JPH0216512B2 - - 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.

Solid-state imaging devices or electrophotographic image forming members in the image forming field are highly sensitive photoconductive materials constituting photoconductive layers in document reading devices, etc.
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, pollution-free properties during use are important.

Based on these points, 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 photoconductive layers 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 cannot be read after repeated use for long periods of time. There are many disadvantages such as accumulation of fatigue and so-called ghost phenomenon, which causes afterimages.

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, the dark decay is extremely fast, compared to ordinary electrophotography. The above-mentioned tendency is remarkable in a humid atmosphere, and in some cases, the electrostatic charge may not be retained at all until the development time, and other points that can be resolved. is known to exist.

Therefore, while efforts are being made to improve the properties of the a-Si material itself, when designing photoconductive members for electrophotography, efforts are being made to obtain the desired electrical, optical, and photoconductive properties as described above. need to be done.

The present invention has been made in view of the above points, and includes a
- As a result of comprehensive and intensive research on Si from the viewpoint of its suitability and applicability as a photoconductive member used in electrophotographic image forming members, we found that Si has a silicon atom as its base material and a hydrogen atom (H ) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as a-Si as a generic notation
(H, When compared with conductive materials, it is superior in most respects, and in particular, as a photoconductive material for electrophotography, it has extremely superior characteristics in terms of photosensitivity and image quality stability. It's based on what you found.

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, and has excellent resistance to light fatigue and does not cause deterioration even after repeated use. The main object of the present invention 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 maintain 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. It is an object of the present invention to provide a photoconductive member for electrophotography, which has sufficient performance and excellent electrophotographic properties in which almost no deterioration in the properties is observed 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 contains a support for a photoconductive member for electrophotography (hereinafter referred to as "photoconductive member"), and at least one or both of hydrogen atoms and halogen atoms, and silicon atoms. In an electrophotographic photoconductive member composed of an amorphous material as a matrix and an amorphous layer exhibiting photoconductivity, the amorphous layer contains nitrogen atoms, and the amorphous A lower layer region in which the nitrogen atoms are substantially uniformly distributed in the layer thickness direction with a distribution amount C ₁ of 60 atomic % or less, and a lower layer region in which the nitrogen atoms are distributed substantially uniformly in the layer thickness direction with a distribution amount C ₂ of 60 atomic % or less sandwiched between the upper layer region where the nitrogen atoms are substantially uniformly distributed and the both layer regions, and where nitrogen atoms are less than 10 atomic % and 0.005 atomic
an intermediate layer region substantially uniformly distributed in the layer thickness direction with a distribution amount C ₃ of % or more;
It is characterized in that C ₁ to C ₃ have a relationship of C ₃ <C ₁ , C ₂ .

A photoconductive member designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and exhibits extremely excellent electrical, optical, photoconductive properties, and use environment characteristics. .

In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, stable electrical characteristics during image formation, high sensitivity, and a high signal-to-noise ratio. It has excellent resistance to light fatigue and repeated use, and can produce high-quality visible images with high density, clear halftones, and high resolution.

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

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 a non-conductive material provided in direct contact with the barrier layer 102. The amorphous layer 103 contains nitrogen atoms, and the distribution of the nitrogen atoms is substantially uniform on the inner surface approximately parallel to the surface of the support 101 and in the thickness direction of the layer. In this case, each part of the layer regions 104, 105, and 106 is different. That is, the amorphous layer 103
is a lower layer region 104 in which nitrogen atoms are substantially uniformly distributed in the layer thickness direction with a distribution amount _C1 , and a lower layer region 104 with a distribution amount C 1
An upper layer region 106 in which nitrogen atoms are distributed substantially uniformly in the layer thickness direction with a distribution amount C ₂ , and nitrogen atoms are sandwiched between these two layer regions and are substantially uniformly distributed in the layer thickness direction with a distribution amount C ₃ . and an intermediate layer region 105 in which oxygen atoms are distributed.

In the present invention, the distribution amount C ₁ , C ₂ , C ₃ of nitrogen atoms in each layer region has a magnitude relationship such that C ₃ <C ₁ ,
Although it can take any desired value such as C ₂ ,
The upper limit for the values of distribution amounts C ₁ and C ₂ is usually
It is desirable that it be 60 atomic% or less, preferably 57 atomic% or less, optimally 50 atomic% or less,
The lower limit is usually 11 atomic % or more, preferably 15 atomic % or more, and optimally 20 atomic % or more.

As for the value of the distribution amount _C3 , its upper limit is usually
It is 10 atomic% or less, preferably 5 atomic% or less, optimally 2 atomic% or less, and the lower limit is usually 0.005 atomic% or more, preferably 0.006 atomic% or more, and optimally 0.007 atomic% or more. is desirable.

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 Nd, 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 conductively 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 if 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, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc.

The barrier layer 102 effectively blocks free carriers from flowing from the support 101 side toward the amorphous layer 103 side or from the amorphous layer 103 side toward the support body 101 side, and prevents electromagnetic waves during electromagnetic wave irradiation. formed in the amorphous layer 103 by the irradiation of
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 functions, but by directly providing the amorphous layer 103 on the support 101, the difference formed between the support 101 and the amorphous layer 103 can be reduced. In the present invention, it is not necessary to provide the barrier layer 102 as long as the same function as that of the barrier layer 102 described above can be sufficiently exhibited in terms of surface area.

Furthermore, by sufficiently containing oxygen atoms in the surface layer region of the amorphous layer 103 on the side of the support 101, the barrier layer 10 can be formed in some regions of the amorphous layer 103.
2 can be loaded with a function similar to that of 2, and the content of nitrogen atoms in this case is usually about 100% compared to silicon atoms in the layer region that exhibits this function.
It is desirable that the content be 25 to 60 atomic %, preferably 30 to 60 atomic %, most preferably 35 to 60 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-[SiX (C,
N, O) _1-x ] _y (H, X) _1-y (however, 0
<x<1, 0<y<1)> or 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 the amorphous material 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 , a-Si _h N _1-h , a-(Si _i N _1-i ) as a nitrogen-based amorphous material _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 , a-Si _p as an oxygen-based amorphous material
O _1-p , a-(Si _p O _1-p ) _q H _1-q , a-(Si _r O _1-r ) _s
X _1-s , a-(Si _t O _1-t ) _u (H+X) _1-u , etc., and further,
Among the above-mentioned amorphous materials, examples include amorphous materials containing at least two types of atoms among C, N, and O 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 most suitable one is selected depending on the ease of continuous production with the amorphous layer 103 stacked on 02 and the like. Particularly 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. Ru.

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 raw material gases 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, 1 carbon atom -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-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), penteso (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, H ₂ is also effectively used 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, silicon hydride, and the like.

Specifically, halogen gases include fluorine, chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, and HBr, and halogen compounds include BrF, ClF, ClF ₃ , ClF ₅ , _BrF5 ,
BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br,
SiCl ₂ Br ₂ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ , examples of silicon hydride include silanes such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc. I can do it.

In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F,
Halogen-substituted paraffinic hydrocarbons such as CH ₃ Cl, CH ₃ Br, CH ₃ I, C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ , SF ₆ , Si(CH ₃ ) ₄ , Si(C ₂ Alkyl silicides such as H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ ,
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 to form a 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. They are 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 , SiH ₂ Cl ₂ ,
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 the 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, a starting material that can be effectively used as a raw material gas for introducing nitrogen atoms to form the barrier layer 102 is nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), gaseous or gasifiable nitrogen, nitrides and azides, etc. The following nitrogen 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. The starting material for introducing an oxygen atom is added to a starting material selected from among the starting materials for the formation as desired.The starting material for introducing an oxygen atom is a gaseous material having at least an oxygen atom as a constituent atom. Most substances or gasified versions of gasifiable substances 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
It is possible to use a mixture of a raw material gas having three constituent atoms: and H.

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) carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitric oxide (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 ), composed of Si, O, and H, For example disiloxane H ₃ SiOSiH ₃ trisiloxane
Examples include lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ and the like.

As mentioned above, the barrier layer 1 is
When forming the barrier layer 102, by selecting and using various starting materials for forming the barrier layer from among the above-mentioned materials, it is possible to form the barrier layer 102 made of a desired constituent material having desired characteristics. I can do it.
Specifically, favorable combinations of starting materials when forming the barrier layer 102 by the glow discharge method include:
For example, single gas such as Si(CH ₃ ) ₄ , SiCl ₂ (CH ₃ ) ₂ or
SiH ₄ -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 source gas for introducing carbon atoms and hydrogen atoms (H) or halogen atoms (X) is
The Si wafer may be sputtered by diluting it with a diluting gas as necessary and introducing it into a deposition chamber for sputtering to form a gas plasma of these gases.

Alternatively, at least hydrogen atoms (H) can be removed by using separate targets for Si and C or by using a single target containing Si and C.
Alternatively, it can be performed by sputtering in a gas atmosphere containing halogen atoms (X).

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 case of 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 the wafers contained in the wafer in various gas atmospheres.

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, Si and Si ₃ N ₄ can be used as separate targets or as a sputtering gas by forming a mixture of Si and Si ₃ N ₄ and using a single target. This is done by sputtering in a dilute 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.

In order 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, by using a target other than Si and SiO ₂ or a single target with a mixture of Si and SiO ₂ , the sputtering can be carried out in an atmosphere of diluent gas as a sputtering gas or at least H
This is accomplished by sputtering in a gas atmosphere containing 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, a so-called rare gas, such as He,
Preferable examples include Ne and Ar.

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

In other words, the dynamic substance whose constituent atoms are Si, at least one of C, N, and O, and H or/and X depending on the composition takes a structural form from crystal to amorphous depending on the conditions of its creation. In terms of electrical properties, properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties,
Therefore, in the present invention, the preparation conditions are strictly selected so that a non-photoconductive amorphous material is formed.

The amorphous material constituting the barrier layer 102 of the present invention has the function of the barrier layer 102 as a free carrier from the support 101 side to the amorphous layer 103 side or from the amorphous layer 103 side to the support 101 side. A material that exhibits electrically insulating behavior because it prevents injection and easily allows photocarriers generated in the amorphous layer 103 to move and pass through to the support 101 side. is formed as.

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 formed as desired.

In order to effectively achieve the purpose of the present invention, the optimum 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. is executed, but
In the case of systems containing hydrogen atoms or halogen atoms, the temperature is usually 100°C to 300°C, preferably 150°C to 250°C.
℃, and when the hydrogen atom does not contain a halogen atom, the temperature is usually 20 to 200℃, preferably 20 to 150℃. The barrier layer 102 can be formed continuously in the same system from the barrier layer 102 to the non-barrier layer 103, and further to the third layer formed on the amorphous layer 103 if necessary. The use of the glow discharge method and sputtering method is 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. However, when forming the barrier layer 102 using these layer forming methods, the discharge power and gas pressure during layer formation, as well as the support temperature described above, are
This can be cited as an important factor that influences 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. The gas pressure in the deposition chamber is usually 3×10 ^-3 to 5 Torr, preferably 8 Torr.
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 made of a-SiaC _1-a , the content of carbon atoms is usually 60 to 90 atomic%, preferably 65 to 80 atomic%, based on silicon atoms.
Optimally 70-75 atomic%, 0.1-75 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 30-90 atomic%, preferably 40-90 atomic%, optimally 50-80 atomic%
%, the content of hydrogen atoms is usually 1 to
40 atomic%, preferably 2 to 35 atomic%, optimally 5 to 30 atomic%, expressed as b, c, b
is typically 0.1 to 0.5, preferably 0.1 to 0.35, optimally
0.15~0.3, c is usually 0.60~0.99 preferably 0.65~
0.98, optimally 0.7 to 0.95, a-(Si _d C _1-d )
_{When composed of e _ _}
90 atomic%, preferably 50 to 90 atomic%, optimally 60 to 80 atomic%, the content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 1.
20 atomic%, preferably 1 to 18 atomic%, optimally 2 to 15 atomic%, and when both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually 19 atomic% or less, preferably 13atomic
% or less, and in the display of d, e, f, g, d,
f is usually 0.1 to 0.47, preferably 0.1 to 0.35, optimally 0.15 to 0.3, and e and g are usually 0.8 to 0.99, preferably 0.85 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 0.43 to 0.60, preferably 0.43 to 0.50.

When composed of a-(Si _i N _1-i ) _j H _1-j , the nitrogen atom content is usually 25 to 55 atomic%,
The water atom content is preferably 35 to 55 atomic%, and the water atom content is usually 2 to 35 atomic%, preferably 5 to 55 atomic%.
30 atomic% and expressed as i, j, i is usually 0.43 to 0.6, preferably 0.43 to 0.5, j is usually 0.65 to 0.98, preferably 0.7 to 0.95, and a-(Si _k N _1-k ) ₁ X _1-l or a-(Si _n N _1-n ) _o
(H+X) When composed of _1-o , the nitrogen atom content is usually 30 to 60 atomic%, preferably 40 to
50 atomic%, the content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 50 atomic%.
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, and k, l, m,
In the representation of n, k and l are 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 combined content of halogen atoms and hydrogen atoms is usually 1 to 20 atomic%, preferably 2 to 15 atomic%, and when both halogen atoms and hydrogen atoms are contained, hydrogen atoms The content is usually less than 19 atomic%, preferably 13 atomic%.
In the representation of r, s, t, u, r, s
is usually 0.33 to 0.40, preferably 0.33 to 0.37t, and u is usually 0.80 to 0.99, preferably 0.85 to 0.98.

In the present invention, the electrically insulating metal oxides constituting the barrier layer 102 include 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 .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 1 can be formed by a sputtering method.
To form 02, He, Ne, Ar
This may be carried out by sputtering in a gas atmosphere for sputtering such as.

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. Since it serves to prevent the photocarriers generated in the amorphous layer 103 from moving and pass through to the support 101 side, it is considered to exhibit electrically insulating behavior. It is formed.

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,
The function of preventing free carriers from flowing from the side of the support 101 toward the side of the amorphous layer 103 or from the side of the amorphous layer 103 toward the side of the support 101 becomes insufficient or insufficient. If it is thicker than a certain amount, the probability that photocarriers generated in the amorphous layer 103 will pass to the support 101 side becomes extremely small, and therefore, in any case, the purpose of the present invention cannot be effectively achieved. can no longer be achieved.

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 nitrogen atoms are doped in the layer thickness direction in the distribution state described above.

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 type of p ^- type a-Si(H,X)... that is lightly doped with a so-called p-type impurity that has a low acceptor concentration (Na).

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 103 include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as.

In the present invention, in order to form the amorphous layer 103 mainly composed of a-Si (H, done by. 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. The a-Si(H,
What is necessary is to form a layer consisting of. To introduce nitrogen atoms into the layer being formed, along with the growth of the layer,
A raw material gas for introducing nitrogen atoms may be introduced into the deposition chamber during formation of the layer. In addition, when forming by sputtering method, for example, the process of sputtering the target on which Si is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases; A gas for introducing hydrogen atoms and/or halogen atoms may be introduced into the deposition chamber for sputtering.

In this case, the method of introducing nitrogen atoms into the amorphous layer 103 is to introduce a raw material gas for introducing nitrogen atoms into the deposition chamber at the time of layer formation, or to At the time of formation, a target for introducing nitrogen atoms, which has been provided in advance in the deposition chamber, may be sputtered.

In the present invention, SiH 4 , SiH ₄ ,
Gaseous or gasifiable silicon hydrides (silanes), such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., can be used effectively, especially in layer formation operations. SiH ₄ , due to its ease of handling and good Si generation efficiency,
Si ₂ H ₆ is preferred.

In the present invention, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer 103.
For example, halogen compounds that can be gasified or gasified are preferably used, such as halogen gas, halides, interhalogen compounds, and halogen-substituted silane derivatives.

Furthermore, silicon compounds containing silicon atoms and halogen atoms, which are in a gaseous state or can be gasified, are also 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 ₅ , 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 the amorphous layer 103 containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for Si generation, and Ar,
It is introduced into a deposition chamber where an amorphous layer is formed at a predetermined mixing ratio and gas flow rate with gases such as H ₂ and He, and a glow discharge is generated to form a plasma atmosphere of these gases. In some cases, the amorphous layer 103 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 added to these gases. May be mixed.

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. In order 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 used by a resistance heating method or an electron beam method. (EB method), etc., and the flying evaporated material is passed 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 if a plasma atmosphere of the gas is formed by introducing the gas into the atmosphere.

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.

Nitrogen atoms contained in the amorphous layer to be formed in a desired distribution state in the layer thickness direction are formed by a glow discharge method, an ion plating method, or a reaction sputtering method. In this case, the raw material gas for introducing nitrogen atoms may be introduced into the deposition chamber for forming the layer at a desired flow rate in accordance with the growth of the layer during the formation of the layer.

In the present invention, a gaseous or easily gaseous starting material is effectively used as a raw material gas for introducing nitrogen atoms into the amorphous layer 103. A large number of nitrogen compounds can be mentioned.

Examples of such starting materials include nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (NH ₃ ), gaseous or gasifiable nitrogen such as ammonium azide (NH ₄ N ₃ ), and nitrogen compounds such as nitrides and azides. In addition to the above, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be used, as they can also introduce halogen atoms in addition to nitrogen atoms. I can list them.

To form the amorphous layer 103 into which nitrogen atoms are introduced by the sputtering method, a single crystal or polycrystalline Si wafer or a Si ₃ N ₄ wafer or
Wafers containing a mixture of Si and Si ₃ N ₄ are targeted and sputtered in various gas atmospheres, or single crystal or polycrystalline Si wafers are sputtered for carbon atom introduction. All it takes is sputtering in the atmosphere of the raw material gas.

For example, if a Si wafer is used as a target, nitrogen atoms and optionally hydrogen atoms or/and
A raw material gas for introducing halogen atoms, such as H ₂ and N ₂ or NH ₃ , is diluted with a diluting gas as necessary and introduced into a sputtering deposition chamber. Forming a gas plasma
All you have to do is sputtering Si.

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.

In the present invention, in addition to nitrogen atoms, carbon atoms and/or oxygen atoms can be introduced into the amorphous layer 103 in order to obtain the same effect as that obtained by introducing nitrogen atoms. .

As a starting material that can be used as a raw material gas for introducing carbon atoms or oxygen atoms, those mentioned above as starting materials for forming a barrier layer are employed as effective starting materials, as well as, for example, oxygen (O ₂ ), ozone ( _O3 ),
Carbon monoxide (CO), carbon dioxide (CO ₂ ), nitric oxide (NO), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitric oxide (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 ), whose constituent atoms are Si, O, and H. , e.g. disiloxane H ₃ SiOSiH ₃ , trisiloxane
Lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ and the like can also be mentioned.

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 atoms used in forming the amorphous layer, but other gases may be used. Hydrogen halides such as HF, HCl, HBr, HI, SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements, such as halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and SiHBr ₃ , can also be cited as effective starting materials for forming an amorphous layer. I can do it.

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 carried out 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 a-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,
It is also possible to introduce a gas such as PH ₃ or PF ₃ .

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 that it be ~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, 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 done 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,
Preferred examples include In, Tl, and the like.

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

In the present invention, the amount of impurities introduced into the amorphous layer in order to have a desired conductivity type is 3×10 ^-2 atomic in the case of impurities in group A of the periodic table.
% or less, and in the case of impurities in group A of the periodic table, 5×
It is sufficient to dope in an amount of 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. 3 installed in a completely shielded clean room, an electrophotographic image forming member was produced by the following operations.

A 0.5 mm thick, 10 cm square molybdenum plate (substrate) 209 whose surface had been cleaned was firmly fixed to a fixing member 203 at a predetermined position in the glow discharge deposition chamber 201 . The substrate 209 is heated with an accuracy of ±0.5° C. by the heater 208 inside the fixing member 203.
Temperature was measured directly on the backside of the substrate by a thermocouple (Almeru Cromel). Next, after confirming that all valves in the system are closed, the main valve 210 is fully opened, and the chamber 201 is closed.
The inside was evacuated to a vacuum level of approximately 5×10 ^-6 Torr.
Thereafter, the input voltage to the heater 208 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 241 and then the outflow valve 2
26, 227, 229 and inflow valves 221, 2
22, 224 were fully opened, and the mass flow controllers 216, 217, 219 were also sufficiently degassed to a vacuum state. Auxiliary valve 226, 227, 229,
After closing 221 and 224, SiH ₄ gas diluted to 10 vol% with H ₂ (purity 99.999%, hereinafter referred to as SiH ₄ /H ₂
It is abbreviated as ) Open the valve 231 of the cylinder 211 and the valve 234 of the O ₂ gas (purity 99.999%) cylinder 214, and set the pressure of the outlet pressure gauges 236 and 239 to 1 kg/
cm ² and gradually open the inflow valves 221 and 224 into the mass controllers 216 and 219.
SiH ₄ /H ₂ gas and NH ₃ gas were respectively introduced. Subsequently, the outflow valves 226, 229 were gradually opened, and then the auxiliary valve 241 was gradually opened. At this time, the ratio of SiH ₄ /H ₂ gas flow rate to NH ₃ gas flow rate is
Mass flow controller 2 so that the ratio is 10:1
16,219 was adjusted. Next, Pirani Gauge 2
The opening of the auxiliary valve 241 was adjusted while observing the reading of 42, and the auxiliary valve 241 was opened until the inside of the chamber 201 became 1×10 ⁻² Torr.

After the internal pressure of the chamber 201 became stable, the main valve 210 was gradually closed and the opening was throttled until the reading on the Pirani gauge 241 reached 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 305 (which also serves as an electrode) is closed, the high frequency power source 243 is turned on, and the electrode 2 is turned on.
Between 03.03 and 205, 13.56MHz high frequency power was applied to generate glow discharge in the room 201, and the input power was 3W. After forming the lower layer to a thickness of 600 Å on the molybdenum substrate by maintaining the above conditions for 10 minutes,
With the high frequency power supply 243 turned off and glow discharge stopped, the outflow valve 229 is closed, and then NH ₃ gas diluted to 0.1 vol% with H ₂ (purity
99.999%, hereinafter abbreviated as NH ₃ /H ₂ . )Cylinder 212
With a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 237) through the valve 222 of the inlet valve 222,
By gradually opening the outflow valve 227 and flowing NH ₃ /H ₂ gas into the mass flow controller 317, by adjusting the mass flow controllers 216 and 217.
The NH ₃ /H ₂ gas flow ratio was adjusted to 10:0.3. Subsequently, the high frequency power supply 243 was turned on again to restart glow discharge. At that time, the input power was set to 10W.

After forming the intermediate layer under the above conditions for 5 hours, the high frequency power supply 343 is turned off to stop glow discharge, the outflow valve 221 is closed, and then the outflow valve 229 is opened again and the mass flow controller 2
By adjusting 19,216, the NH ₃ gas flow rate is
The SiH ₄ /H ₂ gas flow rate was stabilized to 1/10. Subsequently, the high frequency power supply 243 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 15 minutes to form the upper layer with a thickness of 900 Å, the heating heater 208 is turned off, the high frequency power supply 243 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 2 is turned off.
26, 229 and inflow valves 221, 222, 2
24 and fully open the main valve 210.
After reducing the inside of the chamber 201 to 10 ^-5 Torr or less, close the main valve 210 and close the inside of the chamber 201 with the leak valve 20.
6 to bring the pressure to atmospheric pressure and take out the substrate. 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 1.1 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 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation 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 ^-5 Torr was created in the deposition chamber 201 by the same operation as in Example 1. Therefore, fully open the auxiliary valve 241, then the outflow valves 226, 227, 229, 230 and the inflow valves 221, 222, 224, 225,
Mass flow controller 216, 217, 21
9,220 was also sufficiently degassed and vacuumed. Auxiliary valve 241, valves 226, 227, 229, 2
After closing 30, 219, 220, 221, 222, argon (99.999% purity) gas cylinder 215
The valve 235 was closed and the reading of the outlet pressure gauge 240 was adjusted to 1 Kg/cm ² . The inlet valve 225 is then opened, followed by the outlet valve 23.
0 was gradually opened to allow argon gas to flow into chamber 201. Pirani gauge 211 indicates 5
The outflow valve 230 is gradually opened until the indoor pressure reaches ×10 ^-4 Torr, and after the flow rate stabilizes in this state, the main valve 210 is gradually closed until the indoor pressure reaches 1 ×10 ^-2 Torr. Narrowed down. After opening the shutter 205 and confirming that the mass flow controller 220 is stable, turn on the high frequency power supply 243 and install high purity graphite (99.999% purity) on polycrystalline high purity silicon (99.999% purity). (Target 204).
Between the target 204 and the fixed member 203
13.56MHz, 100W AC power was input. Matching was performed under these conditions so that stable discharge could continue, and a layer was formed. Discharge was continued in this manner for 1 minute to form a lower layer with a thickness of 100 Å. Thereafter, the high frequency power supply 243 was turned off to temporarily stop the discharge. Subsequently, the outflow valve 230 and the shutter 20
5, and fully open the main valve 210 to open the chamber 20.
The gas in 1 was removed and the vacuum was evacuated to 5×10 ^-6 Torr. After that, the input voltage of the heater 208 is increased, and the input voltage is changed while detecting the substrate temperature.
It was stabilized until it reached a constant value of 200℃. After that,
A photoconductive layer and an upper layer were formed under the same operations and conditions as in Example 1. 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 3 After forming a lower layer on a molybdenum substrate using the same operations and conditions as in Example 1, the high frequency power source 243 was turned on.
With the off state and the glow discharge stopped, the outflow valve 229 is closed, and then the valve 232 of the NH ₃ /H ₂ gas cylinder 212, B ₂ H ₆ gas (purity 99.999% or less) diluted with H ₂ to 50 volppm. B ₂ H ₆ /H ₂
It is abbreviated as ) Open the valve 233 of the cylinder 213,
Adjust the pressure of the outlet pressure gauges 237, 238 to 1Kg/cm ² and gradually open the inflow valves 222, 223 to increase the pressure inside the mass flow controllers 217, 218.
NH ₃ /H ₂ and B ₂ H ₆ /H ₂ gases were introduced. Subsequently, the outflow valves 227 and 228 are gradually opened,
SiH ₄ /H ₂ gas flow rate and NH ₃ /H ₂ gas flow rate ratio are
The mass flow controllers 216, 217, and 218 were adjusted so that the SiH ₄ /H ₂ gas flow rate and the B ₂ H ₆ /H ₂ gas flow rate ratio were 1:5. Next, the opening of the auxiliary valve 241 was readjusted while observing the reading on the Pirani gauge 242, and the internal pressure in the chamber 201 was set to 1×10 ⁻² Torr. Furthermore,
After the internal pressure of the chamber 201 becomes stable, the main valve 2
10 was also readjusted and the Pirani gauge 242 indicated
It was set to 0.1Torr.

After confirming that the gas inflow was stable and the internal pressure was stable, the high-frequency power supply 243 was turned on again, and 13.56MHz high-frequency power was applied to restart the glow discharge in the chamber 201, resulting in an input power of 10W.
After forming the intermediate layer under the above conditions for 5 hours, the high frequency power supply 243 is turned off to stop the glow discharge, the outflow valves 227 and 228 are closed, and the outflow valve 229 is opened again, and the mass flow controllers 219 and 216 are closed. By adjusting the NH ₃ gas flow rate,
The flow rate was stabilized at 1/10 of the SiH ₄ /H ₂ gas flow rate. Subsequently, the high frequency power supply 243 was turned on again to restart glow discharge.

The input power at that time is the same as when forming the lower layer.
I set it to 3W.

Glow discharge was continued for 15 minutes to remove the upper layer.
After forming the film to a thickness of 900 Å, a heating heater 208 is installed.
off state, and the high frequency power supply 243 is also off state,
After waiting for the substrate temperature to reach 100°C, the outflow valves 226, 227, 228 and the inflow valve 22
1,222, 223, 224 are closed, the main valve 210 is fully opened, and the inside of the chamber 201 is reduced to 10 ^-5 Torr.
After the following, close the main valve 210 and close the chamber 20.
1 was brought to atmospheric pressure using a leak valve 206, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 15μ.

The image forming section thus obtained was installed in a charging exposure experimental device, corona charging was performed at 5.5 KV for 0.2 seconds, and a light image was immediately irradiated. 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 chargeable developer (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.0KV 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
Immediately after image exposure was performed with a light intensity of 1.0 lux·sec, a charged developer was cascaded onto the surface of the member, 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 photoreceptor obtained in this example had no dependence on charging polarity and had the characteristics of an amphipolar image forming member.

Example 4 The SiH ₄ /H ₂ gas cylinder 211 was replaced with a SiF ₄ gas (purity 99.999%) cylinder in advance, and Example 2
A lower layer was formed on the molybdenum substrate using the same operations and conditions as described above. After that, the high frequency power supply 243 is turned off to stop the glow discharge, and the outflow valve 243 is turned off.
0, the shutter 205 was closed, and then the main valve 210 was fully opened to remove gas from the chamber 201, creating a vacuum of 5×10 ^-6 Torr. Thereafter, the input voltage to the heater 208 was increased, and the input voltage was varied while detecting the substrate temperature until it stabilized at a constant value of 200°C. After that, shutter 20
5 and using SiF ₄ gas and NH ₃ /H ₂ gas.
SiF ₄ gas flow rate and NH ₃ /H ₂ gas flow rate ratio of 1:1.2
An intermediate layer was formed under the same operations and conditions as in Example 1, except that the input power for glow discharge was set to 100W.

After the intermediate layer was formed, the heater 208 was turned off, the outflow valves 226 and 228 were closed, and the shutter 205 was opened again. When the substrate temperature dropped to 80° C., an upper layer was subsequently formed on the intermediate layer using the same operations and conditions as when forming the lower layer.

As mentioned above, on the molybdenum substrate, the lower layer,
After forming the middle layer and the upper layer, the high frequency power source 243
is turned off, the outflow valve 230 and inflow valves 221, 222, 225 are closed, and the main valve 210 is fully opened to reduce the temperature inside the chamber 201 to 10 ^-5 Torr or less, and then the main valve 210 is closed and the chamber 201 is turned off.
The inside of the chamber was brought to atmospheric pressure using a leak valve 206, 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 5 In Examples 1 to 4, _N2 , instead of _NH3 ,
Except for using N ₂ O or (N ₂ + O ₂ ), in each of the examples, for photoconductive members prepared under substantially the same conditions and procedures, in each of the corresponding examples, When applying the electrophotographic image formation process,
We were able to obtain extremely high quality transferred images.
Further, no deterioration in transferred image quality was observed even after repeated use over a long period of time.

[Brief explanation of drawings]

FIG. 1 is a schematic explanatory diagram for explaining the layer structure of a preferred embodiment of the photoconductive member of the present invention, and FIG.
The figure is a schematic explanatory view for explaining an example of an apparatus for producing the photoconductive member of the present invention. 100...Photoconductive member, 101...Support, 102
... barrier layer, 103 ... amorphous layer, 104 ... lower layer region, 105 ... upper layer region, 106 ... intermediate layer region,
107...Free surface.

Claims (1)

[Claims] 1. A support for a photoconductive member for electrophotography, and an amorphous material containing at least one or both of hydrogen atoms and halogen atoms and having silicon atoms as a matrix, and exhibiting photoconductivity. In the electrophotographic photoconductive member comprising a layer, the amorphous layer contains nitrogen atoms, and the amorphous layer has nitrogen atoms in a distribution amount C ₁ of 60 atomic % or less in the layer thickness direction. a lower layer region in which nitrogen atoms are substantially uniformly distributed in the layer thickness direction, and an upper layer region in which nitrogen atoms are substantially uniformly distributed in the layer thickness direction with a distribution amount C ₂ of 60 atomic % or less; The nitrogen atoms are sandwiched between the
Distribution amount C ₃ of 10 atomic% or less and 0.005 atomic% or more
and an intermediate layer region that is substantially uniformly distributed in the layer thickness direction, and the distribution amounts C ₁ to C ₃ are such that C ₃ <C ₁ ,
A photoconductive member for electrophotography, characterized by having a C ₂ relationship.