chamber. Or a gas flow rate of a starting material for introducing a Group V atom, a gas flow rate ratio,
It can be arbitrarily controlled by controlling the discharge power, the support temperature, the pressure in the deposition chamber, and the like.

The support temperature for the purpose of effectively achieving the object of the present invention is appropriately selected from the optimum range, but preferably 50 ° C to 35 ° C.
The temperature is preferably 0 ° C, more preferably 100 ° C to 300 ° C.

In the formation of the charge injection blocking layer and the photoconductive 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. It is desirable to adopt a sputtering method or a sputtering method, but when forming the charge injection blocking layer and the photoconductive layer by these layer forming methods, the discharge power and gas at the time of forming the layer are the same as the above-mentioned support temperature. The pressure is an important factor that influences the characteristics of the charge injection blocking layer and the photoconductive layer created.

In producing the charge injection blocking layer and the photoconductive layer having the characteristics capable of achieving the object of the present invention with good productivity and efficiency, the discharge power condition is preferably 10 to 1000.
W, more preferably 20 to 500 W, and
Regarding the gas pressure in the deposition chamber, preferably 0.01 to 1 Tor
r, more preferably about 0.1 to 0.5 Torr.

In the present invention, the above-mentioned ranges are mentioned as the desirable numerical ranges of the support temperature and the discharge power for forming the charge injection blocking layer and the photoconductive layer, but these layer forming factors are usually independently separated. However, it is desirable to determine the optimum value of each layer forming factor based on the mutual and organic relationships so as to form the charge injection blocking layer and the photoconductive layer having desired characteristics.

In the present invention, the amount of carbon atoms, oxygen atoms or nitrogen atoms contained in the photoconductive layer to be formed, and the sum of at least two of them are the electrophotographic light to be formed. It greatly affects the characteristics of the receiving member and must be appropriately determined as desired, but is preferably 0.0005.
~ 30 atom%, more preferably 0.001-20 atom%, optimally
It is desirable to set it to 0.002 to 15 atom%.

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.

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.

Further, in the present invention, since each of the amorphous materials forming the photoconductive layer and the surface layer forming the photoconductive layer has a common constituent element of silicon atom, it is present at the stacking interface. The chemical stability is sufficiently ensured.

The surface layer is an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms [A- (Si _x C _1-x ) _y H _1-y ), where 0 <x, y
It is formed by <1].

The surface layer composed of A- (Si _x C _1-x ) _y H _1-y is formed by the glow discharge method, the sputtering method, the ion implantation method, the ion plating method, the electron beam method, etc. It 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 manufactured. From the advantages that it is relatively easy to control the preparation conditions for manufacturing the electrophotographic light-receiving member having, and that it is easy to 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, A- (Si _x C
_1-x ) _y H _1-y raw material gas for forming is mixed with a dilution gas at a predetermined mixing ratio, if necessary, and introduced into a deposition chamber for vacuum deposition in which a support is installed, The introduced gas is turned into a gas plasma by causing a glow discharge to generate the support 10
A- (Si _x C _1-x ) _y H on the photoconductive layer already formed on
Just deposit _1-y .

In the present invention, the raw material gas for forming A- (Si _x C _1-x ) _y H _1-y is a gaseous substance or gas containing at least one of Si, C and H as a constituent atom. Most of the gasified substances that can be converted can 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. Alternatively, the raw material gas containing Si as a constituent atom and the raw material gas containing Si, C and H as three constituent atoms can be mixed and used.

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

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 ₈ , Si ₄ H _10, etc. Silanes and other hydrogenated silicon 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 (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 include acetylene (C ₂ H ₂ ), methylacetylene (C
₃ H ₄ ), butyne (C ₄ H ₆ ) and the like.

As a source gas containing Si, C and H as constituent atoms, Si (C
Alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ can be mentioned. In addition to these raw material gases, H ₂ is of course also used as an effective raw material gas for introducing H.

In order to form the surface layer by the sputtering method, a single crystal or polycrystal Si wafer or C wafer or a wafer containing Si and C mixed therein is used as a target, and these are sputtered in various gas atmospheres. You can do it by doing things.

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 a diluting gas used when forming the surface layer by the glow discharge method or the sputtering method, a so-called rare gas, for example, He, Ne, Ar or the like can be preferably mentioned.

The surface layer in the present invention is carefully formed to provide the required properties as desired.

That is, a substance having Si, C, and H as constituent atoms structurally takes a form from crystal to amorphous depending on its preparation condition, and has electrical properties from conductive to semiconducting to insulating. , And each of the properties from the photoconductive property to the non-photoconductive property, therefore, in the present invention, A- (Si _x C _1-x ) _y having a desired property according to the purpose. The choice of production conditions is rigorously made as desired so that H _1-y is formed. For example, A- (Si _x C _1-x ) _y H _1-y is an amorphous material with a remarkable electrical insulating behavior in the operating environment in order to provide the surface layer mainly for the purpose of improving the pressure resistance. Created as a material.

Further, when the surface layer is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics, the degree of the above-mentioned electric insulation is relaxed to some extent, and a non-sensitive material having a certain sensitivity to irradiation light is used. A- (Si _x C _1-x ) _y as a crystalline material
H _1-y is created.

When forming a surface layer composed of A- (Si _x C _1-x ) _y H _{1-y on} the surface of the photoconductive layer, the temperature of the support during layer formation influences the structure and properties of the formed layer. In the present invention, it is an important factor, and in the present invention, a support at the time of layer formation so that A- (Si _x C _1-x ) _y H _1-y having desired properties can be formed as desired. It is desirable that the temperature be tightly controlled.

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 to form the surface layer. However, preferably 50 ℃ ~ 350 ℃, more preferably 100 ℃ ~
A temperature of 300 ° C is desirable. For the formation of the surface layer, the glow discharge method and the sputtering method are used because it is relatively easy to control the composition ratio of the atoms that form the layer and the layer thickness compared to other methods. Is advantageous, but when the surface layer is formed by these layer forming methods,
The discharge power and gas pressure during layer formation are one of the important factors that influence the characteristics of A- (Si _x C _1-x ) _y H _1-y , which is created as well as the support temperature. .

A- (S having properties for achieving the object of the present invention
i _x C _1-x ) _y H _1-y is preferably 10 to 1000 W, and more preferably 20 to 500 W, as the discharge power condition for effectively producing it. . The gas pressure in the deposition chamber is preferably 0.01-1 Torr, preferably 0.1-0.5 Torr.
It is desirable to set it as a degree.

In the present invention, the support temperature for forming the surface layer,
Examples of the desirable numerical value range of the discharge power include the values in the above-mentioned range, but these layer forming factors are not independently determined separately, and the desired characteristics of A- (Si _x C
_It is desirable that the optimum value of each layer forming factor be determined based on the mutual inductive relationship so that the surface layer composed of _1-x ) _y H _1-y is formed.

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

The amount of carbon atoms contained in the surface layer in the present invention is preferably 1 × 10 6 with respect to the total amount of silicon atoms and carbon atoms.
^{-3 to} 90 atom%, more preferably 1 to 90 atom%, optimally
It is desirable that the amount be 10 to 85 atom%. The content of hydrogen atoms is usually 41 to 70 at%, preferably 41 to 65 at%, optimally 45 to the total amount of constituent atoms.
It is desirable that the content be in the range of up to 60 atom%, and the light-receiving member formed when the hydrogen content is in these ranges is a material that can be sufficiently applied as a remarkably excellent material in the practical aspect. Is.

That is, defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer composed of A- (Si _x C _1-x ) _y H _1-y are It is known that the characteristics are adversely affected, for example, the deterioration of the charging characteristics due to the injection of charges from the free surface, the fluctuation of the charging characteristics due to the change of the surface structure under the usage environment, for example, high humidity, and during corona charging. In addition, an afterimage phenomenon upon repeated use due to charge injection into the surface layer by the light-receiving layer at the time of light irradiation and trapping of charges in the defects in the surface layer can be mentioned.

However, by controlling the hydrogen content in the surface layer to be 41 atomic% or more, the defects in the surface layer are greatly reduced, and as a result, all of the above problems are eliminated, and in particular, electrical It is possible to make a dramatic improvement in terms of characteristics and high-speed continuous usability.

On the other hand, when the hydrogen content in the surface layer is 71 atomic% or more, the hardness of the surface layer decreases, and it cannot withstand repeated use. Therefore, controlling the hydrogen content in the surface layer to be within the above range is one of the very important factors in obtaining the desired electrophotographic properties that are remarkably excellent. Hydrogen content in the surface layer, H ₂ gas flow rate, support temperature, discharge power,
It can be controlled by gas pressure or the like.

That is, x is preferably 0.1 to 0.99999, more preferably 0.1 to 0.99, optimally 0.15 to 0.9, and y is A- (Si _x C _1-x ) _y H _1-y. Usually 0.3-0.59, preferably 0.35-0.5
9, optimally 0.4 to 0.55 is desirable.

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 ₄ 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 , CH ₃ CF ₃ or the like by a glow discharge decomposition method or a 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 light-receiving 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 0.00
3 to 30μ, more preferably 0.004 to 20μ, optimally 0.005 to 1
It is desirable that the value be 0 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 light receiving layer and the surface layer constituting the light receiving layer are effectively utilized, respectively, and the object of the present invention is effectively achieved. As described above, the layer thickness relationship between the photoconductive layer and the surface layer can be determined as desired, and the layer thickness of the light receiving layer is preferably 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.

In the electrophotographic light-receiving member of the present invention, for the purpose of further improving the adhesion between the support and the photoconductive layer, for example, Si ₃ N ₄ , SiO ₂ , SiO hydrogen atoms and halogens are used. An adhesion layer made of an amorphous material containing at least one of atoms, at least one of nitrogen atoms and oxygen atoms, and silicon atoms may be provided.

Next, the outline of the method for producing the light receiving member of the present invention will be described.

FIG. 24 shows an example of an apparatus for manufacturing a light receiving member for electrophotography.

In the gas cylinders 1102 to 1106 in the figure, raw material gases for forming the respective layers of the present invention are sealed. For example, 1102 is a SiH ₄ (purity 99.999%) cylinder, 11
03 is B ₂ H ₆ gas diluted with H ₂ (purity 99.999%, hereinafter B ₂ H ₆
Abbreviated as / H ₂ . ), 1104 is GeH ₄ gas (purity 99.99999%) cylinder, 1105 is NO gas (purity 99.999%) cylinder, 1106 is CH
_{It is a 4} gas (purity 99.99%) 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 valves 1135 of 1102 to 1106 are closed, and check that the inflow valves 1112 to 111 are closed.
6. After confirming that the outflow valves 11117 to 1121 and the auxiliary valves 1132 and 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 113
2, 1133 and the outflow valves 1117 to 1121 are closed.

Next, an example of forming the electrophotographic light-receiving member having the layer structure shown in FIG. 1 on the cylindrical substrate 1137 will be described.
SiH ₄ gas from gas cylinder 1102, GeH ₄ from gas cylinder 1104
B ₂ H ₆ / H ₂ gas from gas cylinder 1103 and NO gas from gas cylinder 1105 are opened by adjusting valves 1122 to 1125 to adjust outlet pressure gauges 1127 to 1130 to 1 kg / cm ² , respectively, and inflow valve 1112 to 1115 are gradually opened to flow into the mass flow controllers 1107 to 1110, respectively. Subsequently, the outflow valves 1117 to 1120 auxiliary valves 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the mass flow controller 1107 is used so that the ratio of the SiH ₄ gas flow rate to the GeH ₄ gas flow rate, the B ₂ H ₆ / H ₂ gas flow rate, and the NO gas flow rate becomes a desired value.
~ 1110 is adjusted, and 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 base cylinder 1137 is set to a desired temperature by the heater 1138, the power source 1140 is set to a desired electric power to cause glow discharge in the reaction chamber 1101, and at the same time predesigned. GeH ₄ gas or / and B ₂ H ₆ /
A germanium atom contained in a layer formed by performing an operation of gradually changing the flow rate of H ₂ gas or / and NO gas by a method such as a manual or an externally driven motor or the like, valve 1118 or / and 1119 or / and 1120 The distribution concentration of / and / or boron atoms and / or oxygen atoms in the layer thickness direction is controlled.

As described above, at the time when the long-wavelength photosensitive layer containing germanium atoms, boron atoms and oxygen atoms in the desired layer thickness is formed, the outflow valve 1119 is closed and GeH ₄ into the reaction chamber 1101 is closed.
Blocks gas inflow and simultaneously outflow valves 1117, 1118 and 112
By adjusting 0 to control the flow rates of SiH ₄ gas and B ₂ H ₆ / H ₂ gas or / and NO gas, and subsequently performing layer formation, the charge injection blocking layer containing no germanium atom is exposed to long wavelength light. A desired layer thickness is formed on the layer.

When containing a halogen atom in the charge injection blocking layer and the long-wavelength photosensitive layer, for example, SiF ₄ gas in the above gas,
Further added and fed into the reaction chamber 1101.

As described above, when the charge injection blocking layer containing boron and oxygen atoms is formed to the desired layer thickness, the outflow valve is formed.
1120 and 1118 are closed, the inflow of B ₂ H ₆ / H ₂ gas and NO gas into the reaction chamber 1101 is shut off, and at the same time the outflow valve 1117 is adjusted to control the flow rate of SiH ₄ gas to continue layer formation. Thus, a photoconductive layer containing no oxygen atom and boron atom is formed on the charge injection blocking layer to a desired layer thickness.

When a photoconductive layer containing oxygen atoms and / or boron atoms is formed, the flow rate may be adjusted to a desired value instead of closing the outflow valve 1118 or / and 1120.

When a halogen atom is contained in the photoconductive layer, for example, SiF ₄ gas is further added to the above gas and fed 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
If a layer is formed using Si 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, for example, SiH ₄ gas, CH ₄ gas and, if necessary, 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 optionally changing the flow rate ratio of SiH ₄ gas and CH ₄ gas introduced into the reaction chamber 1101. 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.

It goes without saying that all the outflow valves other than the gas necessary for forming each layer are closed, and when forming each layer, the gas used for forming the previous layer is the same as the outflow valve 1117 in the reaction chamber 1101. ~ 1121 to avoid remaining in the piping from the inside of 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. Do as needed.

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. 24, a light-receiving member for electrophotography was formed on an aluminum cylinder which was mirror-finished according to the manufacturing conditions shown in Table 1. Further, a device having the same type as that shown in FIG. 24 was used, and a long-wavelength photosensitive layer alone was formed on a cylinder having the same specifications as a sample for analysis. The light receiving member (hereinafter referred to as a drum) is set in an electrophotographic apparatus with a digital exposure function using a semiconductor laser having a wavelength of 780 nm as a light source, and under various conditions, the initial charging ability and residual charge are retained. Checking electrophotographic characteristics such as electric potential and ghost, and reducing chargeability, sensitivity deterioration after 1.5 million sheets of actual machine durability,
The increase in image defects was investigated. 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. Also, for samples with only the long-wavelength photosensitive layer, the upper, middle, and
After cutting out a portion corresponding to the bottom, a diffraction pattern corresponding to Si (111) having a diffraction angle of about 27 ° was obtained by an X-ray diffractometer, and the presence or absence of crystallinity was examined. Table 2 shows the evaluation results, the hydrogen content in the surface layer, and the presence / absence of crystallinity in the long-wavelength photosensitive layer. As can be seen from Table 2, a significant advantage was recognized especially in the items of initial charging ability, image deletion, residual potential, ghost, and increase in 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 production 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. 24, an electrophotographic light-receiving member was formed on an aluminum cylinder that had been mirror-finished according to the manufacturing conditions shown in Table 5. In addition, a device having the same type as that shown in FIG. 24 and having only the long-wavelength photosensitive layer formed on the same cylinder was separately prepared as a sample for analysis. The light receiving member (hereinafter referred to as a drum) is set in a digital exposure function electrophotographic apparatus using a semiconductor laser having a wavelength of 780 nm as a light source, and the initial charging ability and residual charge are set under various conditions. Checking electrophotographic characteristics such as electric potential and ghost, and reducing chargeability, sensitivity deterioration after 1.5 million sheets of actual machine durability,
The increase in image defects was investigated. Furthermore, the image deletion of the drum in a high temperature and high humidity atmosphere of 35 ° C and 85% was also evaluated.
After the evaluation, the drum is cut out at the upper, middle, and lower parts of the image area, and subjected to quantitative analysis of hydrogen contained in the surface layer using SIMS. The component profiles of boron (B) and oxygen (O) in the layer thickness direction and the component profile of germanium (Ge) in the layer thickness direction in the long wavelength photosensitive layer were investigated. on the other hand,
For the sample with only the long-wavelength photosensitive layer, after cutting out the upper, middle, and lower parts corresponding to the generatrix direction of the sample, the X-ray diffractometer diffracts light corresponding to SI (111) around a diffraction angle of 27 °. The pattern was determined and the presence or absence of crystallinity was examined. Table 6 shows the evaluation results, the hydrogen content in the surface layer, and the presence / absence of crystallinity in the long-wavelength photosensitive layer. Further, FIG. 27 shows the component profile of the element in the long-wavelength photosensitive layer and the component profile of the element in the charge injection blocking layer. As can be seen from Table 6, a remarkable superiority was recognized especially in the initial chargeability, residual potential, ghost, image deletion, image defects, increase in image defects and many interference fringes.

<Example 3 (Comparative Example 2)> A plurality of drums were prepared 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, and the same evaluation was performed. I went to Then, for the drum that has been evaluated, cut out the parts corresponding to the top, middle, and bottom of the image part, and
It was subjected to quantitative analysis of hydrogen contained in the surface layer using MS. Table 8 shows the above evaluation results and the hydrogen content in the surface layer.

<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 A plurality of drums were prepared 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 11. As a result of subjecting these drums to the same evaluation as in Example 1, the results shown in Table 12 were obtained.

Example 6 A plurality of drums were prepared 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. When these drums were subjected to the same evaluations as in Example 1, the results shown in Table 14 were obtained.

<Example 7> The production conditions of the long-wavelength photosensitive layer were changed to several conditions shown in Table 15, and only a plurality of drums and long-wavelength photosensitive layers were formed under the same conditions as in Example 1 except for the above. The prepared sample for analysis was prepared. The drum was subjected to the same evaluation as in Example 1, and the sample was partially cut out to obtain a diffraction pattern corresponding to Si (111) near a diffraction angle of 27 ° with an X-ray diffractometer to obtain crystals. The presence or absence of sex was examined. The above results are shown in Table 16.

<Example 8> A plurality of drums and a long-wavelength photosensitive layer were formed under the same conditions as in Example 1 except that the production conditions of the long-wavelength photosensitive layer were changed to several conditions shown in Table 17. The prepared sample for analysis was prepared. The drum was subjected to the same evaluation as in Example 1, and the sample was partially cut out to obtain a diffraction pattern corresponding to Si (111) near a diffraction angle of 27 ° by an X-ray diffractometer to obtain crystallinity. Was checked for. The above results are shown in Table 18.

Example 9 An adhesion layer was formed on a base cylinder under several kinds of manufacturing conditions shown in Table 19, and a light receiving member was further formed thereon under the same manufacturing 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 20.

<Example 10> An adhesion layer was formed on a base cylinder under several kinds of manufacturing conditions shown in Table 21, and a light receiving member was further formed thereon under the same manufacturing 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 22.

<Embodiment 11> A mirror-finished cylinder is further subjected to lathe machining with a sword bite having various angles, and a plurality of cylinders having the cross-sectional shape shown in FIG. 25 and various cross-sectional patterns shown in Table 23 are provided. I prepared a book. The cylinders were sequentially set in the production apparatus shown in FIG. 24 and subjected to the production of a drum under the same production 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 24 were obtained.

<Example 12> The surface of a cylinder that has been mirror-finished is subjected to a so-called surface dimple treatment that exposes the cylinder surface to countless dents by exposing it to the base of the dropping of a large number of bearing balls, and FIG. It facilitated multiple cylinders with a cross-sectional shape like this and with various cross-sectional patterns as shown in Table 25. The cylinders were sequentially set in the production apparatus shown in FIG. 24 and subjected to the production of a drum under the same production 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 26 were obtained.

[Summary of Effects of the Invention] The light-receiving member of the present invention has the same layer structure as the above-mentioned specific layer structure of the light-receiving member for electrophotography having a photoconductive layer composed of A-Si (H, X). As a result, A-Si (H, X)
Capable of solving all the problems of the conventional electrophotographic light-receiving member composed of, and having particularly excellent moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc. Is. 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. .

In particular, in the electrophotographic light-receiving member of the present invention, the provision of the charge injection blocking layer makes it possible to use a photoconductive layer having a relatively low resistance and having sensitivity to light in a relatively wide range of wavelengths. . Moreover, because of the specific layer structure as described above, a large number of charges that have been irradiated with light and thermally excited are swept sufficiently fast not only in the photoconductive layer but also in the charge injection blocking layer and the surface layer. Even under the exposure condition, no residual potential or ghost is generated at all, and a high-quality image with high resolution can be stably and repeatedly obtained.

[Brief description of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic light-receiving member of the present invention, and FIGS. 2 to 7 are distributions of germanium atoms contained in the long-wavelength photosensitive layer. FIGS. 8 to 12 are explanatory diagrams for explaining the state, and FIGS. 13 to 19 are explanatory diagrams for explaining the distribution state of group III atoms or group V atoms constituting the charge injection blocking layer. Is an explanatory view for explaining the distribution state of oxygen atoms and / or nitrogen atoms constituting each charge injection blocking layer, and FIG. 20 is a schematic view for explaining the vertical cross-sectional shape of the convex and concave projections on the support surface. FIG. 21 is a schematic view of a light receiving member having an uneven support, FIG.
The figure is a schematic diagram for explaining the method of manufacturing the uneven shape,
FIG. 23 is a schematic diagram for explaining the irregular shape of the surface of the support, and FIG. 24 is an example of an apparatus for forming a light receiving layer of the light receiving member for electrophotography of the present invention, which is an apparatus for manufacturing by a glow discharge method It is a schematic explanatory view of. 25 and 26 are schematic diagrams showing the shape of the support, and FIG. 27 is a distribution diagram showing the distribution of each atom contained in the layer. About Fig. 1 100 ... Photoreceptive layer, 101 ... Support, 102 ... Charge injection blocking layer, 103 ... Photoconductive layer, 104 ... Surface layer, 105 ... Free surface, 106 ... Long wavelength light Photosensitive layer, FIG. 21 1500 ... Photoreceptive layer, 1501 ... Support, 1502-1 ... Charge injection blocking layer, 1502-2 ... Photoconductive layer, 1503 ... Surface layer,
1504 …… Free surface, 1505 …… Long wavelength light sensitive layer, about Figures 22 and 23 1601, 1701 …… Support, 1602, 1702 …… Support surface, 160
3,1703 …… Rigid sphere, 1604,1704 …… Spherical trace dent, Fig. 24 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 ……
Base cylinder 1138: heater, 1139: motor, 1140: high frequency power supply.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Minoru Kato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasushi Fujioka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (56) References JP 60-134243 (JP, A) JP 58-140748 (JP, A) JP 59-204048 (JP, A) JP 60-227262 (JP, A) A)

Claims (9)

[Claims] 1. A support, a long-wavelength photosensitive layer having a sensitivity to long-wavelength light, which is composed of a polycrystalline material containing a silicon atom and a germanium atom on the support, and a silicon atom as a base material, A charge injection blocking layer composed of an amorphous material containing an atom belonging to Group III or Group V of the periodic table, a silicon atom as a base material, and at least one of a hydrogen atom and a halogen atom as a constituent element. Photoreceptor having a photoconductive layer composed of an amorphous material containing silicon and exhibiting photoconductivity, and a surface layer composed of an amorphous material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent elements. And a surface layer containing 41 to 70 atomic% of hydrogen atoms. 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 photoreceptive member for electrophotography according to claim 1, wherein the charge injection blocking layer contains at least one of oxygen and nitrogen atoms. 5. The charge injection blocking layer according to claim 1, wherein the charge injection blocking layer contains atoms belonging to group III or group V of the periodic table in a distributed state in which a large amount is distributed on the support side.
The light-receiving member for electrophotography according to the item 1. 6. The electron according to claim 4, wherein the charge injection blocking layer contains at least one of oxygen atom and nitrogen atom in a distributed state in which a large amount is distributed on the support side. Photoreceptive member for photography. 7. The electrophotographic light according to claim 4, wherein at least one of oxygen atoms and nitrogen atoms contained in the charge injection blocking layer is internally present on the support side. Receiving member. 8. The long-wavelength photosensitive layer contains at least one atom selected from the group III or V of the periodic table, an oxygen atom and a nitrogen atom. Item 3. The light-receiving member for electrophotography according to Item 3. 9. The photoreceptive member for electrophotography according to claim 1, wherein the photoconductive layer contains an atom belonging to Group III or Group V of the periodic table.