JPS6410066B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as.

As photoconductive materials constituting photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, document reading devices, etc., highly sensitive,
It has a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)] and has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, especially the emission wavelength characteristics of semiconductor lasers, which have seen remarkable progress in development recently. The solid-state imaging device must have a certain absorption spectrum characteristic, have fast photoresponsiveness, have a desired dark resistance value, be non-polluting to the human body during use, and furthermore, solid-state imaging devices must have a certain afterimage. Characteristics such as being able to easily process within a certain amount of time are required. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the pollution-free nature during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion/reading device is described in JP-A-55-39404.

However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. There are points that can be further improved in terms of usage environment characteristics and stability over time, and practical solid-state imaging devices, reading devices, and electrophotographic images can be used in a wide range of applications. The reality is that forming members and the like cannot be used effectively in consideration of productivity and mass production.

For example, when applied to electrophotographic image forming members, it is often observed that residual potential remains during use, and such photoconductive members may become fatigued due to repeated use if used repeatedly for a long time. There have been many inconveniences such as the so-called ghost phenomenon in which an afterimage occurs due to the accumulation of images.

Furthermore, for example, according to many experiments conducted by the present inventors, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member is superior to conventional Se, CdS, ZnO, PVCz, TNF, etc. Although it has many advantages compared to OPC (organic photoconductive material), a-Si has been given characteristics for use in conventional solar cells.
Even when the photoconductive layer of an electrophotographic image forming member having a single-layer photoconductive layer is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, compared to ordinary electrophotography. The above-mentioned tendency is remarkable in a humid atmosphere, and in some cases, it may not be possible to retain the electrostatic charge at all until the development time.There are some points that can be solved. is known to exist.

Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is also necessary to take measures to obtain the desired electrical, optical, and photoconductive properties as described above when designing photoconductive members. There is.

The present invention has been made in view of the above points, and includes a
-As a result of comprehensive research and study on Si from the viewpoint of its adaptability and applicability as a photoconductive member used in electrophotographic image forming members, we found that silicon is used as a base material and hydrogen atoms ( Amorphous material (amorphous material) containing at least either one of H) or halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] As a generic notation for a-Si(H,
A photoconductive member produced by specifying the layer structure of the amorphous layer that exhibits photoconductivity is not only fully usable for practical use, but is also incomparable with conventional photoconductive members. It has been found that it is superior in most respects when compared, especially as a photoconductive member for electrophotography, and has significantly superior characteristics in terms of photosensitivity and image quality stability. Based on.

The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, has excellent resistance to light fatigue, and does not cause deterioration even after repeated use. First, the main object is to provide a photoconductive member for electrophotography in which no or almost no residual potential is observed.

Another object of the present invention is to provide a photoconductive member for electrophotography that has high photosensitivity in the entire visible light range and quick photoresponsiveness.

Another object of the present invention is to provide charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. An object of the present invention is to provide a photoconductive member for electrophotography, which has sufficient electrophotographic properties and has excellent electrophotographic properties with almost no deterioration of the properties observed even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution.

The photoconductive member for electrophotography of the present invention includes a support for the photoconductive member and an amorphous layer that is composed of an amorphous material having silicon atoms as a matrix and exhibits photoconductivity. The amorphous layer contains oxygen atoms in at least a portion thereof, and has a layer region in which the distribution of oxygen atoms changes continuously in the thickness direction of the layer, and the oxygen atoms are , is characterized in that it is more distributed on the side where the support is provided.

The photoconductive member for electrophotography of the present invention designed to have the above-described layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. and usage environment characteristics.

When used as an electrophotographic image forming member, the photoconductive member for electrophotography of the present invention has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and can be used even in a humid atmosphere. Its electrical characteristics are stable, it is highly sensitive, it has a high signal-to-noise ratio, and it has excellent resistance to light fatigue and repeated use.
A high-quality visible image with high density, clear halftones, and high resolution can be obtained.

Hereinafter, according to the drawings, a photoconductive member for electrophotography of the present invention (hereinafter simply referred to as "photoconductive member") will be described.
This will be explained in detail.

FIG. 1 is a schematic configuration diagram schematically shown to explain a basic configuration example of a photoconductive member of the present invention.

The photoconductive member 100 shown in FIG. 1 includes a barrier layer 102 provided as necessary on a support 101 for the photoconductive member, and an amorphous layer provided in direct contact with the barrier layer 102. The amorphous layer 103 has a layer region containing oxygen atoms in at least a part thereof, and the distribution of oxygen atoms in the layer region is approximately similar to the surface of the support 101. Oxygen atoms contained in the layer region are substantially uniform in parallel planes, are non-uniform in the thickness direction of the layer, and have a region in which the distribution changes continuously. is distributed more on the surface side where the support 101 is provided than on the center of the layer region. Furthermore, in a preferred embodiment,
The content of oxygen atoms in the entire layer region Ot is 0.05
~30 atomic%, and the support 1 of the layer region
The peak of the distribution amount is in the range of 0.3 to 60 atomic % on the surface where 01 is provided or in the vicinity of the surface.

The support 101 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo, Au,
Examples include metals such as Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the dielectrically treated surface side.

For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al , Ag, Pb, Zn, Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If used as an image forming member, it is desirable to have an endless belt shape or a cylindrical shape in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but when flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.,
It is considered to be 10μ or more.

The barrier layer 102 effectively prevents free carriers from flowing from the support 101 side to the amorphous layer 103 side, and prevents free carriers from flowing into the amorphous layer 103 due to electromagnetic wave irradiation. , support 10
It has a function of easily allowing the photo carrier moving toward the support body 101 to pass from the amorphous layer 103 side to the support body 101 side.

The barrier layer 102 has the above-mentioned function, but the amorphous layer 103 is formed on the support 101.
If a function similar to that of the barrier layer 102 described above can be sufficiently exhibited at the interface formed between the support 101 and the amorphous layer 103 by directly providing the barrier layer 102, the present invention is applicable. In this case, the barrier layer 10
There is no need to force the provision of 2.

Further, by containing a sufficient amount of oxygen atoms in the surface layer region of the amorphous layer 103 on the side of the support 101, the barrier layer 1 is formed in a part of the layer region of the amorphous layer 103.
It is possible to provide the same function as 02, and the content of oxygen atoms in this case is usually 39 to 66 atomic%, preferably 39 to 66 atomic%, relative to silicon atoms in the layer region that exhibits this function. is 42~66 atomic%,
Optimally, it is desirable to set it to 48 to 66 atomic%.

The barrier layer 102 is an amorphous material having silicon as its base material and containing at least one kind of atoms selected from carbon atoms, nitrogen atoms, and oxygen atoms, and at least one of hydrogen atoms or halogen atoms as necessary. Material <These are collectively referred to as a-[Si _x (C,
N, O〕 _1-x 〕 _y (H, X) Written as _1-y (however, 0
<x<1, 0<y<1)> or is composed of an electrically insulating metal oxide or an electrically insulating organic compound.

In the present invention, preferred halogen atoms (X) are F, Cl, Br, and I, with F and Cl being particularly preferred.

Specifically, examples of amorphous materials that can be effectively used in the present invention as the amorphous material constituting the barrier layer 102 include carbon-based amorphous materials such as a-Si _a C _1-a , a-( Si _b C _1-b ) _c H _1-c , a-(Si _d C _1-d ) _e X _1-e , a-(Si _f C _1-f ) _g (H+X) _1-g , nitrogen-based As amorphous materials, a-Si _h N _1-h , a-(Si _i N _1-i ) _j H _1-j , a-(Si _k N _1-k ) _l X _1-l , a-(Si _n N _1-n ) _o (H+X) _1-o , as an oxygen-based amorphous material a-Si _p O _1-p , a-(Si _p O _1-p ) _q H _1-q , a-( _{Si r O 1 - r ) s} Examples include amorphous materials containing at least two types of atoms as constituent atoms (provided that 0<a, b, c,
d, e, f, g, h, i, j, k, l, m, n,
o, p, q, r, s, t, u<1).

These amorphous materials have the characteristics required for the barrier layer 102 and the barrier layer 1 depending on the optimized design of the layer configuration.
The optimum one is selected depending on the ease of creating a continuous layer with the amorphous layer 103 stacked on 02 and the like. In particular, from the viewpoint of properties, it is more preferable to select carbon-based or nitrogen-based amorphous materials.

When the barrier layer 102 is made of the above-mentioned amorphous material, the layer formation method may be a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, or the like. .

In order to form the barrier layer 102 by the glow discharge method, the raw material gas for forming the amorphous material is mixed with a dilution gas at a predetermined mixing ratio as necessary;
The support 101 is introduced into a deposition chamber for vacuum deposition in which the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, thereby forming the support 101.
The amorphous material described above may be deposited thereon.

In the present invention, SiH ₄ and Si ₂ containing Si and H as constituent atoms are effectively used as the raw material gas for forming the barrier layer 102 made of a carbon-based amorphous material. Silicon hydride gas such as silanes such as H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., saturated hydrocarbons containing C and H as constituent atoms, e.g. 1 to 5 carbon atoms, 2 carbon atoms -5 ethylene hydrocarbons, C2-4 acetylene hydrocarbons, and the like.

Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₆ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like.

Examples of the source gas containing Si, C, and H as constituent atoms include alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ . In addition to these raw material gases, H
Of course, _H2 is also effective as the raw material gas for introduction.

Among the raw material gases for layer formation to configure the barrier layer 102 from a carbon-based amorphous material containing halogen atoms, raw material gases for introducing halogen atoms include, for example, simple halogen, hydrogen halide, and interhalogen compounds. , silicon halide, halogen-substituted silicon hydride, and the like.

Specifically, halogen gases include fluorine, chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, and HBr, and interhalogen compounds include BrF, ClF, ClF ₃ , and ClF ₃ ,
BrF ₅ , BrF ₃ , IF ₃ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br,
SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₃ , SiH ₂ Cl ₂ ,
SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃
etc. can be mentioned.

In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F,
Halogen-substituted paraffin hydrocarbons such as CH ₃ Cl, CH ₃ Br, CH ₃ I, C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ , Si(C ₂ Alkyl silicides such as H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (Cl ₃ ) ₂ , etc.
Derivatives of silanes such as halogen-containing alkyl silicides such as SiCl ₃ CH ₃ may also be mentioned as useful.

These barrier layer forming substances are used during the formation of the barrier layer so that the formed barrier layer contains silicon atoms, carbon atoms, and optionally halogen atoms and hydrogen atoms in a predetermined composition ratio. be selected and used as desired.

For example, SiHCl _{3 and} SiCl contain Si(CH ₃ ) ₄ and halogen atoms, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and form a barrier layer with desired characteristics. ₄ , _{SiH2Cl2 ,}
Alternatively, a-(Si _f C _1-f ) _g (X+H) 1 can be obtained by introducing SiH ₃ Cl or the like in a gaseous state at a predetermined mixing ratio into a device system for forming a barrier layer to generate a _glow discharge. _-
A barrier layer consisting of _g can be formed.

When employing the glow discharge method to form the barrier layer 102 with a nitrogen-based amorphous material, select the desired material from the materials listed above for forming the barrier layer, and add Then, the next raw material gas for introducing nitrogen atoms may be used. That is, starting materials that can be effectively used as raw material gases for introducing nitrogen atoms to form the barrier layer 102 include those containing N as a constituent atom, or nitrogen (for example) containing N and H as constituent atoms. _{N _ _ _ _ _ _} Nitrogen compounds such as compounds can be mentioned. In addition, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be mentioned because they can introduce halogen atoms in addition to nitrogen atoms. I can do it.

When forming the barrier layer 102 using an oxygen-based amorphous material by a glow discharge method, the starting materials that serve as the raw material gas for forming the barrier layer 102 include the above-mentioned barrier layer. Starting materials for introducing oxygen atoms are added to those selected as desired from among the starting materials for formation. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used.

For example, when using a raw material gas containing Si as a constituent atom, a raw material gas containing Si as a constituent atom, a raw material gas containing O as a constituent atom, and a raw material gas containing H or and X as a constituent atom as necessary. or mix a raw material gas containing Si at a desired mixing ratio with a raw material gas containing O and H at a desired mixing ratio. mosquito,
Alternatively, a raw material gas containing Si as a constituent atom and Si, O
and a raw material gas containing three constituent atoms of H can be used in combination.

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

Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Carbon monoxide (CO), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), Si, O, and H as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane ( Examples include lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ ).

As described above, when forming the barrier layer 102 by the glow discharge method, a desired structure having desired characteristics can be obtained by selecting and using various starting materials for forming the barrier layer from among the above-mentioned materials. A barrier layer 102 can be formed of a material. Specifically, a good combination of starting materials when forming the barrier layer 102 by a glow discharge method includes a single gas such as Si( _CH3 ) ₄ , _SiCl2 ( _CH3 ) _2, or _SiH4 -N. ₂ O system, SiH ₄ −O ₂ (−Ar) system, SiH ₄
−NO ₂ system, SiH ₄ −O ₂ −N ₂ system, SiCl ₄ −CO ₂ −H ₂
system, SiCl ₄ −NO−H ₂ system, SiH ₄ −NH ₃ system, SiCl ₄ −
NH ₄ system, SiH ₄ −N ₂ system, SiH ₄ −NH ₃ −NO system, Si
Examples include mixed gases such as (CH ₃ ) ₄ -SiH ₄ system and SiCl ₂ (CH ₃ ) ₂ -SiH ₄ system.

To form the barrier layer 102 made of a carbon-based amorphous material by the sputtering method, a monocrystalline or polycrystalline Si wafer or a C wafer or a mixture of Si and C is used. This can be carried out by sputtering a wafer as a target in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing carbon atoms and hydrogen atoms (H) or halogen atoms (X) may be diluted with a diluent gas as necessary. The Si wafer may be sputtered by introducing the gas into a deposition chamber and forming a gas plasma of these gases.

Alternatively, a gas containing at least a hydrogen atom (H) or a halogen atom (X) can be produced by using separate targets for Si and C or by using a single target containing a mixture of Si and C. This is done by sputtering in an atmosphere.

As the raw material gas for introducing carbon atoms, hydrogen atoms, or halogen atoms, the raw material gases shown in the glow discharge example described above can be used as effective gases also in the sputtering method.

To form the barrier layer 102 made of a nitrogen-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer, a Si ₃ N ₄ wafer, or a mixture of Si and Si ₃ N ₄ is used. This can be carried out by sputtering these wafers in various gas atmospheres, using them as targets.

For example, if a Si wafer is used as a target, nitrogen atoms and optionally hydrogen atoms or/and
and a raw material gas for introducing halogen atoms, such as H ₂ and N ₂ or NH ₃ , diluted with diluting gas as necessary and introduced into a deposition chamber for sputtering,
The Si wafer may be sputtered by forming a gas plasma of these gases.

Alternatively, it can be diluted as a sputtering gas by using separate targets for Si and Si ₃ N ₄ or by using a single target formed by mixing Si and Si ₃ N ₄ . This is done by sputtering in a gas atmosphere or in a gas atmosphere containing at least H atoms and/or X atoms.

Possible raw material gases for introducing N atoms include the raw material gases for introducing N atoms among the starting materials for forming the barrier layer shown in the glow discharge example mentioned above.
It can also be used as an effective gas in sputtering.

To form the barrier layer 102 made of an oxygen-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer, a SiO ₂ wafer, or a mixture of Si and SiO ₂ is used. This can be carried out by sputtering a wafer or a SiO ₂ wafer in various gas atmospheres.

For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it.

Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing H atoms and/or X atoms as constituent elements. 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 glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, the diluent gas used when forming the barrier layer 102 by a glow discharge method or a sputtering method is a so-called rare gas such as He,
Preferable examples include Ne, Ar, and the like.

Barrier layer 102 in the present invention is carefully formed to provide the desired properties.

In other words, a substance containing at least one of Si, C, N, and O, and optionally H or/and , in terms of electrical properties, the properties range from conductivity to semiconductivity to insulation.
In addition, since each exhibits properties ranging from photoconductive properties to non-photoconductive properties, in the present invention, the preparation conditions are selected so that a non-photoconductive amorphous material is formed. done strictly.

The amorphous material constituting the barrier layer 102 of the present invention has the function of blocking the injection of free carriers from the support 101 side to the amorphous layer 103 side, and preventing the injection of free carriers in the amorphous layer 103. Since it is intended to easily allow the generated photo carrier to move and pass to the support body 101 side, it is formed to exhibit electrically insulating behavior.

Further, when the photocarrier generated in the amorphous layer 103 passes through the barrier layer 102, the barrier has a mobility value with respect to the passing carrier to such an extent that the photocarrier passes through the barrier layer 102 smoothly. Layer 102 is formed.

An important factor in the layer forming conditions for forming the barrier layer 102 made of the amorphous material having the above characteristics is the temperature of the support during layer forming.

That is, when forming the barrier layer 102 made of the amorphous material on the surface of the support 101, the temperature of the support during layer formation is an important factor that influences the structure and characteristics of the formed layer. In the present invention, the temperature of the support during layer formation is strictly controlled so that the amorphous material having the desired properties can be produced as desired.

In order to effectively achieve the purpose of the present invention, the optimal range of the support temperature when forming the barrier layer 102 is selected as appropriate in accordance with the method of forming the barrier layer 102. Formation is carried out, typically between 100°C and 300°C, preferably at 150°C.
It is desirable that the temperature is between ℃ and 250℃. For forming the barrier layer 102, the barrier layer 102 is formed in the same system.
The amorphous layer 103 can be formed continuously from the amorphous layer 103 to the third layer formed on the amorphous layer 103 if necessary. Glow discharge method and sputtering method are advantageous because delicate control of the composition ratio of atoms constituting each layer and control of layer thickness are relatively easy compared to other methods. When forming the barrier layer 102 using these layer forming methods,
Similar to the support temperature described above, discharge power and gas pressure during layer formation can be cited as important factors that influence the characteristics of the barrier layer 102 to be created.

The discharge power conditions for effectively creating the barrier layer 102 with good productivity, which has the characteristics to effectively achieve the purpose of the present invention, are usually 1.
-300W, preferably 2-150W, and the gas pressure in the deposition chamber is usually 3 x 10 ^-3 -5Torr, preferably 8
It is desirable that it be approximately ×10 ^-3 to 0.5 Torr.

The amounts of carbon atoms, nitrogen atoms, oxygen atoms, hydrogen atoms, and halogen atoms contained in the barrier layer 102 in the photoconductive member of the present invention, as well as the conditions for forming the barrier layer 102, achieve the object of the present invention. This is an important factor in forming a barrier layer with desired properties.

When the barrier layer 102 is composed of a-Si _a C _1-a , the content of carbon atoms is usually 60 to 90 atomic %, preferably 65 to 80 atomic %, based on silicon atoms.
Preferably 7 to 75 atomic%, 0.1 to 75 atomic% for a
0.4, preferably 0.2 to 0.35, optimally 0.25 to 0.3, and when composed of a-(Si _b C _1-b ) _c H _1-c , the carbon atom content is usually 30 to 0.3. 90atomic%, preferably 40-90atomic%, optimally 50-80atomic%,
The hydrogen atom content is usually 1 to 40 atomic
%, preferably 2 to 35 atomic%, optimally 5 to 35 atomic%
When expressed in 30atomic%, b, c, b is usually 0.1 to 0.5, preferably 0.1 to 0.35, optimally 0.15 to
0.3, c is usually 0.60 to 0.99, preferably 0.65 to 0.98,
The optimum value is 0.7 to 0.95, and when composed of a-(Si _d C _1-d ) _e X _1-e or a-(Si _f C _1-f ) _g (H+X) _1-g ,
The content of carbon atoms is usually 40-90 atomic%, preferably 50-90 atomic%, optimally 60-80 atomic%
%, the content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 20 atomic%, preferably 1 to 18 atomic%, optimally 2 to 15 atomic%.
When both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually
19 atomic% or less, preferably 13 atomic% or less, and in the representation of d, e, f, g, d and f are usually
0.1 to 0.47, preferably 0.1 to 0.35, optimally 0.15 to
0.3, e, and g are usually 0.8 to 0.99, preferably 0.82 to
0.99, optimally 0.85 to 0.98.

When the barrier layer 102 is made of a nitrogen-based amorphous material, first of all, in the case of a-Si _h N _1-h , the content of nitrogen atoms is usually 43 to 43 to silicon atoms.
60 atomic %, preferably 43 to 50 atomic %, h usually 0.40 to 0.57, preferably 0.5 to 0.57.

When composed of a-(Si _i N _1-i ) _j H _1-j , the nitrogen atom content is usually 25 to 55 atomic%,
The content of hydrogen atoms is preferably 35 to 55 atomic%, usually 2 to 35 atomic%, preferably 5 to 55 atomic%.
30 atomic%, and if expressed as i and j, i is usually 0.43 to 0.6, preferably 0.43 to 0.5, and j is usually 0.65 to 0.98, preferably 0.7 to 0.95,
a-(Si _k N _1-k ) _l H _1-l or a-(Si _n N _1-n ) n(H+
X) When composed of _1-o , the content of nitrogen atoms is
Usually 30-60 atomic%, preferably 40-60 atomic%,
The content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 20 atomic%, preferably 2 to 15 atomic%, and the content of hydrogen atoms when both halogen atoms and hydrogen atoms are contained. The amount is usually less than 19 atomic%, preferably 13 atomic%.
In the representation of k, l, m, and n, kl is usually 0.43 to 0.60, preferably 0.43 to 0.49, and m and n are usually 0.8 to 0.99, preferably 0.85 to 0.98.

When the barrier layer 102 is made of an oxygen-based amorphous material, first, in a-Si _p O _1-p , the content of oxygen atoms is 60 to 67 atomic with respect to silicon atoms.
%, preferably 63 to 67 atomic %, and in terms of O, it is usually 0.33 to 0.40, preferably 0.33 to 0.37.

In the case of a-(Si _p O _1-p ) _q H _1-q , the content of oxygen atoms is usually 39 to 66 atomic%, preferably 42 to 66 atomic%.
64 atomic%, the hydrogen atom content is usually 2 to 35 atomic%, preferably 5 to 30 atomic%,
In terms of p and q, p is usually 0.33 to 0.40, preferably 0.33 to 0.37, and q is usually 0.65 to 0.98, preferably 0.70 to 0.95.

a-(Si _r O _1-r ) _s X _1-s , or a-(Si _t O _1-t ) _u (H
+X) When composed of _1-u , the content of oxygen atoms is usually 48 to 66 atomic%, preferably 51 to
66 atomic%, the content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 1.
20 atomic%, preferably 2 to 15 atomic%,
When both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually 19 atomic% or less,
It is preferably 13 atomic% or less, r, s, t,
In the representation of u, r and s are usually 0.33 to 0.40, preferably 0.33 to 0.37, and t and u are usually 0.80 to 0.99.
It is preferably 0.85 to 0.98.

In the present invention, the electrically insulating metal oxide constituting the barrier layer 102 includes TiO ₂ , Ce ₂ O ₃ ,
ZrO ₂ , HfO ₂ , GeO ₂ , CaO, BeO, P ₂ O ₅ ,
Y ₂ O ₃ , Cr ₂ O ₃ , Al ₂ O ₃ , MgO, MgO・Al ₂ O ₃ ,
Preferred examples include SiO ₂ and MgO. Two or more of these may be used in combination to form a barrier layer.

Barrier layer 1 made of electrically insulating metal oxide
02 is formed by vacuum evaporation method, CVD (chemical
This is accomplished by a vapor deposition method, a glow discharge decomposition method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, or the like. These manufacturing methods are appropriately selected and employed depending on factors such as manufacturing conditions, load on equipment capital, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured.

For example, the barrier layer 10 can be formed by sputtering.
2 can be formed by sputtering using a wafer as a starting material for forming a barrier layer as a target in an atmosphere of a sputtering gas such as He, Ne, Ar, or the like.

When using the electron beam method, the starting material for forming the barrier layer may be placed in a vapor deposition boat and irradiated with an electron beam for vapor deposition. The material exhibits electrically insulating behavior because it serves to prevent the photocarriers generated in the amorphous layer 103 from moving and to easily pass through to the support 101 side. is formed as.

The numerical range of the layer thickness of the barrier layer 102 is one of the important factors for effectively obtaining the required characteristics.

If the layer thickness of the barrier layer 102 is sufficiently thin,
If the flow of free carriers from the side of the support 101 toward the amorphous layer 103 or from the side of the amorphous layer 103 toward the side of the support 101 cannot be sufficiently achieved, or if the If it is thicker than this, the probability that the photo carrier generated in the amorphous layer 103 will pass to the side of the support 101 becomes extremely small, and therefore, in any case, the object of the present invention cannot be effectively achieved. becomes impossible to achieve.

In view of the above points, the thickness of the barrier layer 102 to effectively achieve the object of the present invention is usually 30 to 1000 Å, preferably 50 to 600 Å.

In the present invention, in order to effectively achieve the purpose, an amorphous layer 10 provided on the barrier layer 102 is used.
3 is a-Si(H,
X), and oxygen atoms are doped in the layer thickness direction in a distribution state as described below.

p-type a-Si(H,X)...Contains only acceptor. Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na).

A p ^- type a-Si (H,

n-type a-Si(H,X)...Contains only a donor. Or one that contains both donor and acceptor and has a high donor concentration (Nd).

An n ^- type a-Si (H,

i-type a-Si(H,X)...NaNdO or NaNd.

In the present invention, specific examples of the halogen atoms (X) contained in the amorphous layer 100 include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it.

In the electrophotographic photoconductive member 100 of the present invention, in a preferred example, the amorphous layer 103 includes:
The distribution is substantially uniform in a plane substantially parallel to the surface of the support 101, and is non-uniform in the thickness direction of the layer, so that the oxygen atoms contained in the layer region are It is more distributed on the surface side where the support body 101 is provided than in the center, and the value is 0.3 ~
A layer region is formed that has a peak amount in the range of 67 atomic % on or near the surface of the support 101.

2 to 8 show typical examples of the distribution of oxygen atoms contained in the amorphous layer 103 in the thickness direction of the amorphous layer 103.

In FIGS. 2 to 8, the vertical axis represents the amorphous layer 1
03 is the layer thickness t, _t0 is the interface position (lower surface position) between the support 101 or other material such as the barrier layer 102, and the amorphous layer 103, _{and ts} is the layer thickness t of the amorphous layer on the free surface 104 side. The interface position (upper surface position) of the layer 103 (the position of the free surface 104 in FIG. 1) is represented respectively, and the layer thickness t increases from _tp to _ts , and the horizontal axis represents the distribution amount C of oxygen atoms at any position in the layer thickness direction of the amorphous layer 103,
It is shown that the amount of distribution is large in the direction of the arrow.

In the example shown in FIG. 2, the distribution state of oxygen atoms contained in the amorphous layer 103 in the layer 103 is a distribution amount C ₁ from the lower surface position t ₀ to the position t ₁ . From the position t ₁ to the upper surface t _s , the distribution amount decreases in a linear function from the distribution amount C ₂ , and at the upper surface position t _s , the content of oxygen atoms substantially decreases. has become 0.

In the present invention, as described above, the amorphous layer 103
The fact that the content of oxygen atoms is essentially 0 at a certain layer thickness indicates that the amount of oxygen atoms is below the detection limit in that layer region, and it is actually This also includes cases where oxygen atoms are contained in amounts below the detection limit.

At present, at our technological level,
The detection limit for the amount of oxygen atoms is 200 atomic ppm relative to silicon atoms.

Therefore, the fact that the oxygen atom content is substantially 0 includes cases where the oxygen atom content is less than 200 atomic ppm.

In the example shown in FIG. 2, by extremely increasing the distribution amount C of oxygen atoms between layer thickness positions _t0 and _t1 , the lower surface layer region of the amorphous layer 103 can have a sufficient barrier layer function.

In the example shown in FIG. 3, the distribution amount C ₁ is constant from the lower surface position t ₀ to the position t ₁ , and gradually increases from the position t ₁ to the upper surface position t _s . The distribution follows a curve and gradually decreases.

In the example shown in Figure 4, from t ₀ to t ₁ ,
The distribution amount C is constant at ₁ , the distribution amount decreases in a linear function from t ₁ to t ₂ , and the distribution amount C ₂ is constant between t ₂ and t _s . .

If the distribution amount C ₂ in the upper surface layer region (the part between t ₂ and t _s in the figure) is made to contain enough oxygen atoms to exhibit the barrier function, the amorphous layer It is possible to sufficiently provide the upper surface layer region with the function of a barrier layer.

In the case of the example shown in FIG. 4, the distribution amount C of oxygen atoms on both surface sides of the amorphous layer is extremely large compared to the inside. It has become possible for the barrier layer to fully perform its function.

In the example shown in Figure 5, from t ₀ to t ₂ the distribution state is similar to that shown in Figure 3, but between t ₂ and t _s , the overall distribution state is selected such that the distribution amount increases rapidly and has a value of C ₂ .

The example in Figure 6 has a distribution state similar to that of the example shown in Figure 3 from t ₀ to t ₃ , but between t ₃ and t ₂ , the oxygen atoms The content is
A layer region of substantially 0 is formed, and a large amount of oxygen atoms are contained between t ₂ and t _s , and the distribution amount is
C is to get ₂ .

In the example shown in FIG. 7, between t ₀ and t ₁ , the distribution amount C ₁ is constant, and between t ₁ and t ₂ ,
An example is shown in which the distribution amount decreases linearly from the distribution amount C ₃ to the distribution amount C ₄ from the t ₁ side, and the distribution amount increases again between t ₂ and t _s and takes a constant value C ₂ . .

In the example shown in Figure 8, a constant distribution amount C ₁ is taken between t ₀ and t ₁ , and a constant distribution amount C ₂ is taken between t ₂ and t _s . The distribution state taken is t ₂ and
From _{the t 1 side} to the center of the layer,
The distribution state is such that it gradually decreases, gradually increases from the center of the layer until t ₂ , and takes a distribution amount C ₄ at t ₂ .

In the present invention, a peak having a distribution amount that is larger in steps than in the center of the amorphous layer on the surface of the amorphous layer on the support side or near the surface as explained in FIGS. 2 to 8 is obtained. It has a layer region having
Furthermore, if necessary, a layer region having an extremely higher content than the central portion of the layer is also formed in the surface region of the amorphous layer on the side opposite to the support.

In the present invention, it is desirable that a layer region is formed at or near the lower surface of the amorphous layer so that the function of the barrier layer can be sufficiently exhibited.

In this case, the peak value of the distribution amount of the layer region is usually 0.3 to 67 atomic%, preferably 0.5 to 67 atomic%, and optimally 1.0 to 67 atomic%, as described above.
It is desirable that the range is 67 atomic%.

In the photoconductive member of the present invention, the amorphous layer 103
As described above, the content of oxygen atoms contained in the amorphous layer 103 is unevenly distributed in the thickness direction, and extends from the vicinity of the lower layer region to the center of the amorphous layer. Therefore, although it can be contained in the amorphous layer so that the distribution state can be such that the amount of distribution is reduced, it is contained in the entire amorphous layer 103 that is formed. The content of oxygen atoms is also one of the important factors in achieving the intended purpose of the present invention.

In the present invention, the value of the total amount of oxygen atoms contained in the amorphous layer 103 is usually 0.05 as described above.
It can take values in the range ~30atomic%,
Furthermore, preferably 0.05 to 20 atomic%, optimally 0.05
It is desirable to select from a range of ~10 atomic%.

In the present invention, in order to form the amorphous layer 103 mainly composed of a-Si (H, It is made by a deposition method. For example, in order to form an amorphous layer by the glow discharge method, the internal pressure of the raw material gas for introducing hydrogen atoms and/or for introducing halogen atoms is reduced, along with the raw material gas for Si generation that can generate Si. A glow discharge is generated in the deposition chamber to form a layer of a-Si(H, .

In order to introduce oxygen atoms into the layer to be formed, a raw material gas for introducing oxygen atoms may be introduced into the deposition chamber at the time of forming the layer, in conjunction with the growth of the layer.
In addition, when forming by a sputtering method, for example, when sputtering a target formed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms or / Then, a gas for introducing halogen atoms may be introduced into a deposition chamber for sputtering. At this time, the method for introducing oxygen atoms into the amorphous layer is to introduce a raw material gas for introducing oxygen atoms into the deposition chamber at the time of layer formation, in conjunction with the growth of the layer;
Alternatively, when forming the layer, a target for introducing oxygen atoms, which has been provided in advance in the deposition chamber, may be sputtered.

In the present invention, the Si generation raw material gas used when forming the amorphous layer includes SiH ₄ , Si ₂ H ₆ ,
Gaseous or gasifiable silicon hydrides (silanes), such as Si ₃ H ₆ and Si ₄ H ₁₀ , can be effectively used. SiH ₄ ·Si ₂ H ₆ is preferred in terms of high production efficiency.

In the present invention, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer, such as halogen gas, halides, interhalogen compounds,
Preferred examples include gaseous or gasifiable halogen compounds such as halogen-substituted silane derivatives.

Further, silicon compounds containing halogen, which are in a gaseous state or can be gasified and which have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, and IBr.

Preferred examples of silicon compounds containing halogens, so-called halogen-substituted silane derivatives include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . .

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing halogen, silicon hydride gas is used as a raw material gas that can generate Si. At least, an amorphous layer made of a-Si:X can be formed on a predetermined support.

When manufacturing an amorphous layer containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for Si generation, and Ar, H ₂ ,
By introducing a gas such as He into a deposition chamber in which an amorphous layer is formed at a predetermined mixing ratio and gas flow rate, a glow discharge is generated to form a plasma atmosphere of these gases. Therefore, an amorphous layer can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of silicon compound gas containing hydrogen atoms is also mixed with these gases to form a layer. It may be formed.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. To form an amorphous layer made of a-Si(H, In the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is heated using a resistance heating method or an electron beam method (EB method). This can be done by heating and evaporating the flying evaporated material using a method such as the method (method), etc., and passing the flying evaporated material through a predetermined gas plasma atmosphere.

At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Good.

Oxygen atoms contained in the amorphous layer to be formed in a desired distribution state in the layer thickness direction can be obtained when the amorphous layer is formed by a glow discharge method, an ion plating method, or a reactive sputtering method. for,
The raw material gas for introducing oxygen atoms may be introduced into the deposition chamber for layer formation at a desired flow rate in accordance with the growth of the layer during formation of the layer.

When forming an amorphous layer by sputtering, in addition to the above, a target for introducing oxygen atoms may be provided in the deposition chamber, and the target may be sputtered as the layer grows. .

In the present invention, oxygen (O ₂ ), ozone (O ₃ ), Si, O, and OH are constituent atoms that are effectively used as the raw material gas for introducing oxygen atoms. Examples include lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ).

Further, as materials capable of forming a target for introducing oxygen atoms, SiO ₂ , SiO, etc. are effectively used in the present invention.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen used when forming the amorphous layer. In addition, hydrogen halides such as HF, HCl, HBr, and HI, SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and SiHBr ₃ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents can also be mentioned as effective starting materials for forming the amorphous layer.

These halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming an amorphous layer, so the present invention It is used as a suitable raw material for introducing halogen.

In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be done by causing a discharge by causing a silicon hydride gas such as Si ₃ H ₈ or Si ₄ H ₁₀ to coexist with a silicon compound for producing Si in a deposition chamber.

For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. has certain characteristics, mainly a-Si
An amorphous layer consisting of (H,X) is formed.

Furthermore, B ₂ H ₆ , which also serves as impurity doping,
Gases such as PH ₃ and PF ₃ can also be introduced.

In the present invention, the amount of H or X contained in the amorphous layer of the photoconductive member to be formed or (H+X)
The amount of is usually 1 to 40 atomic%, preferably 5
It is desirable to set it to ×30 atomic%.

The amount of H and/or All you have to do is control the force.

In order to make the amorphous layer have an n-type tendency, a p-type tendency, or an i-type tendency, an n-type impurity, a p-type impurity, or both impurities are formed during layer formation by a glow discharge method, a reactive sputtering method, etc. This is accomplished by doping the layer in a controlled amount.

In order to make the amorphous layer i-type or p-type, impurities doped into the amorphous layer include elements of group A of the periodic table, such as B, Al, Ga,
Suitable examples include In and Tl.

In the case of an n-type tendency, suitable elements include elements of group A of the periodic table, such as N, P, As, Sb, and Bi.

In the present invention, in order to have a desired conductivity type,
The amount of impurities introduced into the amorphous layer is 3× in the case of impurities in group A of the periodic table.
Doping may be done in an amount range of 10 ^-2 atomic % or less, and in the case of impurities in group A of the periodic table, doping may be done in an amount range of 5×10 ^-3 atomic % or less.

The layer thickness of the amorphous layer 103 is appropriately determined as desired so that the photocarriers generated in the amorphous layer 103 are efficiently transported, and is usually 3 to 3.
The thickness is 100μ, preferably 5 to 50μ.

Example 1 Using the apparatus shown in FIG. 9 installed in a completely shielded clean room, an electrophotographic image forming member was produced by the following operations.

A molybdenum plate (substrate) 909 having a surface cleaned and having a thickness of 0.5 mm and 10 cm square was firmly fixed to a fixing member 903 at a predetermined position in the glow discharge deposition chamber 901 . The substrate 909 is heated with an accuracy of ±0.5° C. by a heater 908 within the fixing member 903.
Temperature was measured directly on the backside of the substrate by a thermocouple (alumel-chromel).

Next, after confirming that all valves in the system were closed, the main valve 910 was fully opened to evacuate the chamber 901 to a degree of vacuum of approximately 5×10 ^-6 Torr. Thereafter, the input voltage of the heater 908 was increased, and the input voltage was varied while detecting the temperature of the molybdenum substrate until it stabilized at a constant value of 250°C.

Then the auxiliary valve 941 and then the outflow valve 9
26,927,929 and inflow valve 921,9
22,924 were fully opened, and the mass flow controllers 916, 917, and 919 were also sufficiently degassed to a vacuum state. Auxiliary valve 941, valves 926, 92
After closing 7,929,921,922,924, _SiH4 gas diluted to 10 vol% with _H2 (purity
99.999%, hereinafter abbreviated as SiH ₄ (10)/H ₂ . ) cylinder 9
Open the valve 931 of 11 and the valve 934 of the O ₂ gas (purity 99.999%) cylinder 914, adjust the pressure of the outlet pressure gauges 936, 939 to 1 Kg/cm ² , gradually open the inflow valves 921, 924, and gradually open the mass flow controller 916. , SiH ₄ (10)/H ₂ gas into 919,
_O2 gas was injected into each. Subsequently, the outflow valves 926 and 929 were gradually opened, and then the auxiliary valve 941 was gradually opened. At this time SiH ₄ (10)/H ₂
Mass flow controllers 916 and 919 were adjusted so that the ratio of gas flow rate to O ₂ gas flow rate was 10:1. Next, while watching the reading on the Pirani gauge 942, adjust the opening of the auxiliary valve 941, and
Auxiliary valve 94 until the inside of 1 becomes 1×10 ^-2 Torr.
I opened 1.

After the internal pressure in the chamber 901 is stabilized, the main valve 9
10 was gradually closed, and the aperture was narrowed down until the reading on the Pirani gauge 941 became 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 905 (which also serves as an electrode) is closed, the high frequency power source 943 is turned on, and the electrode 90 is turned on.
Injecting 13.56MHz high frequency power between 3,905 and
A glow discharge was generated in the chamber 901, and the input power was 3W.

After forming a lower barrier layer with a thickness of 600 Å on the molybdenum substrate by maintaining the above conditions for 10 minutes, the high frequency power source 943 is turned off, and the outflow valve 929 is closed while the glow discharge is stopped.
O ₂ gas (purity 99.999%, hereinafter abbreviated as O ₂ ( ^0.1 )/He) diluted to 0.1 vol. Gradually open the inflow valve 922 and outflow valve 927 to flow O ₂ (0.1)/He gas into the mass flow controller 917, and by adjusting the mass flow controllers 916 and 917.
The flow ratio of O ₂ (0.1)/He gas and SiH ₄ (10)/H ₂ gas was adjusted to 1:1. Subsequently, the high frequency power supply 943 was turned on again to restart glow discharge. The input power at that time was 10W.

Under the above conditions, at the same time as the photoconductive layer was started to be deposited on the lower barrier layer, the flow rate setting value of the mass flow controller 917 was continuously decreased for 3 hours.
The SiH ₄ (10)/H ₂ gas flow rate and the O ₂ (0.1)/He gas flow rate ratio after the time were adjusted to be 10:0.3. After forming the layer in this way for 3 hours, the heating heater 908 is turned off, and the high frequency power source 943 is also turned off.
After waiting for the substrate temperature to reach 100°C, open the outflow valves 926, 927 and the inflow valve 92.
1,922,924 is closed, main valve 910
After fully opening the chamber 901 to bring the pressure within the chamber 901 to 10 ^-5 Torr or less, the main valve 910 was closed, the chamber 901 was brought to atmospheric pressure by the leak valve 906, and the substrate was taken out. In this case, the total thickness of the formed layer is approximately
It was 9μ.

The image forming member thus obtained was placed in a charging exposure experimental device, corona discharge was performed at 5.5 KV for 0.2 seconds, and a light image was also irradiated immediately. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux·sec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the member surface by cascading a charged developer (including toner and carrier) onto the member surface. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good tone reproducibility was obtained.

Example 2 A molybdenum substrate was installed in the same manner as in Example 1, and then a vacuum of 5×10 ^-6 Torr was created in the glow discharge deposition chamber 901 by the same operation as in Example 1, and the substrate temperature was raised to 250°C. After being maintained, the auxiliary valve 941, then the outflow valves 926, 927, and the inflow valves 921, 922 are opened by the same operation as in Example 1.
fully open, and mass flow controller 916,9
The interior of No. 17 was also sufficiently degassed and vacuumed. Auxiliary valve 941, valve 926, 927, 921, 922
After closing the valve 931 of SiH ₄ (10)/H ₂ gas cylinder 911, O ₂ (0.1)/He gas cylinder 91
2 valve 932 is opened, and the outlet pressure gauge 936,
Adjust the pressure of 937 to 1Kg/cm ² and open the inflow valve 9.
Gradually open 21,922 and introduce SiH ₄ (10)/H ₂ gas, O ₂ into mass flow controllers 916, 917.
(0.1)/He were respectively injected. Subsequently, the outflow valves 926 and 927 were gradually opened, and then the auxiliary valve 941 was gradually opened. At this time SiH ₄
The inflow valves 921 and 922 were adjusted so that the ratio of the (10)/H ₂ gas flow rate and the O ₂ (0.1)/He gas flow rate was 1:10.

Next, the opening of the auxiliary valve 941 was adjusted while observing the reading on the Pirani gauge 942, and the auxiliary valve 941 was opened until the inside of the chamber 901 reached 1×10 ⁻² Torr. After the internal pressure of the chamber 901 stabilizes, the main valve 910 is gradually closed, and the Pirani gauge 941 is closed.
The aperture was narrowed down until the reading was 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter (also serving as an electrode) 905 is closed and the high frequency power source 943 is turned on, and 13.56 MHz high frequency power is applied between the electrodes 903 and 905. and generate a glow discharge in the chamber 901,
The input power was 10W. At the same time as the photoconductive layer was started to be deposited on the substrate under the above conditions, the flow rate setting value of the mass flow controller 917 was continuously decreased for 5 hours, and the SiH ₄ (10)/H ₂ gas flow rate after 5 hours was
The O ₂ (0.1)/He gas flow ratio was adjusted to 10:0.3.

After forming the photoconductive layer in this manner, the heating heater 908 is turned off, the high frequency power source 943 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 926, 927 and the inflow valve 92 are turned off.
1,922 was closed and the main valve 910 was fully opened to bring the inside of the chamber 901 to 10 ^-5 Torr or less, then the main valve 910 was closed and the inside of the chamber 901 was brought to atmospheric pressure by the leak valve 906 and the substrate was taken out. . In this case, the total thickness of the layer formed was approximately 15μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained.

Example 3 After forming a lower barrier layer and a photoconductive layer on a molybdenum substrate using the same operations and conditions as in Example 1, the high frequency power source 943 was turned off, and the outflow valve 927 was closed while the glow discharge was stopped. Then, the outflow valve 929 is opened again, and the O ₂ gas flow rate is adjusted by adjusting the mass flow controllers 919 and 196.
The flow rate was stabilized at 1/10 of the SiH ₄ /H ₂ gas flow rate. Subsequently, the high frequency power supply 943 was turned on again to restart the glow discharge. The input power at that time was also 3W as before.

After continuing the glow discharge for another 15 minutes to form an upper barrier layer with a thickness of 900 Å, the heater 908 is turned off, and the high frequency power source 943 is also turned off.
off state, wait until the substrate temperature reaches 100°C, and then open the outflow valves 926, 929 and the inflow valve 9.
21, 922, 924 and close the main valve 91.
After fully opening the chamber 901 to bring the pressure below 10 ^-5 Torr, the main valve 910 was closed, and the chamber 901 was brought to atmospheric pressure by the leak valve 906, and the substrate was taken out. The total thickness of the layer formed in this case is approximately
It was 9μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained.

Example 4 After forming a photoconductive layer on a molybdenum substrate using the same operations and conditions as in Example 2, the high frequency power source 943 was turned on.
The outflow valve 927 is closed in the off state and the glow discharge is stopped, and then the outflow valve 927 is closed again.
Open the mass flow controller 919, 91
6, the O ₂ gas flow rate was stabilized to 1/10 of the SiH ₄ (10)/H ₂ gas flow rate. Subsequently, the high frequency power supply 943 was turned on again to restart glow discharge. The input power at that time was also 3W as before.

After continuing the glow discharge for another 10 minutes to form an upper barrier layer with a thickness of 900 Å, the heater 908 is turned off, and the high frequency power source 943 is also turned off.
off state, wait until the substrate temperature reaches 100°C, and then open the outflow valves 926, 929 and the inflow valve 9.
21, 922, 924 and close the main valve 91.
After fully opening the chamber 901 to bring the pressure below 10 ^-5 Torr, the main valve 910 was closed, and the inside of the chamber 901 was brought to atmospheric pressure through the leak valve 906 and taken out to the substrate. In this case, the total thickness of the layer formed was approximately 15μ. Example 1 of this image forming member
When an image was formed on transfer paper under the same conditions and procedures as above, an extremely clear image was obtained.

Example 5 A molybdenum substrate was installed in the same manner as in Example 1, and then a vacuum of 5×10 ^-6 Torr was created in the glow discharge deposition chamber 901 by the same operation as in Example 1, and the substrate temperature was raised to 250°C. After being maintained, the auxiliary valve 941 and then the outflow valve 9 are opened by the same operation as in Example 1.
26, 927 and inflow valves 921, 922, and mass flow controllers 916, 91.
7 was also sufficiently degassed and vacuumed. Auxiliary valve 9
41. After closing the valves 926, 927, 921, 922, open the valve 931 of the SiH ₄ (10)/H ₂ gas cylinder 911 and the valve 932 of the O ₂ (0.1)/He gas cylinder 912, and check the outlet pressure gauges 936, 937.
Adjust the pressure to 1Kg/cm ² and open the inflow valves 921, 9.
22 gradually open the mass flow controller 9.
16,917 into, SiH ₄ (10)/H ₂ gas, O ₂
(0.1)/He were respectively injected. Subsequently, the outflow valves 926 and 927 were gradually opened, and then the auxiliary valve 941 was gradually opened. At this time SiH ₄
The inflow valves 921 and 922 were adjusted so that the ratio of the (10)/H ₂ gas flow rate and the O ₂ (0.1)/He gas flow rate was 1:10.

Next, the opening of the auxiliary valve 941 was adjusted while observing the reading on the Pirani gauge 942, and the auxiliary valve 941 was opened until the inside of the chamber 901 reached 1×10 ⁻² Torr. After the internal pressure of the chamber 901 stabilizes, the main valve 910 is gradually closed, and the Pirani gauge 941 is closed.
The aperture was narrowed down until the reading was 0.3Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter (also serving as an electrode) 905 is closed and the high frequency power source 943 is turned on, and 13.56 MHz high frequency power is applied between the electrodes 903 and 905. and generate a glow discharge in the chamber 901,
The input power was 10W. Under the above conditions, the flow rate setting value of the mass flow controller 917 was continuously decreased for 2.5 hours at the same time as the _{photoconductive} layer was started to _be deposited on the substrate. ₂ (0.1)/He gas flow rate ratio was adjusted to 10:0.3. After that, after maintaining the same conditions for 30 minutes, change the mass flow controller 91 to
Continuously increase the flow rate setting value of 7, and after 2.5 hours.
The ratio of SiH ₄ (10)/H ₂ gas flow rate to O ₂ (0.1)/He gas flow rate was adjusted to 1:10.

After forming the photoconductive layer in this manner, the heating heater 908 is turned off, the high frequency power source 943 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 926, 927 and the inflow valve 92 are turned off.
1,922 was closed and the main valve 910 was fully opened to bring the inside of the chamber 901 to 10 ^-5 Torr or less, then the main valve 910 was closed and the inside of the chamber 901 was brought to atmospheric pressure by the leak valve 906 and the substrate was taken out. . In this case, the total thickness of the layer formed was approximately 17μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained.

Example 6 After forming a lower barrier layer on a molybdenum substrate under the same operation and conditions as in Example 1, a high frequency power source 943 was applied.
After closing the outflow valve 929 with the gas turned off and the glow discharge stopped, the valve 932 of the O ₂ (0.1)/He gas cylinder 912 is turned on to 50 volppm of H _{2 .
B2H6} gas diluted to (purity 99.999%, below ₎
Abbreviated as B ₂ H ₆ (50)/H ₂ . ), open the valve 933 of the cylinder 913, adjust the pressure of the outlet pressure gauges 937, 938 to 1 Kg/cm ² , and open the inlet valves 922, 92.
3 gradually open the mass flow controller 91.
7,918 into O ₂ (0.1)/He gas, B ₂ H ₆
(50)/H ₂ gas was introduced. Subsequently, the outflow valves 927 and 928 are gradually opened, and SiH ₄ (10)/H ₂
The ratio of gas flow rate and O ₂ (0.1)/He gas flow rate is 1:10,
Mass flow controllers 916, 917, and 918 were adjusted so that the ratio of SiH ₄ (10)/H ₂ gas flow rate to B ₂ H ₆ (50)/H ₂ gas flow rate was 1:5. Next, the opening of the auxiliary valve 941 was readjusted while observing the reading on the Pirani gauge 942, and the internal pressure in the chamber 901 was set to 1×10 ⁻² Torr. Further room 9
After the internal pressure of 01 is stabilized, the main valve 910
Readjust the Pirani gauge 942 and readjust it.
It was set to 0.1Torr.

After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 943 again.
A high frequency power of 13.56 MHz was applied to restart glow discharge in the chamber 901, resulting in an input power of 10 W.

Under the above conditions, the photoconductive layer was deposited using a mass flow controller 917 for 5 hours at the same time as the deposition started.
After 5 hours, the flow rate setting value of
The SiH ₄ (10)/H ₂ gas flow rate and O ₂ (0.1)/He gas flow rate ratio were adjusted to be 10:0.3. After forming the layer in this manner for 5 hours, the heating heater 908
is turned off, the high frequency power supply 943 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 926, 927, 928 and the inflow valve 9 are turned off.
21, 922, 923, and 924, and fully open the main valve 910 to open the chamber 901.
After reducing the pressure to 10 ^-5 Torr or less, the main valve 910 was closed, and the inside of the chamber 901 was brought to atmospheric pressure by the leak valve 906, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 15μ.

The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.5 KV for 0.2 seconds, and immediately irradiated with a light image. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux·sec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.5KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Next, the image forming member was corona charged for 0.2 seconds at 6.0KV using a charging exposure experiment device, and immediately
Image exposure was performed at a light intensity of 1.0 lux·sec, and then a charged developer was immediately applied to the surface of the member in a gascade, and then transferred and fixed onto transfer paper, resulting in an extremely clear image.

From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member.

Example 7 SiH ₄ (10)/H ₂ gas cylinder 911 was replaced with SiF ₄ gas (purity 99.999%) cylinder, O ₂ (0.1)/H ₂ gas cylinder 912 was replaced with argon containing 0.2 vol% oxygen (hereinafter O ₂ ( 0.2)/Ar gas (abbreviated as 99.999% purity) gas at the initial stage of deposition of the photoconductive layer.
SiF ₄ gas flow rate and O ₂ (0.2)/Ar gas flow rate ratio is 1:
18 to start layer formation, and then increase O ₂ (0.2)/Ar so that the ratio of SiF ₄ gas flow rate and O ₂ (0.2)/Ar gas flow rate at the end of photoconductive layer deposition is 1:0.6. A photoconductive layer was formed on a molybdenum substrate under the same operating conditions as in Example 2, except that the gas flow rate was continuously reduced and the input power for glow discharge was 100 W.
In this case, the thickness of the layer formed was approximately 18μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained.

Example 8 Using the apparatus shown in FIG. 9, an electrophotographic image forming member was produced by the following operations.

A molybdenum (substrate) 0.5 mm thick and 10 cm square whose surface was cleaned was firmly fixed to a fixing member 903 at a predetermined position in the deposition chamber 901 . target 90
4 has high purity graphite (99.999%) placed on polycrystalline high purity silicon (99.999%). The substrate 909 is heated with an accuracy of ±0.5° C. by a heater 908 within the fixing member 903.
Temperature was measured directly on the back side of the substrate by a thermocouple (alumel-chromel). Next, after confirming that all valves in the system are closed, fully open the main valve 10 and once
The vacuum is evacuated to about 10 ^-6 Torr (at this time, all valves in the system are closed), the auxiliary valve 941 and the outflow valves 926, 927, 929, 930 are opened, and the mass flow controllers 916, 91
After the inside of No. 7,919,920 was sufficiently degassed, outflow valves 926, 927, 929, 930 and auxiliary valve 941 were closed. Argon (purity
99.999%) After opening the valve 935 of the gas cylinder 915 and adjusting the reading of the outlet pressure gauge 940 to be 1 Kg/cm ² , the inflow valve 925 is opened, followed by the outflow valve 930 being gradually opened,
Argon gas was flowed into chamber 901. The outflow valve 930 is gradually opened until the Pirani gauge 911 indicates 5×10 ^-4 Torr, and after the flow rate has stabilized in this state, the main valve 910 is gradually closed and the indoor pressure is reduced to 1×10 -4 Torr. The aperture was narrowed down to ^-2 Torr. After opening the shutter 905 and confirming that the mass flow controller 920 was stable, the high frequency power source 943 was turned on, and 13.56 MHz, 100 W AC power was input between the target 904 and the fixed member 903. Matching was performed under these conditions to maintain stable discharge, and a layer was formed. Discharge was continued in this manner for 1 minute to form a lower barrier layer with a thickness of 100 Å. Thereafter, the high frequency power source 943 was turned off to temporarily stop the discharge. Subsequently, the outflow valve 930 was closed, and the main valve 910 was fully opened to remove gas from the chamber 901, creating a vacuum of 5×10 ⁻⁶ Torr. After that, the input voltage of the heater 908 was increased, and the input voltage was changed while detecting the substrate temperature, and the temperature reached 200℃.
It was stabilized until it reached a constant value.

Thereafter, a photoconductive layer was formed using the same operations and conditions as in Example 2. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 9 A photoconductive layer was formed on a molybdenum substrate under the same operations and conditions as in Example 7, except that the argon gas cylinder 912 containing 0.2 vol% oxygen in Example 7 was replaced with a helium gas cylinder containing 0.2 vol% oxygen. did. The thickness of the layer formed in this case was approximately 15μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained.

[Brief explanation of drawings]

FIG. 1 is a schematic configuration diagram for explaining the layer structure of a preferred embodiment of the electrophotographic photoconductive member of the present invention, and FIGS. 2 to 8 are respectively the electrophotographic photoconductive members of the present invention. FIG. 9 is a schematic explanatory diagram for explaining the distribution state of oxygen atoms contained in the amorphous layer of FIG. It is an explanatory diagram. 100... Photoconductive member for electrophotography, 101...
Support, 102... Barrier layer, 103... Amorphous layer.

Claims (1)

[Scope of Claims] 1. Consisting of a support and an amorphous material having silicon atoms as a matrix and containing at least one of hydrogen atoms and halogen atoms, containing either or both of the hydrogen atoms and the halogen atoms. The amount is 1~
40 atomic% and an amorphous layer exhibiting photoconductivity, the amorphous layer contains oxygen atoms at least in part, and the distribution concentration of oxygen atoms is A photoconductive member for electrophotography, characterized in that the layer has a region that changes continuously in the thickness direction, and the oxygen atoms are more distributed on the side where the support is provided. . 2. The photoconductive member for electrophotography according to claim 1, further comprising a lower barrier layer between the support and the amorphous layer. 3 Between the support and the amorphous layer, an amorphous material having silicon atoms as a matrix and containing at least one type of atom selected from carbon atoms, nitrogen atoms, and oxygen atoms is formed. The photoconductive member for electrophotography according to claim 1, further comprising a lower layer. 4. Claim 3, wherein the lower layer contains at least either hydrogen atoms or halogen atoms.
A photoconductive member for electrophotography as described in 1. 5. The photoconductive member for electrophotography according to claim 1, further comprising a lower layer made of an electrically insulating metal oxide between the support and the amorphous layer. . 6. The photoconductive member for electrophotography according to claim 1, wherein a barrier layer is provided between the support and the amorphous layer. 7 The content of oxygen atoms in the entire layer region is
The photoconductive member for electrophotography according to claim 1, wherein the content is 0.05 to 30 atomic%. 8. The photoconductive member for electrophotography according to claim 1, wherein the maximum distribution amount of oxygen atoms in the layer region is 0.3 to 67 atomic%. 9 The content of oxygen atoms in the amorphous layer is
The photoconductive member for electrophotography according to claim 1, wherein the content is 0.05 to 30 atomic%. 10. The photoconductive member for electrophotography according to claim 1, wherein the maximum distribution amount of oxygen atoms in the amorphous layer is 0.3 to 67 atomic%. 11. The photoconductive member for electrophotography according to claim 1, further comprising an upper barrier layer on the amorphous layer. 12. The photoconductive member for electrophotography according to claim 1, wherein the amorphous layer contains a p-type or n-type impurity.