JPH0756571B2 - Light receiving member - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to light (here, light in a broad sense, which means ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). The present invention relates to a light receiving member that is sensitive to electromagnetic waves.

[Description of Prior Art]

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an image forming member for electrophotography in an image forming field, or a document reading device, it has high sensitivity and an SN ratio [photocurrent (Ip) / dark current (Id) ], Having an absorption spectrum characteristic adapted to the spectrum characteristic of an electromagnetic wave to be irradiated, having a fast photoresponsiveness and having a desired dark resistance value, being non-polluting to the human body during use, The solid-state image pickup device is required to have a characteristic such that an afterimage can be easily processed within a predetermined time. Particularly, in the case of an electrophotographic image forming member incorporated in an electrophotographic apparatus used as an office machine as an office machine, the pollution-free property at the time of use is an important point.

Amorphous assilicon (hereinafter referred to as a-Si) is a light-receiving material that has recently received attention based on such a point. For example, German Patent Publication Nos. 2746967 and 2855718 disclose the same. Use as an image forming member for electrophotography, and application to German Patent Publication No. 2933411 describes a photoelectric conversion reader.

However, the conventional light-receiving member having a light-receiving layer composed of a-Si has the following problems in terms of electrical resistance, darkness, photosensitivity, photoresponsiveness, and other electrical, optical, and photoconductive characteristics, and operating environment characteristics. ,
Furthermore, in terms of stability over time and durability, each has been individually improved in characteristics, but in reality there is a lot of room for further improvement in measuring overall characteristics. is there.

For example, when it is applied to an electrophotographic image forming member, it is often observed that a residual potential remains in the conventional method when it is attempted to obtain high photosensitivity and high dark resistance at the same time. However, when it is used repeatedly for a long time, fatigue is accumulated due to repeated use, and a so-called ghost phenomenon that causes an afterimage is generated.

When the light-receiving layer is made of an a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type are used. A boron atom, a phosphorus atom, etc. are contained in the light-receiving layer as constituent atoms, respectively, for the purpose of controlling, or other atoms for improving other characteristics. The manner of containing these constituent atoms is not limited. As a result, problems may occur in the electrical or photoconductive properties or the electrical withstand voltage of the formed layer.

That is, for example, the life of the photocarriers formed by light irradiation in the formed light-receiving layer is not sufficient in the layer, or the injection of charges from the support side in the dark part is not sufficiently blocked, or , The image transferred to the transfer paper is generally called "white blank", which is considered to be an image defect which is considered to be caused by a local discharge breakdown phenomenon, and which is considered to be caused by the rubbing when a blade is used for cleaning, which is commonly called "white". Image defects called "streaking" have occurred. Further, when used in a humid atmosphere or used immediately after being left in a humid atmosphere for a long time, the so-called blurring of an image rarely occurs.

Furthermore, when the layer thickness is more than 10 μm, the layer is taken out from the vacuum deposition chamber for layer formation, and then the layer floats or peels from the surface of the support, or the layer is cracked with the passage of time in the air. You will win by causing phenomena such as occurring. This phenomenon occurs particularly in the case of a drum-shaped support which is usually used in the electrophotographic field, and there are some problems to be solved in terms of stability over time. is there.

Furthermore, a light-receiving member having a light-receiving layer composed of a-Si has high sensitivity over all wavelengths, and is particularly excellent in light sensitivity in the long wavelength region as compared with selenium-based photoreceptors. It has the characteristic of being However, in recent years, there has been an attempt to put a laser printer using an electrophotographic method using a light guide laser (770 to 800 μm) as a light source into practical use.
Since high speed is required for this type of printer, further sensitization in the long wavelength region of the light receiving member having the light receiving layer made of a-Si is required.

Therefore, while the characteristics of the a-Si material itself are improved, it is necessary to devise so as to solve the above-mentioned problems and satisfy the above-mentioned requirements when designing the light receiving member.

[Object of the Invention]

An object of the present invention is to solve the above-mentioned problems and to satisfy the above-mentioned requirements in a light-receiving member having a light-receiving layer composed of a-Si.

That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially stable regardless of the use environment, are substantially stable to light, and have excellent light fatigue resistance, and even when repeatedly used, a deterioration phenomenon. It is an object of the present invention to provide a light-receiving member having a light-receiving layer composed of a-Si, which does not cause deterioration, has excellent durability and moisture resistance, and has no or almost no residual potential observed.

Another object of the present invention is to provide a photoreceptive member having a photoreceptive layer composed of a-Si, which has a high photosensitivity in the entire visible light region, an excellent matching property with a semiconductor laser, and a fast photoresponse. To provide.

Still another object of the present invention is to provide a light-receiving member having a light-receiving layer composed of a-Si, which has high photosensitivity, high SN ratio characteristics, and high electrical withstand voltage.

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 layers,
The structure is precise and stable, and the layer quality is high.
It is to provide a light receiving member having a light receiving layer composed of Si.

Still another object of the present invention is to obtain a high-quality image having no image defects or image blurring, high density, clear halftone and high resolution even during long-term use. Another object of the present invention is to provide a light-receiving member for electrophotography having a light-receiving layer composed of a-Si.

Another object of the present invention is that, when applied as an electrophotographic image forming member, it has a sufficient charge retention capacity during charging processing for electrostatic image formation, and the ordinary electrophotographic method is extremely effective. A-, which has excellent electrophotographic properties that can be applied
It is to provide a light receiving member having a light receiving layer composed of Si.

[Structure of Invention]

The present invention achieves the above-mentioned object, and is product applicability, applicability of a-Si as a light receiving member used in an image forming member for electrophotography, a solid-state imaging device, a reading device, and the like,
As a result of continuing comprehensive and comprehensive research including applicability, etc., an amorphous material having silicon atoms (Si) and germanium atoms (Ge) as a base, particularly silicon atoms and germanium atoms as a base, and hydrogen atoms (H) or an amorphous material containing at least one of halogen atoms (X), so-called hydrogenated amorphous silicon germanium, amorphous hydrogenated silicon germanium, or halogen-containing amorphous hydrogenated silicon germanium [hereinafter, referred to as " a-SiGe (H, X) ". ] The light-receiving member produced by specifying the layer structure of the light-receiving member having the layer region constituted by the following not only exhibits remarkably excellent characteristics in practical use, but also a conventional light-receiving member. Compared with all, it is superior in all respects, has particularly excellent characteristics as a light receiving member for electrophotography, and has excellent absorption spectrum characteristics in the long wavelength side. It was completed based on the finding.

That is, the light receiving member of the present invention is a support and a first layer region containing silicon atoms as a matrix and containing germanium atoms in a uniform distribution state in the layer thickness direction and a silicon atom as a matrix and not containing germanium atoms. A second layer region and
And a non-uniform distribution state in the layer thickness direction so that the concentration distribution of atoms belonging to Group III or Group V of the periodic table becomes higher toward the support side and decreases toward the surface side. 1-100 μm composed of amorphous material contained in
A first layer having a layer thickness of, a silicon atom as a base material, a carbon atom, and further a hydrogen atom or a hydrogen atom and a halogen atom in the content of the hydrogen atom or the content of the hydrogen atom and the halogen atom. amorphous material sum of the amount is an amount containing a 0.01~40atomic%, that and a periodic table group III or V atoms belonging to a uniform distribution state in the layer thickness direction contained 1.0 to 10 ⁴ atomic ppm And a second layer having a layer thickness of 3 × 10 ^{−3 to} 30 μm, which is laminated in this order from the support side, and has a light-receiving layer, and at least one of the first layer and the second layer. In addition, nitrogen atoms are contained in a uniform distribution state in the layer thickness direction.

Then, as an amorphous material having a silicon atom as a base material constituting the first layer, particularly, an amorphous material containing a silicon atom (Si) as a base material and containing at least one of a hydrogen atom (H) and a halogen atom (X). Material, ie a-
Si (H, X) is used. An amorphous material containing a silicon atom forming the second layer as a host and containing a carbon atom (C) and a substance for controlling conductivity, particularly a silicon atom (Si) as a host, and a carbon atom (C), A substance that controls conductivity and an amorphous material containing a hydrogen atom (H) or a hydrogen atom (H) and a halogen atom (X) [hereinafter referred to as "a
-SiCM (H, X) "(where M represents a substance that controls conductivity). ] Is used. In the present specification, the hydrogen atom or the hydrogen atom and the halogen atom contained in the second layer may be expressed as “hydrogen atom and / or halogen atom” for convenience.

Examples of the substance that controls the conductivity include so-called impurities in the field of semiconductors, and an atom belonging to Group III of the periodic table that gives P-type conductivity (hereinafter simply referred to as “Group III atom”). Or an atom belonging to Group V of the periodic table that gives n-type conductivity (hereinafter simply referred to as “Group V atom”). Specific examples of the group III atom include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). Particularly preferably, B and Ga are To use. Examples of the Group V atom include P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), and the like, but P and As are particularly preferably used. The conductivity-controlling substance contained in the first layer and the conductivity-controlling substance contained in the second layer may be the same or different.

By the way, in the light receiving member of the present invention, the purpose of incorporating germanium in a uniform distribution state in a part of the layer region in contact with the support of the first layer is to improve the absorption spectrum characteristic on the long wavelength side. . Then, the light receiving member of the present invention having a first layer containing a germanium atom in a uniform distribution state in a part of the layer region in contact with the support is used particularly as a light receiving member for electrophotography. ,
It exhibits outstanding characteristics when it has high photosensitivity and excellent photoresponsiveness in the entire visible light range. Further, in the light receiving member of the present invention, in order to contain a germanium atom in a part of the layer region in contact with the support, especially when using a long wavelength one such as a semiconductor laser, the layer region containing a germanium atom is Since the light on the long wavelength side is completely absorbed, it is possible to prevent the phenomenon of interference caused by the reflection from the surface of the support.

Further, the light receiving member of the present invention is a material which controls the conductivity in the whole layer region or a part of the layer region of the first layer II
Although it contains a group I atom or a group V atom in a non-uniform distribution state, the conductivity type and / or conduction of the first layer can be improved by incorporating a substance that controls conductivity into the first layer. Rate control, formation of a charge blocking layer, improvement of charge transfer between the first layer and the second layer, or increase of apparent dark resistance during charging treatment. is there. Then, as will be described later in detail, the layer region of the first layer containing the substance for controlling the conductivity is the whole layer region or a part of the layer region, or the conductivity contained in the first layer is Depending on whether the conductivity type of the controlling substance is the same as or different from the conductivity type of the substance controlling the conductivity contained in the second layer, the above-mentioned action and effect are different. It is necessary to appropriately select the layer region containing the substance controlling the conductivity and the conductivity type of the substance controlling the conductivity according to the expected effect.

Further, the light receiving member of the present invention contains a nitrogen atom in a uniform or non-uniform state in at least one of the entire layer region or a part of the first layer and the entire region of the second layer. Yes, by incorporating a nitrogen atom, the photoreceptive member has high photosensitivity and high dark resistance, and improved adhesion between the support and the first layer or between the first layer and the second layer. And the like. Also, regarding these actions and effects, whether the nitrogen atom is contained in the entire layer region of the first layer, or in a part of the layer region of the first layer, or in the second layer. Or, it is different depending on whether it is contained in a uniform distribution state or a non-uniform distribution state, and depending on the purpose and expected effect, the layer or layer region and the distribution in which the nitrogen atom is contained. It is necessary to select the state appropriately.

The second layer of the photoreceptor of the present invention is the moisture resistance of the photoreceptor,
It is provided on the first layer in order to improve continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability, which is due to the inclusion of carbon atoms in the second layer. Can be achieved. Further, when such a second layer is provided on the first layer, problems such as generation of residual potential and generation of electrostatic trace scratches during charging treatment often occur. By containing a group III atom or a group V atom, which is a substance that controls the conductivity of, the occurrence of such a problem can be prevented.

The first layer and the second layer of the light receiving member of the present invention may contain a hydrogen atom (H) or a halogen atom (X), if necessary. Specific examples of the halogen atom (X) include fluorine, chlorine, bromine and iodine, and particularly preferable ones are fluorine and chlorine. Then, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first layer and the second layer of the present invention, or the sum of the amounts of hydrogen atoms and halogen atoms (H + X) (however, In the two layers, the amount of hydrogen atoms (H) or the sum of the amounts of hydrogen atoms and halogen atoms (H + X) is generally 1 × 10 5.
^-2 to 4 x 10 atomic%, preferably 5 x 10 ^{-2 to} 3
× 10 atomic%, optimally 1 × 10 ^{-1 to} 25 atomic%.

Hereinafter, the specific layer structure of the light receiving member of the present invention will be described in more detail with reference to the drawings.

1 to 4 are schematic views for explaining the layer structure of the light receiving member of the present invention, in each of which 100 is a light receiving member, 101
Is a support, 102 is a first layer, 103 is a second layer, 104 is a free surface, and 105 to 110 are layer regions.

Support The support 101 used in the present invention may be either conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, Al, Cr, Mo,
Examples include metals such as Au, Nb, Ta, V, Ti, Pt, and Pb, and alloys thereof. Examples of the electrically insulating support include films or sheets of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, ceramics, paper and the like. It is preferable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and a light receiving layer is provided on the surface side subjected to the conductive treatment.

For example, if it is glass, NiCr, Al, Cr,
Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , I
Conductivity is provided by providing a thin film made of TO (In ₂ O ₃ + SnO ₂ ) or the like, or synthetic resin film such as polyester film is made of NiCr, Al, Ag, Pb, Zn, Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is given to the surface. The support may have any shape such as a cylindrical shape, a belt shape, or a plate shape.
The shape can be appropriately determined depending on the application and the desire. For example, in the case of continuous high-speed copying, when used as an electrophotographic image forming member, an endless belt shape or a cylindrical shape. Is desirable. The thickness of the support is appropriately determined so that a desired light receiving member can be formed, but when flexibility is required as the light receiving member,
It can be made as thin as possible within a range where the function as a support can be sufficiently exhibited. However, in terms of mechanical strength and the like in terms of manufacturing and handling the support, it is usually 10 μm.
That is all.

First Layer The first layer 102 is provided on the support 101, and is a-Si containing a germanium atom from the support side.
(H, X), that is, a layer region 105 composed of a-SiGe (H, X)
And a layer region 106 made of a-Si (H, X) containing no germanium atom are laminated in this order. FIG. 2 schematically shows the layer structure. Then, in the first layer 102 of the light receiving member of the present invention,
A group III atom or a group V atom which is a substance for controlling conductivity, and a nitrogen atom if necessary, and the group III atom or the group V atom is the whole layer region of the layer 102 or The nitrogen atoms are distributed in a uniform distribution state in a part of the layer area, and the nitrogen atoms are distributed in a uniform distribution state in the entire layer area or a part of the layer area of the layer 102. Here, the uniform distribution state means that the distribution state of the contained atoms is uniform in both the plane direction parallel to the support surface of the first layer and the layer thickness direction of the first layer. A uniform distribution state means that the distribution concentration of atoms contained is uniform in the plane direction parallel to the support surface of the first layer, but non-uniform in the layer thickness direction of the first layer. Say.

The light-receiving member of the present invention contains germanium atoms in a uniform distribution state in a part of the layer region 105 in contact with the support of the first layer 102, so that the absorption spectrum characteristic on the long wavelength side is improved, If the photosensitivity is high and the photoresponsiveness is excellent in the entire visible light region from a relatively short wavelength to a relatively long wavelength, it will have outstanding characteristics. When a long-wavelength laser such as a semiconductor laser is used as a light source, a layer region containing no germanium atom
Light in the long wavelength range, which is hardly absorbed by 106, can be substantially completely absorbed by the layer region 105 containing germanium atoms, so that interference due to reflection from the support surface and a phenomenon Occurrence can be prevented in advance. Therefore, it is particularly important to incorporate germanium atoms in a part of the layer region 105 which is in contact with the support. The amount of germanium atoms contained in a part of the layer region 105 in contact with the support of the first layer is appropriately determined according to the desired characteristics that can achieve the object of the present invention, and is usually 1 〜9.5 × 10 ⁵ atomic ppm, preferably 1 × 10 ²
~ 8 x 10 ⁵ atomic ppm, optimally 5 x 10 ^{2 to} 7 x 10 ⁵ atomi
It is desirable to use c ppm.

The layer thickness of the layer region 105 containing germanium atoms (T _G ) and the layer thickness of the layer region 106 not containing germanium atoms (T)
Is one of the important factors for efficiently achieving the object of the present invention, and is important in designing the light receiving member so that the light receiving member to be formed can be sufficiently provided with desired characteristics. However, the layer thickness (T _B ) of the layer region 105 is usually 3 × 10 ^{−3 to} 50 μ, but preferably 4 × 10 ^{−3 to} 40 μ, Optimal 5 × 10 ^-3 to 50
It is desirable to set to μ. Also, the layer thickness (T) of the layer region 106
Is usually 0.5 to 90 μ, preferably 1 to 80 μ, and most preferably 2 to 50 μ.

Furthermore, the sum (T _B + T) of the layer thickness of the layer region 105 (T _B ) and the layer thickness of the layer region 106 (T _B + T) is required for both the layer regions and for the entire first layer. Characteristics, and further, based on the mutual and organic relationship with the characteristics required for the entire light-receptive layer, it needs to be sufficiently taken into consideration when forming the layer of the light-receptive member, and usually 1 Although it is set to ˜100 μ, preferably 1 to 80 μ, and optimally 2 to 50 μ.

Furthermore, the layer thickness (T _B ) of the layer region 105 and the layer region 106 are
The layer thickness (T) of is to satisfy the relationship of T _B / T ≦ 1,
It is desirable to determine each, more preferably T _B / T ≤ 0.
9. Optimally, it is desirable to determine so as to satisfy the relationship of T _B /T≦0.8.

It is necessary to determine the layer thickness of the layer region 105 in consideration of the amount of germanium atoms contained in the layer region 105. For example, the amount of germanium atoms contained is 1 × 10 ⁵ atomi.
When it is c ppm or more, it is desirable that the layer thickness (T _B ) of the layer region 105 is considerably thin, specifically, 30 μm or less,
It is preferably 25 μm or less, and most preferably 20 μm or less.

The first layer of the present invention is a conductivity controlling substance III
As will be described later, the action and effect obtained by containing a group atom or a group V atom depends on the distribution state of the atom or a group III atom or a group V atom contained in the first layer. The conductivity type of the group atom differs depending on whether it is the same as or different from the conductivity type of the group III atom or the group V atom contained in the second layer. Therefore, in order to obtain a light-receiving member having desired characteristics depending on the purpose, the layer region containing the group III atom or the group V atom in a non-uniform distribution state is used as the whole layer region, or It is necessary to appropriately select whether to form a part of the layer region and to make the group III atom have the same conductivity type as the group V atom or that of the second layer. Further, the amount of the group III atom or the group V atom contained in the first layer is also
The amount of the Group III atom or the Group V atom to be contained in the first layer is also different in order to obtain a light-receiving part having desired characteristics depending on the purpose because it depends on the intended action and effect. It is necessary to select it appropriately.

That is, when a group III atom or a group V atom is contained in the entire layer region of the first layer, the effect of controlling the conductivity and / or the conductivity of the first layer is obtained. In this case, the amount of the group III atom or the group V atom contained in the first layer region may be relatively small, usually 1 × 10 ⁻³ to
The concentration is set to 1 × 10 ³ atomic ppm, preferably 5 × 10 ^{−2 to} 5
× 10 ² atomic ppm, optimally 1 × 10 ^-1 to 2 × 10 ² atomic p
pm is preferred. Further, in this case, even if the conductivity type of the substance controlling the conductivity contained in the first layer is the same as that of the substance contained in the second layer described later,
Alternatively, they may be different.

In addition, regarding the first layer, the first layer is provided on the side in contact with the support.
The content of the group III atom or the group V atom becomes relatively large, and the group III atom or the group V atom is present on the side in contact with the second layer.
When the content of the group atom is set to be relatively small or substantially close to zero, the group III atom or the group V atom
The charge-blocking layer is formed by the layer region containing a relatively large amount of group atoms. In this case, the first layer contains a relatively large amount of group III atoms or group V atoms, and is usually 3 × 10 to 5 × 10 ⁴ atomic.
ppm, but preferably 5 × 10 to 1 × 10 ⁴ atomic ppm,
The optimum value is 1 × 10 ^{2 to} 5 × 10 ³ atomic ppm.

Next, the amount of the group III atom or the group V atom contained in the first layer is relatively large on the support side and decreases from the support side toward the interface with the second layer. In the vicinity of the interface with the second layer, the amount of the group III atom or the group V atom should be relatively small or substantially zero.
Some typical examples of distributing group atoms are described in
Although the description will be made with reference to FIGS. 13 to 13, the present invention is not limited to these examples. In each drawing, the horizontal axis represents the distribution concentration C of the group III atom or the group V atom, the vertical axis represents the layer thickness of the first layer 102, and t _B represents the side of the support 101 and the first layer. The interface position, t _T, represents the interface position between the second layer 103 and the first layer.

FIG. 5 shows a first typical example of the distribution state of the group III atoms or the group V atoms contained in the first layer in the layer thickness direction. In this example, from the interface position t _{B at} which the first layer containing a Group III atom or a Group V atom and the surface of the support are in contact with each other, t ₁
Until the distribution concentration C of group III atoms or group V atoms is C ₁
From the position t ₁ to the interface position t _T where the first layer is in contact with the second layer, the distribution concentration C of the group III atom or the group V atom is continuously changed from the concentration C ₂ to the position. Decrease interface position
At t _T , the distribution concentration C of group III atoms or group V atoms C
Becomes C ₃ .

FIG. 6 shows one of other typical examples. In that example,
The distribution concentration C of the group III atom or the group V atom contained in the first layer is C ₄ from the position t _B to the position t _T.
It continuously decreases from and reaches the concentration C ₅ at the position t _T.

In the example shown in FIG. 7, from the position t _B to t ₂ keeps the constant value distribution concentration C of the group III atoms or group V atoms is concentration C _6, up to the position t _T from the position t ₂ , The distribution concentration C of the group III atom or the group V atom gradually and continuously decreases from the concentration C _7, and the distribution concentration C of the group III atom or the group V atom is substantially zero at the position t _T. Becomes However, the term "substantially zero" here means that the amount is less than the detection limit amount.

In the example shown in FIG. 8, the distribution concentration C of the group III atom or the group V atom gradually decreases continuously from the concentration C ₈ until reaching the position t _T from the position t _B , and at the position t _T. The distribution concentration C of the group III atom or the group V atom is substantially zero.

In the example shown in FIG. 9, the distribution concentration C of the group III atoms or group V atoms is a constant value of the concentration C ₉ is between the position t ₃ from the position t _B, the position t _T from the position t ₃ Between the concentrations
It decreases in a linear function from C ₉ to the concentration C ₁₀ .

In the example shown in FIG. 10, the distribution concentration C of the group III atom or the group V atom is the concentration C ₁₁ from the position t _B to the position t _4.
Is constant and decreases from the position t ₄ to the position t _{T in} a linear function from the concentration C ₁₂ to the concentration C ₁₃ .

In the example shown in FIG. 11, the distribution concentration C of the group III atom or the group V atom has a linear function from the position t _B to the position t _T and from the concentration C ₁₄ to substantially zero. Decrease.

In the example shown in FIG. 12, the distributed concentration C of the group III atom or the group V atom decreases linearly from the position t _B to the position t ₅ until the concentration C ₁₅ to the concentration C ₁₆ . The constant value of the concentration C ₁₆ is maintained from the position t ₅ to the position t _T.

Finally, in the example shown in FIG. 13, the distribution concentration C of the group III atom or the group V atom is the concentration C ₁₇ at the position t _B ,
From the position t _B to the position t ₆ , the concentration C ₁₇ starts to decrease gradually, and then decreases sharply near the position t ₆ and reaches the concentration C ₁₈ at the position t ₆ . Next, from the position t ₆ to the position t _7, at the beginning, it decreases sharply, and thereafter it gradually decreases gradually,
The concentration is C _{19 at the} position t ₇ . Furthermore, position t ₇ and position t ₈
Between them, the concentration is extremely slow and gradually decreases, and the concentration becomes C ₂₀ at the position t ₈ . Furthermore, from the position t ₈ to the position t _T , the concentration C ₂₀ gradually decreases until it becomes substantially zero.

As in the example shown in FIGS. 5 to 13, the distribution concentration C of group III atoms or group V atoms C on the side of the first layer close to the support side.
In the case where the distribution concentration C has a considerably low concentration portion or a concentration portion substantially close to zero on the interface side of the first layer with the second layer. Providing a localized region having a relatively high concentration distribution of group III atoms or group V atoms in a portion near the support side, preferably from the interface position where the localized region A contacts the surface of the support By providing the thickness within 5 μm, the above-described effect that the layer region in which the distribution concentration of the group III atom or the group V atom is high forms the charge injection blocking layer is more efficiently achieved.

Contrary to the above-mentioned case, a relatively large amount of a group III atom or a group V atom, which is a substance that controls conductivity, is contained on the side of the first layer which is in contact with the second layer. In this case, if the conductivity types of the substances controlling the conductivity contained in the first layer and the second layer are the same, the energy level consistency between the first layer and the second layer is improved, The effect of enhancing the transfer of charges between the two layers is exhibited, and this effect is particularly remarkable when the layer thickness of the second layer is large and the dark resistance is high.

Furthermore, in the case where a group III atom or a group V atom, which is a substance that controls conductivity, is contained so that the amount of the first layer is in contact with the second layer in a relatively large amount, If the conductivity type of the substance that controls the conductivity contained in the second layer is different, the layer region containing a large amount of the substance positively becomes a junction between the first layer and the second layer. The effect of increasing the apparent dark resistance during the charging process is achieved.

In any case, a group III atom or a group V atom when a relatively large amount of a group III atom or a group V atom is contained on the side of the first layer in contact with the second layer Some of the typical examples of the distribution state in the first layer are those obtained by reversing the layer thickness direction of the typical example shown in FIGS. 5 to 13, that is, t _B is the second layer 103. First layer 102
The same explanation will be made by using the position of the interface between and as t and the position of the interface between the support and the first layer as t _T. When a relatively large amount of Group III atom or Group V atom is contained on the side in contact with the second layer, the amount thereof may be relatively small, usually 1 × 10 ^-3 to 1 The concentration is set to x10 ³ atomic ppm, preferably 5 x 10 ^{-2 to} 5 x 10 ² atomic ppm, and most preferably 1 x 10 ^-1 to 2 x 10 ² atomic ppm.

As described above, the action and effect of each of the distribution states of the group III atoms or the group V atoms have been described individually. For obtaining the light receiving member having the characteristics capable of achieving the desired purpose,
It is said that the distribution state of these Group III atoms or Group V atoms and the amount of Group III atoms or Group V atoms contained in the first layer are used in an appropriate combination as necessary. There is no end.

In the light-receiving member of the present invention, by containing a nitrogen atom in the first layer, the photosensitivity and dark resistance of the first layer are increased, and further, the support and the first layer or the first layer and the first layer. The adhesion of the second layer is improved.

The layer region containing nitrogen atoms in the first layer may be the entire layer region of the first layer or a part of the layer region. Further, the distribution state of nitrogen atoms in the layer region may be uniform or non-uniform. Then, as described later, whether the layer region containing the nitrogen atoms is the whole layer region or a part of the layer region, or whether the distribution state of the nitrogen atoms in the region is uniform or non-uniform Therefore, the action and effect to be played are different. Therefore, in order to obtain a light-receiving member that can efficiently achieve the desired purpose and expected effect, it is necessary to appropriately select the layer region containing nitrogen atoms and the distribution state. Furthermore, since the amount of nitrogen atoms contained in the first layer also differs depending on the purpose and the expected effect, it is necessary to obtain the light receiving member having the desired purpose and effect. It is also necessary to appropriately select the amount of nitrogen atoms contained in the layer.

That is, as schematically shown in FIG. 1, when nitrogen atoms are contained in the entire layer region of the first layer, the photosensitivity and dark resistance of the first layer are increased.
In this case, the amount of nitrogen atoms contained in the first layer is made relatively small in order to maintain high photosensitivity.

Further, as schematically shown in FIG. 2, a part of the layer region 105 which is in contact with the support of the first layer is made to contain nitrogen atoms in a uniform distribution state, or is contacted with the support of the first layer. When nitrogen atoms are contained so that the distribution concentration of nitrogen atoms is relatively high on the side, the effect of improving the adhesion between the support 101 and the first layer is achieved. Further, as schematically shown in FIG. 3, a part of the layer region 106 of the first layer which is in contact with the second layer is made to contain nitrogen atoms in a uniform distribution state, or the second layer of the first layer is included. When nitrogen atoms are contained so that the distribution concentration of nitrogen atoms on the side in contact with the layer is relatively high, the effect of improving the adhesion between the first layer and the second layer is achieved. . Furthermore, the effect of improving the adhesion between the first layer and the second layer can also be achieved by incorporating nitrogen atoms in the second layer, which will be described later, in a uniform distribution state. It is a thing.

Regarding the non-uniform distribution of the nitrogen atoms in the first layer on the side of the support or on the side of the first layer which is in contact with the second layer, the non-uniform distribution of the nitrogen atoms is described in Group III atoms or V It is similar to the case where the group atoms are nonuniformly distributed, and typical examples thereof are shown in FIGS. 5 to 11, but the present invention is not limited to these examples.

Then, in order to improve the adhesion between the support and the first layer or between the first layer and the second layer, when a nitrogen atom is contained, the amount of the nitrogen atom contained in the first layer is It is preferable to use a relatively large amount to ensure the stability.

Further, as described above, in the present invention, by containing a nitrogen atom in a relatively high concentration on the side of the first layer which is in contact with the support, it is possible to improve the adhesion between the support and the first layer. However, in this case, if a localized region containing a high concentration of nitrogen atoms is provided, the adhesion can be further improved. If such a localized region is described by using the symbols shown in FIGS. 5 to 13, it is desirable to provide it within 5 μm from the interface position t _B. Such a localized region contains a nitrogen atom. It may be the whole of the partial layer region 105 or a part of the partial layer region.

In the above, the action and effect are described for each distribution state of nitrogen atoms. However, in the light receiving member of the present invention, in order to simultaneously exhibit two or more of these action and effects, a layer containing a nitrogen atom is included. It goes without saying that the regions and the distribution state of nitrogen atoms are appropriately combined and used. For example, in order to improve both the adhesion between the support and the first layer and the improvement of the photosensitivity and dark resistance of the first layer, the support of the first layer is required. Nitrogen atoms may be distributed so as to have a relatively high concentration on the body side, and nitrogen atoms may be distributed so as to have a relatively low concentration in other layer regions.

In the present invention, the amount of nitrogen atoms contained in the first layer is adjacent to each other in the properties required for the first layer itself or in the case where it is contained in a partial layer region in contact with the support or the second layer. Determined in consideration of mutual and organic relationships such as the relationship with the characteristics of the layer or support, usually 1 x 10
^{-3 to} 50 atomic%, more preferably 2 x 10 ^-3 to 40
atomic%, optimally 3 × 10 ^{−3 to} 30 atomic%. In addition, by including nitrogen atoms in the entire layer region of the first layer,
Alternatively, when the proportion of a part of the layer region containing nitrogen atoms in the first layer is sufficiently large, the upper limit of the amount of nitrogen atoms is preferably sufficiently smaller than the above value. For example, when the layer thickness of a part of the layer region containing nitrogen atoms is two fifths or more of the layer thickness of the first layer, the amount of nitrogen atoms contained in the part of the layer region is The upper limit is usually 30 at
Omic%, but more preferably 20 atomic%, optimally
It should be 10 atomic% or less.

Further, when forming a localized region containing a high concentration of nitrogen atoms, the maximum distribution value of nitrogen atoms, C _max, is usually 5 × 10 ² atomic ppm or more, as the distribution state of nitrogen atoms in the layer thickness direction. It is desirable to form a distribution state of preferably 8 × 10 ² atomic ppm or more, and most preferably 1 × 10 ³ atomic ppm or more.

In the present invention, by containing a nitrogen atom in the first layer, to obtain the effects as described above,
For the purpose of further promoting these effects, oxygen atoms can be further contained in the first layer in addition to the above-mentioned nitrogen atoms. Further, as described above, the nitrogen atom of the present invention may be contained in the second layer, but in this case as well, an oxygen atom can be further contained for the same purpose. In containing the oxygen atom, the distribution state and the content thereof are the same as in the case of the nitrogen atom, that is, when the main purpose is to achieve high photosensitivity and high dark resistance,
It is contained in the entire area of the first layer, and its amount is relatively small, and its main purpose is to improve the adhesion between the support and the first layer or between the first layer and the second layer. In this case, as shown in FIGS. 2 and 3 described above, a relatively large amount is contained in a part of the first layer in a uniform or non-uniform distribution state. The layer regions containing nitrogen atoms and oxygen atoms, the contents thereof, or the distribution state of these atoms may be the same or different.

As described above, the first layer of the present invention may contain a germanium atom, a Group III atom or a Group V atom, a nitrogen atom, and an oxygen atom. In order to efficiently obtain the desired characteristics in the above, the content of each atom and the distribution state of each atom are appropriately selected for use, and the layer regions containing each atom are different from each other. Alternatively, they may partially overlap with each other. Hereinafter, one example thereof is shown in FIG. 4, but the present invention is not limited to the example. In the example shown in FIG. 4, the first layer is from the support side,
The layer region 108, the layer region 109, and the layer region 110 are layer regions, and the layer region 108 contains a germanium atom and a group III atom or a group V atom at a high concentration, and further contains a nitrogen atom. It is assumed that the layer region 109 contains a group III atom or a group V atom at a low concentration and further contains a nitrogen atom. The layer region 110 is assumed to contain neither germanium atom, group III atom or group V atom, nor nitrogen atom.

The layer thickness of the first layer 102 is one of the important factors for efficiently achieving the object of the present invention, and is appropriately determined according to the desired object. Further, the amount of germanium atom, group III atom or group V atom, nitrogen atom, oxygen atom, and hydrogen atom and / or halogen atom contained in the first layer, or the mutual amount of the first layer and the second layer. It is also necessary to determine mutual relations and organic relations depending on required characteristics in relation to the layer thickness of the. In addition, it is necessary to fully consider the economical efficiency in consideration of productivity and mass productivity. For this reason, the layer thickness of the first layer is usually 1 to 1 × 10 ² μ, preferably 1 to 80 μ, and most preferably 2 to 50 μ.

The second layer 103 of the light receiving member of the present invention is a-SiC (H, X).
Which contains a substance for controlling conductivity in a uniform distribution state in all layer regions of the layer, wherein the moisture resistance is
It is provided on the first layer for the purpose of improving continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability and the like. This object can be achieved by structurally introducing carbon atoms into the amorphous material forming the second layer. When the carbon atoms are structurally introduced into the second layer, the above-mentioned properties are improved with the increase of the amount of carbon atoms, but if the amount of carbon atoms is too large, the layer quality is deteriorated, and the electrical and Mechanical properties are also reduced. Therefore, the content of carbon atoms is usually 1 × 10 ^{−3 to} 90 atomic%,
It is preferably 1 to 90 atomic%, and most preferably 10 to 80 atomic%.

Further, in order to improve the characteristics of continuous repeated use and durability, it is preferable to increase the layer thickness of the second layer, but when the layer thickness is increased, residual potential is generated. The generation of such residual potential should be prevented by containing a substance that controls conductivity in the second layer, that is, a group III atom or a group V atom, or should be suppressed to such an extent that there is no substantial effect. You can Further, the second layer of this kind in the usual case is excellent in mechanical durability, but when the surface of the layer is rubbed or pressed with a sharp tip, the surface of the layer is Even if it does not remain as a so-called scratch, it often appears as an electrostatic charge trace scratch during the charging process, and often causes deterioration of the image quality of the toner transfer image.
Even in such a case, by causing the second layer to contain the above-mentioned substance that controls the conductivity, it is possible to prevent such a problem from occurring. Therefore, the inclusion of a Group III atom or a Group V atom, which is a substance that controls conductivity, in the second layer makes it possible for the second layer to have a desired property for achieving the object of the present invention. Important for forming layers.
Then, a Group III atom or a V group contained in the second layer
The amount of family atoms, usually is a 1.0 to 10 ⁴ atomic ppm, preferably 10~5 × 10 ³ atomic ppm, and optimally 10 ² to 5 × 10
³ atomic ppm is preferable.

In the second layer 103 of the light receiving member of the present invention, in order to improve the adhesion between the first layer 102 and the second layer 103, nitrogen atoms or oxygen atoms are added to all layers of the layer 103. It can also be contained in the region in a uniform distribution state, particularly in the case where the first layer 102 contains at least nitrogen atoms, and also does not contain oxygen atoms, the second layer 103 contains at least nitrogen atoms. , And, if necessary, contain an oxygen atom. The amount of nitrogen atoms or oxygen atoms contained in the second layer 103 is usually 1 × 10 ^{−3 to} 50 atomic%, more preferably 2 × 10 ^{−3 to} 40 atomic%, most preferably 3 ×. 10 ^{-3 to} 30 atom
ic%.

The second layer 103 needs to be carefully formed to obtain the desired properties. That is, a substance having a silicon atom, a carbon atom, a hydrogen atom and / or a halogen atom, and a group III atom or a group V atom as a constituent atom has a morphology depending on the content of each constituent atom and other preparation conditions. Is a crystalline state to an amorphous state, and the electrical properties are conductive, semiconductive, and insulating, and the photoelectric property is photoconductive to non-photoconductive. It is important to select the content of each constituent atom, the preparation conditions, etc. so that the second layer 103 having desired characteristics according to the purpose can be formed.

For example, when the second layer 103 is provided mainly for the purpose of improving electrical withstand voltage, the amorphous material forming the second layer 103 has a remarkable electrical insulating behavior under use conditions. Form. Further, when the second layer 103 is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics, the amorphous material forming the second layer 103 has a degree of electrical insulation described above. Although it is relaxed to some extent, it is formed so as to have some sensitivity to irradiation light.

Further, in the present invention, the layer thickness of the second layer is also one of the important factors for efficiently achieving the object of the present invention, and is appropriately determined according to the intended purpose. , According to the amount of Group III atom, Group V atom, carbon atom, halogen atom, hydrogen atom contained in the layer, or the characteristics required for the second layer, under mutual and organic relationships. Need to decide. In addition, it is necessary to consider the economical aspect in consideration of productivity and mass productivity. For this reason, the layer thickness of the second layer is usually 3 × 10 ^{−3 to} 30 μ,
More preferably 4 × 10 ^{−3 to} 20 μ, and particularly preferably 5 × 10 3.
^{-3 to} 10μ.

The light-receiving member of the present invention has the layer structure as described above, and can solve all of the problems of the light-receiving member having the light-receiving layer composed of the amorphous silicon described above, and have an extremely excellent electrical property. It exhibits optical and photoconductive characteristics, electrical withstand voltage characteristics, and operating environment characteristics, and has high photosensitivity in the entire visible light range, particularly high light sensitivity in the long wavelength range, and photoresponsiveness. Is excellent and excellent in matching property with a semiconductor laser. Furthermore, when applied as an electrophotographic image forming member, there is no effect of residual potential on image formation, its electrical characteristics are stable and highly sensitive, and it has a high SN ratio. It is possible to stably and repeatedly obtain a high-quality image having excellent light resistance and repeated use characteristics, high density, clear halftone, and high resolution.

Further, in the light-receiving member of the present invention, the light-receiving layer formed on the support has a strong layer itself, and can be repeatedly used at high speed for a long time continuously.

Next, a method for forming the light receiving layer of the present invention will be described.

Any of the amorphous materials forming the light receiving layer of the present invention is formed by a vacuum deposition method utilizing a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method. These manufacturing methods are appropriately selected and adopted depending on factors such as the manufacturing conditions, the load level of capital investment, the manufacturing scale, and the desired characteristics of the light receiving member to be manufactured. Since it is relatively easy to control the conditions for producing the light receiving member having, and the carbon atom and the hydrogen atom can be easily introduced together with the silicon atom, the glow discharge method or the sputtering method is used. It is suitable. Then, the glow discharge method and the sputtering method may be used together in the same apparatus system.

For example, in order to form a layer composed of a-Si (H, X) by the glow discharge method, basically, silicon atoms (S
Introducing a source gas for introducing hydrogen atoms (H) and / or for introducing halogen atoms (X) together with a source gas for supplying Si capable of supplying i) into a deposition chamber where the pressure inside can be reduced,
A glow discharge is generated in the deposition chamber to form a layer of a-Si (H, X) on the surface of a predetermined support placed in advance at a predetermined position.

Specific examples of the halogen atom (X) to be contained in the layer as needed include fluorine, chlorine, bromine and iodine, but fluorine and chlorine are preferable.

The raw material gas for supplying Si includes SiH ₄ , Si ₂ H ₆ , and Si.
Examples thereof include silicon hydrides (silanes) in a gas state such as ₃ H ₈ and Si ₄ H ₁₀ , which can be gasified, and particularly SiH _{4 in} terms of ease of layer formation work and good Si supply efficiency. , Si ₂ H ₆ are preferred.

As the raw material gas for supplying the hydrogen atoms, H ₂ gas, HC
l, HF, HBr, HI and other halides, SiH ₄ , Si ₂ H ₆ , Si
₃ H _8, Si ₄ H ₁₀ the hydrogenation, such as silicon or SiH ₂ F _2, SiH,
₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr _{3 and the} like halogen-substituted silicon hydride or the like in the gas state or gasifiable can be used, when using these source gases Is
This is effective because it is easy to control the content of hydrogen atoms, which is extremely effective in controlling electrical or photoelectric properties. Further, when a hydrogen halide or a halogen-substituted silicon hydride is used, a halogen atom is introduced together with the introduction of a hydrogen atom, which is effective.

Further, as the source gas for introducing the halogen atom, many halogen compounds can be mentioned, for example, a halogen gas,
Gaseous or gasifiable halogen compounds such as halides, interhalogen compounds, halogen-substituted silane derivatives are preferred. Specifically, halogen compounds include fluorine, chlorine, bromine, iodine halogen gas, Br
_{F, ClF, ClF 3, BrF} 5, BrF 3, IF 3, IF 7, ICl, may be mentioned interhalogen compounds such as IBr, silicon compounds containing halogen atoms, what is called, silane derivatives substituted by halogen atom As preferable examples, silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ are preferable.

In the case of forming by a glow discharge method using a silicon compound containing such a halogen atom, a halogen atom can be formed on a predetermined support without using a silicon hydride gas as a raw material gas capable of supplying Si. It is possible to form a layer of a-Si containing The halogen compound or a halogen-containing silicon compound can be effectively used as a raw material gas for introducing a halogen atom, but in addition to these, HF,
Hydrogen halide such as HCl, HBr, HI, SiH ₂ F ₂ , SiH ₂ I ₂ , Si
Halogen-substituted silicon hydrides such as H ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , and SiHBr _{3 and the} like, which are in a gas state or can be gasified, and which have a hydrogen atom as one of the constituent elements are also effective starting materials. I can name it.

Halides containing these hydrogen atoms, since it is possible to introduce a hydrogen atom very effective in controlling the electrical or photoelectric properties simultaneously with the introduction of a halogen atom in the layer during layer formation,
It can be used as a suitable raw material for introducing a halogen atom.

When a layer containing halogen atoms is formed by using the glow discharge method, basically, a halogen gas, which is a raw material gas for supplying Si, and a gas such as Ar and He are mixed at a predetermined mixing ratio and gas flow rate. As described above, a layer can be formed on a predetermined support by introducing a glow discharge into the deposition chamber to form a plasma atmosphere of these gases.
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.

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 this is used for a predetermined gas plasma. In the case of ion plating, which is sputtered in the atmosphere, 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, an electron beam method (EB method), etc. Therefore, it can be carried out by heating and evaporating and allowing the flying evaporate to pass through a predetermined gas plasma atmosphere.

At that time, in the case of introducing a halogen atom into the layer formed by any of the sputtering method and the ion plating method, the gas of the halogen compound or the silicon compound containing the halogen atom is introduced into the deposition chamber. Then, a plasma atmosphere of the gas may be formed.

When introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, a gas such as H ₂ or the above-mentioned silanes is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. You can do it. Specifically, 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 also introduced into the deposition chamber together with an inert gas such as He and Ar as necessary to form a plasma atmosphere. Then, the Si target is sputtered to form a layer of a-Si (H, X) on the support.

A-Si (H, X) was made to contain germanium atom, group III atom or group V atom, nitrogen atom or further oxygen atom or carbon atom by glow discharge method, spattering method or ion plating method. To form a layer composed of an amorphous material, the a-Si (H,
X) when forming a layer composed of germanium atoms,
A starting material for introducing a group II atom or a group V atom, a nitrogen atom, an oxygen atom, or a carbon atom is used together with a starting material for forming a-Si (H, X), and the respective amounts in the layer to be formed. Control.

For example, in order to form a layer composed of a-SiGe (H, X) by the glow discharge method, basically, a source gas for supplying Si capable of supplying silicon atoms (Si) is used together with germanium. Source gas for supplying Ge, which can supply atoms (Ge),
A source gas for supplying H, which can supply hydrogen atoms (H), and / or X, which can supply halogen atoms (X), is introduced into a deposition chamber whose inside can be decompressed, and a glow gas is introduced into the deposition chamber. A discharge is generated to form a layer of a-SiGe (H, X) on the surface of a predetermined support placed in advance at a predetermined position.

As the raw material gas for supplying Ge, GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ ,
_{Ge 4 H 10, Ge 5 H} 12, Ge 6 H 14, Ge 7 H 16, Ge 8 H 18, Ge 9 H 20 , etc. germanium hydride capable or gasified gas state are exemplified in, particularly during layer formation working GeH ₄ , Ge ₂ H _6, and Ge ₃ H ₈ are preferable from the viewpoints of easy handling, good Ge supply efficiency, and the like.

To form a layer made of a-SiGe (H, X) by using the reactive sputtering method or the ion plating method, for example, in the case of the sputtering method, two targets of Si and Ge are used, or Using a target composed of Si and Ge, this is sputtered in a desired gas plasma atmosphere, and in the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are used. Are respectively accommodated in vapor deposition boats as vaporization sources, and the vaporization sources are heated and vaporized by a resistance heating method, an electron beam method (EB method) or the like, and flying evaporates are passed through a desired 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 the above-mentioned silanes and / or gases such as germanium hydride are introduced into the deposition chamber for sputtering and A plasma atmosphere of gases may be formed.

For example, in order to form a layer or a layer region composed of a-Si (H, X) containing a group III atom or a group V atom by a glow discharge method, the a-Si (H, X) described above is used. ) A raw material gas for forming, a raw material gas for introducing a group III atom or a group V atom, and, if necessary, a diluting gas such as He gas or Ar gas are mixed at a predetermined mixing ratio and supported. The support 101 is introduced into a deposition chamber for vacuum deposition of the body 101, and the introduced gas is turned into gas plasma by causing glow discharge.
A-Si (H, containing a Group III atom or a Group V atom thereon
X) should be deposited. 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, 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 hydrogenated such silicon, but BF _3, BCl _3, can be exemplified BBr ₃ and halogenated silicon or the like, this addition, AlCl _3, GAC
l ₃ , InCl ₃ , TlCl _{3 and the} like 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
Other examples include F ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , and BiBr ₅ .

Further, for example, in order to form a layer or a layer region containing a nitrogen atom, a starting material for introducing a nitrogen atom is added to the above a-Si.
It is used together with the starting material for forming a layer composed of (H, X) and is contained in the formed layer or layer region in a controlled amount.

That is, in order to form a layer or layer region containing a nitrogen atom by the glow discharge method, the starting material used when forming the layer composed of a-Si (H, X) described above by the glow discharge method. A starting material for introducing a nitrogen atom is added to the above selected ones as desired. 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. Used as a raw material gas mixed 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 also mixed at a desired mixing ratio and used. be able to.

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.

As a starting material for introducing such a nitrogen atom, any material may be used as long as it is a gasified substance containing at least nitrogen atoms as constituent atoms or a gasifiable substance.

As a starting material for introducing a nitrogen atom, specifically, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H) having a nitrogen atom as a constituent atom or a nitrogen atom and a hydrogen atom as constituent atoms is used. ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide
Examples thereof include nitrogen such as (NH ₄ N ₃ ), and 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 mentioned. When these halogenated nitrogen compounds are used, in addition to the introduction of the nitrogen atom (N), the introduction of the halogen atom (X) is also required. it can.

In the present invention, as described above, in order to further promote the effect obtained by containing a nitrogen atom, an oxygen atom can be further contained in addition to the nitrogen atom, but the oxygen atom is contained. Examples of the raw material gas for introducing oxygen atoms for quenching include oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and nitrogen monoxide (N ₂ ).
₂ O), nitrogen trioxide (N ₂ O ₃ ), trinitrogen trioxide (N ₂ O ₄ ), nitrogen pentoxide (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 ), trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ), and the like. You can

According to the sputtering method, in order to form a layer region containing a nitrogen atom, a single crystal or polycrystalline Si wafer or Si ₃ N ₄ wafer, or Si and Si ₃ N ₄ are mixed and contained. This may be performed by using the existing wafer as a target and sputtering these 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, if necessary, and then introduced into a deposition chamber for a sputter, and gas of these gases is introduced. Plasma may be formed and the Si wafer may be sputtered.

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 hydrogen atoms (H) or / and halogen atoms (X) are contained in an atmosphere of a diluting gas as a gas for a sputter. It is formed by sputtering in a gas atmosphere containing the constituent atoms. As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen atoms in the raw material gas shown in the example of the glow discharge described above,
It can also be used as an effective gas for spattering.

To form a layer containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or SiO _{2 is used.}
It may be carried out by using a wafer or a wafer containing Si and SiO ₂ mixed as a target, and sputtering these in various gas atmospheres.

For example, if you use a Si wafer as a target,
A raw material gas for introducing hydrogen atoms and / or halogen atoms, if necessary, is diluted with a diluting gas, if necessary, and then introduced into a deposition chamber for spatters. Plasma may be formed and the Si wafer may be sputtered.

Alternatively, by using Si and SiO ₂ as separate targets, or by using a single target of Si and SiO ₂ mixture, in the atmosphere of diluting gas as a gas for the sputter or at least hydrogen. It is formed by sputtering in a gas atmosphere containing atoms (H) and / or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the example of glow discharge described above can be used as an effective gas in the case of sputtering.

For example, the second layer contains a-SiC (H, X) [hereinafter a-SiCM (H, X) (however, containing a Group III atom or a Group V atom.
M represents a Group III atom or a Group V atom. ). ] In order to form the second layer by the glow discharge method, a raw material gas for forming a-SiCM (H, X) is diluted with a diluting gas and a predetermined amount if necessary. The mixture is mixed at a mixing ratio of 1, and is introduced into a deposition chamber for vacuum deposition in which the support 101 is installed, and the introduced gas is converted into gas plasma by causing glow discharge to be already formed on the support. It is sufficient to deposit a-SiCM (H, X) on the first layer.

Source gases for forming a-SiCM (H, X) include Si, C,
H and / or halogen atom, and group III atom or group V
If a gaseous substance or a gasifiable substance having at least one of the group atoms as a constituent atom is gasified,
It may be either one.

When a source gas containing Si as a constituent atom as one of Si, C, H and / or a halogen atom, a Group III atom or a Group V atom is used, for example, a source gas containing Si as a constituent atom is used. , C as a constituent atom, and a source gas having a constituent atom of H and / or a halogen atom are mixed at a desired mixing ratio with a raw material gas having a group III atom or a group V atom as a constituent atom. Used or a source gas containing Si as a constituent atom, a source gas containing C and H and / or a halogen atom as a constituent atom, and a source gas containing a Group III atom or a Group V atom as a constituent atom Is also mixed in a desired mixing ratio, or a source gas containing Si as a constituent atom and Si, C
Further, a raw material gas containing three H and / or halogen atoms as constituent atoms and a raw material gas containing group III atoms or group V atoms as constituent atoms can be mixed and used.

In addition, separately, a source gas containing Si and H and / or a halogen atom as a constituent atom and a source gas containing C as a constituent atom
You may use it, mixing the raw material gas which makes a group I atom or a group V atom a constituent atom.

Effectively used as a raw material gas for forming a layer composed of a-SiC (H, X) is Si containing Si and H as constituent atoms.
Silicates such as H ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ and the like, hydrogenated silicon gas such as silanes, and saturated carbons having C and H as constituent atoms, for example, having 1 to 4 carbon atoms. Hydrogen, C2-C4 ethylene hydrocarbon, C2-C3 acetylene hydrocarbon, etc. are mentioned.

Specifically, the saturated hydrocarbons include methane (CH _4), ethane (C ₂ H _6), propane (C ₃ H _8), n- butane (nC ₄ H _10),
As pentane (C ₅ H ₁₂ ), ethylene-based hydrocarbon, ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ). , Isobutylene (C ₄ H ₈ ), pentene (C
₅ H ₁₀ ), acetylene-based hydrocarbons include acetylene (C ₂
H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ) and the like.

As a source gas containing Si, C and H as constituent atoms, Si (C
Mention may be made of alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ . In addition to these raw material gases, H ₂ can of course be used as the raw material gas for introducing H.

Specifically as a starting material for introducing a group III atom, 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 borohydride such _{as, BF 3, BCl 3, BBr} 3
And the like. In addition to this, AlCl ₃ , G
Other examples include aCl ₃ , Ga (CH ₃ ) ₂ , InCl ₃ and TlCl ₃ .

As a starting material for introducing a Group V atom, specifically, for introducing a phosphorus atom, phosphorus hydride such as PH ₃ , P ₂ H _4, etc., PH ₄ I, PF ₃ ,
Examples thereof include phosphorus halides such as PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , As
F ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , B
iBr _{5 and the} like can also be mentioned as effective starting materials for introducing a Group V atom.

To form the second layer composed of a-SiCM (H, X) by the sputtering method, a single crystal or polycrystalline Si wafer or C (graphite) wafer, or Si and C
This is performed by using a wafer containing mixed and contained as a target, and sputtering these in a desired gas atmosphere.

For example, when a Si wafer is used as a target, a raw material gas for introducing a carbon atom, a group III atom or a group V atom, and a hydrogen atom and / or a halogen atom, Ar, He It is only necessary to dilute the Si wafer with a diluting gas and introduce it into the deposition chamber for the sputtering, form a gas plasma of these gases, and sputter the Si wafer.

Also, Si and C should be different targets or Si
When used as a single target of a mixture of C and C, a group III atom or a group V atom and a raw material gas for introducing a hydrogen atom and / or a halogen atom as a gas for the spatula may be added, if necessary. It may be diluted with a diluting gas and then introduced into a deposition chamber for spatters to form gas plasma for spattering. As the raw material gas for introducing each atom used in the sputtering method, the raw material gas used in the glow discharge method can be used as it is.

As described above, the first layer and the second layer of the light-receiving layer of the light-receiving member of the present invention are formed by using the glow discharge method, the sputtering method, or the like. The content of each germanium atom, group III atom or group V atom, nitrogen atom or oxygen atom, carbon atom, or hydrogen atom and / or halogen atom contained in the layer is controlled by flowing into the deposition chamber. , By controlling the gas flow rate of each starting material for atom supply or the gas flow rate ratio between the starting materials for atom supply.

The conditions such as the temperature of the support during formation of the first layer and the second layer, the gas pressure in the deposition chamber, and the discharge power are important factors for obtaining a light receiving member having desired characteristics. It is appropriately selected in consideration of the function of the layer to be formed. Furthermore, these layer forming conditions may differ depending on the type and amount of each of the above-mentioned atoms to be contained in the first layer and the second layer. It is also necessary to make a decision after careful consideration.

Specifically, when a layer made of a-Si (H, X) is formed, or when a group III atom or a group V atom, a nitrogen atom,
When forming a layer made of a-Si (H, X) containing oxygen atoms, carbon atoms, etc., the support temperature is usually 50 to
The temperature is 350 ° C., but particularly preferably 50 to 250 ° C. The gas pressure in the deposition chamber is usually 0.01 to 1 Torr, but particularly preferably 0.1 to 0.5 Torr. The discharge power is 0.005
It is usually set to 50 W / cm ² , but more preferably 0.0
1 to 30 W / cm ² , and particularly preferably 0.01 to 20 W / cm ² . a
-When forming a layer of SiGe (H, X), or
When a layer made of a-SiGe (H, X) containing a group II atom or a group V atom, a nitrogen atom, an oxygen atom or the like is formed, the support temperature is usually 50 to 350 ° C. , More preferably 50 to 300 ° C, particularly preferably 100 to 300 ° C. The gas pressure in the deposition chamber is usually 0.01-5 Torr.
However, it is preferably 0.001 to 3 Torr, and particularly preferably 0.1 to 1 Torr. Also, the discharge power is 0.005-50W
It is usually set to / cm ² , but preferably 0.01 to 30 W / cm
² and particularly preferably 0.01 to 20 W / cm ² .

However, the support temperature for performing these layer formations,
The specific conditions of the discharge power and the gas pressure in the deposition chamber are usually difficult to determine individually and independently. Therefore, in order to form the amorphous material layer having the desired characteristics, it is desirable to determine the optimum conditions for forming the layer based on the mutual and organic relationships.

By the way, in order to make the distribution state of the germanium atom, the group III atom or the group V atom, the nitrogen atom, the oxygen atom, and the carbon atom contained in the first layer and the second layer in the present invention uniform. It is necessary to keep the above conditions constant when forming the first layer and the second layer.

Further, in the present invention, at the time of forming the first layer, the distribution concentration of the group III atom or the group V atom, the nitrogen atom or the oxygen atom contained in the layer is changed in the layer thickness direction to obtain a desired value. To form the first layer having a distribution in the layer thickness direction, if a glow discharge method is used, a starting material for introducing a group III atom or a group V atom or a starting material for introducing a nitrogen atom Alternatively, the gas flow rate when introducing the gas of the starting material for introducing oxygen atoms into the deposition chamber is appropriately changed according to the desired rate of change, and other conditions are kept constant. Then, in order to change the gas flow rate, specifically, for example, manually or by some commonly used method such as an external drive motor, gradually open the opening of a predetermined needle valve provided in the middle of the gas flow path system. It suffices to perform an operation to change. At this time, the rate of change of the flow rate does not need to be linear, and the desired rate of content curve can be obtained by controlling the flow rate according to a previously designed rate-of-change curve using, for example, a microcomputer.

When the first layer is formed by using the sputtering method, the distribution concentration of the group III atom, the group V atom, the oxygen atom or the nitrogen atom in the layer thickness direction is changed in the layer thickness direction to obtain a desired layer thickness. As in the case of using the glow discharge method, a starting material for introducing a group III atom or a group V atom, a starting material for introducing a nitrogen atom, or a starting material for introducing an oxygen atom is used to form a directional distribution state. The substance is used in the gaseous state and the gas flow rate in introducing the gas into the deposition chamber is varied as desired.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples 1 to 13, but the present invention is not limited thereto.

In each example, the first layer and the second layer were formed using the glow discharge method. FIG. 14 shows an apparatus for manufacturing the light receiving member of the present invention by the glow discharge method.

The gas cylinders 202, 203, 204, 205, and 206 in the figure are sealed with the raw material gas for forming each layer of the present invention. As an example, for example, 202 is S diluted with He.
iH ₄ gas (purity 99.999%, hereinafter abbreviated as SiH ₄ / He) cylinder,
203 is B ₂ H ₆ gas diluted with He (purity 99.999%, hereinafter B ₂ H
₆ / He) cylinder, 204 is NH ₃ gas (purity 99.999%, hereinafter abbreviated as NH ₃ / He) cylinder diluted with He, 205 is C ₂ H ₄ gas (purity 99.999%) cylinder, 206 is He GeH ₄ diluted in
It is a gas (purity 99.999%, hereinafter abbreviated as GeH ₄ / He) cylinder.

When halogen atoms are introduced into the formed layer, Si is used.
Instead of the H ₄ gas, for example, the cylinder may be replaced by using SiF ₄ gas.

A gas cylinder 2 is used to allow these gases to flow into the reaction chamber 201.
Check that the valves 222 to 226 and the leak valve 235 of 02 to 206 are closed, and that the inflow valves 212 to 216, the outflow valves 217 to 221, and the auxiliary valves 232 and 233 are opened. The main valve 234 is opened to exhaust the reaction chamber 201 and the gas pipe. Next, the reading of the vacuum gauge 236 is about 5 x 10
^{When the} pressure reaches ^-6 torr, the auxiliary valves 232 and 233 and the outflow valves 217 to 221 are closed.

1 when forming the first layer 102 on the base cylinder 237
Here's an example. Valve 222, SiH ₄ / He gas from gas cylinder 202, B ₂ H ₆ / He gas from gas cylinder 203, NH ₃ / He gas from gas cylinder 204, GeH ₄ / He gas from gas cylinder 206
223, 224, 226 are opened to adjust the pressure of the outlet pressure gauges 227, 228, 229, 231 to 1 kg / cm ² , the inflow valves 212, 213, 214, 216 are gradually opened to flow into the mass flow controllers 207, 208, 209, 211. Continued outflow valves 217,218,219,221,
The auxiliary valves 232 and 233 are gradually opened to allow the gas to flow into the reaction chamber 201. The SiH ₄ / He gas flow rate, B ₂ H ₆ / He gas flow rate, NH ₃ / He gas flow rate and GeH ₄ / He gas flow rate at this time are adjusted so that the ratio becomes a desired value, and the outflow valves 217,218,219,221 are adjusted, or The opening of the main valve 234 is adjusted while watching the reading of the vacuum gauge 236 so that the pressure in the reaction chamber 201 becomes a desired value. The temperature of the base cylinder 237 is the heater 2
After it is confirmed by 38 that the temperature is set in the range of 50 to 400 ° C., the power supply 240 is set to a desired power to cause glow discharge in the reaction chamber 201, and a micro computer (not shown). ) According to a predesigned rate-of-change line, B ₂ H ₆ / He gas flow rate, NH ₃ / He
First, a layer region containing germanium atoms, boron atoms and nitrogen atoms is formed on the base cylinder 237 while controlling the gas flow rate and the SiH ₄ / He gas flow rate ratio.

Next, after a predetermined time, GeH ₄ / He gas, NH ₃ / He gas and B ₂ H
₆ / He gas is introduced into the reaction chamber 201 by shutting off the valve of each corresponding gas introduction pipe and shutting off, and by continuing glow discharge for a predetermined time, germanium atom, boron atom, and nitrogen atom are contained. Not allowed to form a layer.

When a halogen atom is contained in the first layer, SiF ₄ / He gas, for example, may be further added to the above gas and fed into the reaction chamber.

In order to form the second layer on the first layer formed on the base cylinder 237 by the operation as described above, the same valve operation as in the formation of the first layer is performed. For example, SiH ₄
Each of the gas, C ₂ H ₄ gas and PH ₃ gas is diluted with a diluting gas such as He, if necessary, and allowed to flow into the reaction chamber 201 at a desired flow ratio, and glow discharge according to desired conditions. It is done by giving rise to.

Needless to say, all of the outflow valves other than the gas outflow valves 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 reaction chamber.
In order to avoid remaining in the gas pipe from 201, the outflow valves 217 to 221 to the reaction chamber 201, the outflow valves 217 to 221 are closed and the auxiliary valves 232 and 233 are opened and the main valve 234 is fully opened as necessary. The system is temporarily evacuated to a high vacuum.

Further, during the layer formation of the second layer, the base cylinder 237 is rotated at a desired speed by the motor 239 in order to make the layer formation uniform.

Example 1 Using the manufacturing apparatus shown in FIG. 14, layers were formed on a drum-shaped aluminum substrate that had been washed by a usual method under the layer forming conditions shown in Table 1. At this time, the change in the B ₂ H ₆ / SiH ₄ gas flow rate ratio was automatically adjusted by micro computer control according to the flow rate change line shown in FIG. 15 which was designed in advance.

The drum-shaped light receiving member for electrophotography thus obtained,
It was installed in a Canon high-speed copying machine modified for experiment, and Canon test chart was used as a manuscript, the image forming process conditions (using a tungsten lamp as a light source) were appropriately selected, and a copying test was performed. Excellent resolution was obtained. I was able to get high quality images.

Example 2 The B ₂ H ₆ / SiH ₄ gas flow rate ratio and the NH ₃ / SiH ₄ gas flow rate ratio were controlled according to the flow rate change lines shown in FIGS. 16 and 17, respectively, under the layer forming conditions shown in Table 2. A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1 except that
When a copying test similar to the above was conducted, a high quality image excellent in resolution was obtained.

Example 3 Under the layer forming conditions shown in Table 3, the B ₂ H ₆ / SiH ₄ gas flow rate ratio and the NH ₃ / SiH ₄ gas flow rate ratio were changed according to the flow rate change lines shown in FIGS. 16 and 17, respectively. A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1 except that it was controlled, and a copying test was conducted in the same manner as in Example 1. As a result, a high-quality image excellent in resolution was obtained. It was

Example 4 For electrophotography in the same manner as in Example 1 except that the B ₂ H ₆ / SiH ₄ gas flow rate ratio was controlled according to the flow rate change line shown in FIG. 18 under the layer forming conditions shown in Table 4. The drum-shaped light receiving member of No. 1 was obtained and the same copying test as in Example 1 was conducted. As a result, a high-quality image excellent in resolution was obtained.

Example 5 For electrophotography in the same manner as in Example 1 except that the B ₂ H ₆ / SiH ₄ gas flow rate ratio was controlled according to the flow rate change line shown in FIG. 19 under the layer forming conditions shown in Table 5. The drum-shaped light receiving member of No. 1 was obtained and the same copying test as in Example 1 was conducted. As a result, a high-quality image excellent in resolution was obtained.

Example 6 Under the layer forming conditions shown in Table 6, the NH ₃ / SiH ₄ gas flow rate ratio and the B ₂ H ₆ / SiH ₄ gas flow rate ratio were set according to the flow rate change lines shown in FIGS. 17 and 20, respectively. A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1 except that it was controlled, and a copying test was conducted in the same manner as in Example 1. As a result, a high-quality image excellent in resolution was obtained. It was

Example 7 For electrophotography in the same manner as in Example 1 except that the B ₂ H ₆ / SiH ₄ gas flow rate ratio was controlled according to the flow rate change line shown in FIG. 15 under the layer forming conditions shown in Table 7. The drum-shaped light receiving member of No. 1 was obtained and the same copying test as in Example 1 was conducted. As a result, a high-quality image excellent in resolution was obtained.

Example 8 For electrophotography in the same manner as in Example 1 except that the B ₂ H ₆ / SiH ₄ gas flow rate ratio was controlled according to the flow rate change line shown in FIG. 15 under the layer forming conditions shown in Table 8. The drum-shaped light receiving member of No. 1 was obtained and the same copying test as in Example 1 was conducted. As a result, a high-quality image excellent in resolution was obtained.

Example 9 The procedure was substantially the same as that of Example 1 except that the layer thickness was changed variously as shown in Table 9 when the second layer (II) in Table 1 was formed. Under the conditions of each light receiving member (Sample No. 9
Nos. 01 to 907) were prepared, and the same image forming process as in Example 1 was applied to each and evaluated, and the results shown in Table 9 were obtained.

Example 10 Gas flow rate ratio when forming the second layer (II) in Table 1
Except that the values of C ₂ H ₄ / SiH ₄ shown in Table 10 were used, each of the light receiving members (Sample N
1001 to 1007) and evaluated in the same manner as in Example 1, it was possible to obtain a high quality image with good halftone reproducibility in each case.

Also, in a durability test by repeated continuous use, it was proved that an image having a quality comparable to the initial image quality could be obtained and the durability was excellent.

Example 11 Gas flow rate ratio when forming the first layer (I) in Table 1
Except that the values of GeH ₄ / SiH ₄ shown in Table 11 are used, each light receiving member (Sample N
Nos. 1101 to 1105) were prepared and evaluated in the same manner as in Example 1. In each case, halftone reproducibility was good and a high quality image could be obtained.

Also, in a durability test by repeated continuous use, it was proved that an image having a quality comparable to the initial image quality could be obtained and the durability was excellent.

Example 12 For electrophotography in the same manner as in Example 1 except that the B ₂ H ₆ / SiH ₄ gas flow rate ratio was controlled according to the flow rate change line shown in FIG. D under the layer forming conditions shown in Table 12. The drum-shaped light receiving member of No. 1 was obtained and the same copying test as in Example 1 was conducted. As a result, a high-quality image excellent in resolution was obtained.

Example 13 In each of Examples 1 to 12, except that a 810 nm GaAs semiconductor laser (10 mW) was used as a light source instead of a tungsten lamp to form an electrostatic image and reverse development was performed. When the image quality of the toner transfer image was evaluated by applying the same image forming process, it was possible to obtain a clear high quality image having excellent resolution and good gradation reproducibility.

[Outline of Effects of Invention]

The light-receiving member of the present invention has a light-receiving layer composed of a-Si (H, X), and the layer structure of the light-receiving member is specified as described above to obtain a- It is possible to solve all the problems in the conventional light receiving member having the light receiving layer composed of Si. That is, the light receiving member of the present invention has particularly excellent moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc., and also improves light sensitivity and dark resistance. It has a high photosensitivity in the entire visible light region, in particular, an excellent mating property with a semiconductor laser, and a fast photoresponsive property has outstanding characteristics. When the light-receiving member of the present invention is applied as an electrophotographic image forming member, there is no effect of residual potential, its electrical characteristics are stable, and an image obtained using it is , High density, clear halftone, etc. Further, the light receiving member of the present invention has a light receiving layer formed on a support, and the layer itself is tough,
Further, since it is excellent in the adhesiveness with the support and the adhesiveness between the layers provided on the support, it can be repeatedly used continuously at high speed for a long time.

[Brief description of drawings]

FIGS. 1 to 4 are diagrams schematically showing the layer structure of the light receiving member of the present invention, and FIGS. 5 to 13 are group III atoms or groups in the first layer of the light receiving member of the present invention. FIG. 14 is a concentration distribution diagram showing a typical example of the distribution state of group V atoms, nitrogen atoms or oxygen atoms. FIG. 14 is an example of an apparatus for producing the light receiving member of the present invention, which is produced by a glow discharge method. FIG. 15 is a schematic explanatory view of the apparatus, and FIGS. 15 to 20 are views showing a change state of the gas flow rate ratio during layer formation of the light receiving member of the present invention. 100 ... Photoreceptive member, 101 ... Support, 102 ... First layer, 103 ...
2nd layer, 104 ... Free surface, 105-110 ... Layer area, 201 ... Reaction chamber, 202-206 ... Gas cylinder, 207-211 ... Mass flow controller, 212-216 ... Inflow valve, 217-221 ... Outflow valve, 222-226 ... Valve, 227-231 ... Pressure regulator, 232,23
3 ... Auxiliary valve, 234 ... Main valve, 235 ... Leak valve, 236 ... Vacuum gauge, 237 ... Base cylinder, 238 ... Heating heater, 239 ... Motor, 240 ... High frequency power supply.

Claims (3)

[Claims] 1. A support, a first layer region containing silicon atoms as a matrix and containing germanium atoms in a uniform distribution state in the layer thickness direction, and a second layer region containing silicon atoms as a matrix and not containing germanium atoms. And has the periodic table
Amorphous containing atoms belonging to Group III or Group V in a non-uniform distribution state in the layer thickness direction so as to have a region whose concentration distribution increases toward the support side and decreases toward the surface side. A first layer having a layer thickness of 1 to 100 μm composed of a material, a silicon atom as a base material, a carbon atom, and further a hydrogen atom or a hydrogen atom and a halogen atom, the content of the hydrogen atom or the hydrogen The total amount of atoms and halogen atoms is 0.01 to 40 atomic%, and the atoms belonging to Group III or V of the periodic table are 1.0 to 10 ⁴ in a uniform distribution state in the layer thickness direction. a light-receiving layer in which a second layer composed of an amorphous material containing atomic ppm and having a layer thickness of 3 × 10 ^{−3 to} 30 μm is sequentially laminated from the support side, and the first layer or the above At least one of the second layers contains nitrogen atoms in a uniform distribution state in the layer thickness direction. Light-receiving member, characterized in that it is. 2. The light receiving member according to claim 1, wherein at least one of the first layer and the second layer further contains an oxygen atom. 3. The light receiving member according to claim 2, wherein the oxygen atoms are contained in a state of being uniformly distributed in the layer thickness direction.