JPS60144750A - Photoconductive member - Google Patents

Abstract

PURPOSE:To enhance characteristics by forming a photoreceptor composed of each amorphous layer made of Si, Si-Ge, Si-O, contg. Ge in the second layer in a concn. distribution nonuniform in the layer thickness direction, and C in one of the first layer and the second layer. CONSTITUTION:A photoreceptor 102 formed on a substrate 101 is composed, upward from the substrate 101, of the first layer 103 made of a-Si (H, X), a layer 104 made of a-SiGe (H, X), a layer 105 made of a-SiO (H, X), and one of the layers 103 and 104 contains C and a conductivity governor, suchf as p type or n type impurity. The layer 103 or 104 contains F, Cl, Br, or I as halogen X, and the layer 104 contains Ge in a nonuniform distribution in the layer thickness direction.

Description

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

[Prior Art] Photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices have high sensitivity and a high signal-to-noise ratio [photocurrent (Ip
)/dark current (Id)], has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, and has a desired dark resistance value.
Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use, and being able to easily dispose of 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, the above-mentioned non-polluting property during use is an important point.

Based on this viewpoint, amorphous silicon (hereinafter referred to as a-9i) is a photoconductive material that has recently attracted attention. The application to photographic image forming members and the application to photoelectric conversion/reading devices are described in Japanese Publication No. 2!33340.

However, the conventional photoconductive member having a leading conductive layer composed of a-5i has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are problems that need to be further improved in terms of environmental characteristics and furthermore, stability over time, which requires comprehensive improvement of characteristics.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of When a conductive member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, and a so-called ghost phenomenon, which causes an afterimage, may occur.
In addition, there are many disadvantages such as a gradual decrease in responsiveness when used repeatedly at high speeds.

Furthermore, compared to the short wavelength side of the visible light region, a-9i is
The absorption coefficient in the long wavelength region is relatively smaller than that in the long wavelength region, making it suitable for matching with semiconductor lasers currently in practical use, and when using commonly used halogen lamps or fluorescent lamps as a light source. There remains room for improvement in that the light on the long wavelength side cannot be used effectively. Alternatively, if the irradiated light is not sufficiently absorbed in the photoconductive layer and the amount of light that reaches the support increases, the support itself has a high reflectance to the light that passes through the photoconductive layer. In this case, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "poke" in the image. This effect becomes larger as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source.

Furthermore, when the photoconductive layer is composed of a-5i material,
In order to improve its electrical and photoconductive properties, hydrogen atoms or halogen atoms such as fluorine atoms and chlorine atoms are added, and boron atoms and phosphorus atoms are added to control the electrical conductivity type, or other properties are improved. Therefore, other atoms are contained in the photoconductive layer as constituent atoms, but depending on the manner in which these constituent atoms are included, problems may arise in the electrical or photoconductive properties of the formed layer. There are cases.

That is, for example, sufficient image density may not be obtained because the life of photocarriers generated in the formed photoconductive layer by light irradiation is not sufficient, or in dark areas, photocarriers generated by light irradiation may not have sufficient image density. Problems often arise due to insufficient prevention of charge injection.

Therefore, while efforts are being made to improve the properties of the a-3i material itself, it is necessary to take measures to obtain the desired electrical and optical properties as described above when designing photoconductive members.

The present invention has been made in view of the above points, and from the viewpoint of applicability and applicability of a-3i as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of intensive comprehensive research, we have discovered that an amorphous material with silicon (Si) as its base material, especially a silicon atom (Si) as its base material, with either a hydrogen atom (H) or a halogen atom (X). An amorphous material containing at least a so-called hydrogenated amorphous silicon, a halogenated amorphous silicon, or a halogen-containing hydrogenated amorphous silicon [hereinafter collectively referred to as a-9i(H,X)], and a silicon atom ( S
An amorphous material containing a manium atom (Ge) and a manium atom (Ge), especially an amorphous material containing a hydrogen atom (H
) or a halogen atom (X), i.e., Wt m hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter these will be collectively referred to as a- 3iGe (H, In addition, it is superior in all respects to conventional photoconductive materials, and in particular has outstanding properties as a photoconductive material for electrophotography, and has excellent absorption on the long wavelength side. This is based on the discovery that it has excellent spectral characteristics.

[Purpose of the Invention] The present invention is an all-environment type product whose electrical, optical, and photoconductive properties are always stable and are hardly affected by the environment in which it is used.
The main object of the present invention is to provide a photoconductive member which has excellent photoreceptivity on the long wavelength side, has remarkable photofatigue resistance, does not cause deterioration even after repeated use, and has no or almost no residual potential observed.

Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers, and has fast photoresponse.

Another object of the present invention is to have charge retention properties 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 having sufficient electrophotographic properties and excellent electrophotographic properties.

Still another object of the present invention is to provide a method for electrophotography which can easily obtain high-quality images with high density, clear half-I-tones, high resolution, and no image defects or image deletions. An object of the present invention is to provide a photoconductive member.

Yet another object of the present invention is to provide a photoconductive member with sufficiently high dark resistance and sufficient acceptance potential, and to improve productivity by improving adhesion between each layer. It is in.

Yet another object of the present invention is to provide a photoconductive member having high photosensitivity and high signal-to-noise ratio characteristics.

[Structure of the Invention] That is, the photoconductive member of the present invention includes a support for the photoconductive member and a photoreceptive layer provided on the support and having photoconductivity. The photoreceptive layer includes, from the support side, a first layer (I) made of an amorphous material containing silicon atoms, and a second layer (I) made of an amorphous material containing silicon atoms and germanium atoms. Layer (II
) and a third layer (III) made of an amorphous material containing silicon atoms and oxygen atoms, and the germanium atoms contained in the second layer (■) is distributed nonuniformly in the layer thickness direction of the first layer (I
) and the second layer (II) contain carbon atoms.

It is desirable that at least one of the first layer (I) and the second layer (II) contain hydrogen atoms and/or halogen atoms, and the first layer (I) It is preferable that at least one of the inside and the second layer (■) contains a substance that controls conductivity.

The photoconductive member of the present invention, in which the photoreceptive layer has the layer structure described above, can solve all of the problems described above, and has extremely excellent electrical, optical, and optical properties. Indicates conductive properties, electrical voltage resistance, and usage environment characteristics.

In particular, when applied as an electrophotographic image forming member, it has no influence of residual potential on image formation, has stable electrical characteristics, has high sensitivity, and has a high signal-to-noise ratio. Therefore, high-quality images with high light fatigue resistance and repeated use characteristics, high image density, clear halftones, and high resolution can be repeatedly obtained stably.

Furthermore, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in matching with semiconductor lasers.
And the light response is fast.

[BEST MODE FOR CARRYING OUT THE INVENTION] The photoconductive member of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a diagram schematically showing a layer structure for explaining the layer structure of a photoconductive member of the present invention.

As shown in FIG. 1, the photoconductive member 100 of the present invention includes a photoreceptive layer 102 having sufficient volume resistance and photoconductivity on a support 101 for the photoconductive member.

have The light-receiving layer 102 is a −5 from the support side.
i(H,X) caranal 117th) layer (I) 103, a-
a second layer (II) 104 made of 3iGe(H,X),
Third layer (III) consisting of a-3iO(H,X) 10
5. Photoconductivity may be applied to either the first layer (I) or the second layer (n), but in any case, it is necessary to ensure that the layer that the incident light reaches has photoconductivity. Needs to be designed in layers.

Moreover, in this case, the first layer (I) and the second layer (n)
It is desirable that both of the layers have photoconductivity for light in a desired wavelength spectrum and are designed as layers capable of generating a sufficient amount of photocarriers.

In the photoconductive member of the present invention, in order to achieve high photosensitivity and high dark resistance, or to improve the adhesion between the support and the photoreceptive layer or between each layer constituting the photoreceptive layer, , carbon atoms are contained in at least one of the first layer (I) and the second layer (II).

In order to achieve these objectives even more effectively, the first
It is preferred that both the layer (I) and the second layer (II) contain carbon atoms.

The carbon atoms contained in at least one of the first layer (I) and the second layer (■) may be contained evenly in the entire layer area of these layers, or may be partially unevenly distributed. It may also be contained.

Regarding the distribution state of carbon atoms, the distribution concentration C (C) may be uniform or non-uniform in the thickness direction of the photoreceptive layer.

In the present invention, the carbon atom-containing layer region (C) provided in at least one of the first layer (I) and the second layer (II) improves photosensitivity and darkness. When the main purpose is to improve resistance, these layers are provided so as to occupy the entire area. In addition, the support and the first
When the purpose is to strengthen the adhesion of a desired adhesion surface among the adhesion surfaces with R(I) and the adhesion surfaces between the layers constituting the light-receiving layer, for example, 1 layer (I)
If you want to strengthen the adhesion between the first layer (I) and the support side end layer region, and between the first layer (I) and the second layer (II), strengthen the adhesion between the first layer (I) and the second layer (II). If desired, the layer interface between the first layer (I) and the second layer (II) and the area near the layer interface may be If the purpose is to strengthen the third layer of the second layer (II),
Provided so as to occupy the layer (III) side end layer region, etc.
It is provided so as to occupy the layer interface and the area near the layer interface where adhesion is to be enhanced.

In order to achieve these objectives even more effectively, the first
It is preferable that both the layer (I) and the second layer (II) contain carbon atoms.

When trying to achieve the former purpose, layer area (G)
It is desirable that the content of carbon atoms contained therein be relatively low in order to maintain high photosensitivity, and in the latter case relatively high in order to enhance adhesion in the living room.

In addition, in order to simultaneously achieve the former and latter objectives, it is necessary to have a relatively large concentration distributed on the support side and a relatively low concentration distribution in the layer region on the free surface side of the photoreceptive layer. (C) may be formed.

Furthermore, if the purpose is to prevent charge injection from the support or the first layer (I) and increase the apparent dark resistance, carbon atoms may be added to the support side of the first layer (I). or the interface between the first layer (I) and the second N(n) and/or
Alternatively, it is desirable to have a high distribution near the interface.

In addition, in the present invention, the layer region CG) as described above is not limited to only one, but a plurality of layer regions (C) may be provided in the photoreceptive layer depending on the above purpose. Also good.

In the present invention, the content of carbon atoms contained in the layer region (C) provided in at least one of the first layer (I) and the second layer ('LT) is as follows: The characteristics required of the layer region (G) itself to achieve the above objectives, and if the layer region (C) is provided in direct contact with the support, the contact interface with the support If the layer region (C) is provided in direct contact with another layer region, the properties required for the layer region (C) and the characteristics of the layer region of the layer and the relationship between the layer region (C) and the other layer region. They can be selected as appropriate depending on the organic relationship, such as the properties required at the contact interface.

The amount of carbon atoms contained in the layer region (C) is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001 to 50 atoms.
mic%, more preferably 0.002 to 40ato+*
ic%, optimally 0.003 to 30 ato+*ic%.

In the photoconductive member of the present invention, at least one of the first layer (I) and the second layer (II) contains a substance (G) that controls conductivity. The conductivity can be controlled as desired. The substance (C
) is contained in at least one of the first layer (I) and the second layer (n) so that it may be distributed uniformly or non-uniformly in the layer thickness direction. Also,
In the layer region (PM) containing the substance (C), the substance (C) is continuously contained in a uniform or non-uniform distribution state in the layer thickness direction.

For example, the second layer (■) is made thicker than the first layer (I), and the second layer (II) mainly functions as a charge generation layer and a charge transport layer, When using the substance (C) that controls the conductivity, it is desirable that the substance (C) that controls the conductivity is distributed in such a manner that it is concentrated on the support side in the first layer (I). In the second layer (II), the dominating substance (C) is
It is desirable to have a distribution state in which the amount is increased at or near the interface with I).

Examples of the substance (C) that governs conductivity include so-called impurities in the semiconductor field, and in the present invention, p-type impurities that give p-type conductivity to Si or Ge Mention may be made of impurities and n-type impurities that provide n-type conduction properties. Specifically, the P-type impurities include atoms belonging to Group ■ of the periodic table (Group ■ atoms);
For example, B, A1. There are Ga, In, TI, etc., and B and Ga are particularly preferably used. As n-type impurities, atoms belonging to group V of the periodic table (group V atoms)
, for example, P, As, Sb, Bi, etc., and P and ^S are particularly preferably used.

In the present invention, the content of the substance controlling conductivity (C) contained in the layer region (PN) containing the substance controlling conductivity (C) provided in the photoreceptive layer is , the conductive properties required for the layer region (PN), or when the layer region (PN) is provided in direct contact with the support, the relationship with the properties at the contact interface with the support, etc. , can be selected as appropriate depending on the organic relationship. In addition, the material controlling conductivity ( The content of C) is selected as appropriate.

In the present invention, the content of the substance (C) that controls conductivity contained in the layer region (PN) is preferably 0.
．． 001~5X 104104ato pp+s, more preferably 0.5~LX 10' ato+sic p
pm, preferably 1 to 5×103103ato ppr.

In the present invention, the content of the substance (C) controlling conductivity in the layer region (PN) is preferably 30 atos
+ic PP1 or more, more preferably 50ato+si
c pps+ or more, optimally 100ata+wic
ppm or more, for example, when the substance (C) is the p-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, it is possible to prevent the material from entering the photoreceptor layer from the support side. can effectively prevent the electron injection of
When the substance (C) is the n-type impurity, when the free surface of the photoreceptive layer is charged to e-polarity, holes can be effectively injected from the support side into the photoreceptor layer. can be prevented.

In the above case, the layer region (Z) excluding the layer region (PM) has a polarity different from the polarity of the substance (C) that controls conductivity contained in the layer region (PM). A substance (C) controlling the conductivity of the same polarity may be contained in the layer region (PN
) may be contained in a much smaller amount than the amount contained in .

In such a case, the content of the substance (C) that controls the conductivity contained in the layer region (Z) is as follows:
It is determined appropriately depending on the polarity and content of the substance (C) contained in PN), but preferably 0.00
1 = 1001000 atomic ppm, more preferably 0.05-500 atomic ppm, optimally 0
．． It is desirable that it be 1 to 200 atomic pp.

In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably It is desirable that the amount is less than 30atomin. In addition to the above-mentioned cases, in the present invention, a layer region containing a substance (C) that controls conductivity having one polarity in the photoreceptive layer, and a layer region controlling conductivity having the other polarity. It is also possible to provide a so-called depletion layer in the contact region by providing a layer region containing a substance (C) in direct contact with the contact region. That is, for example, a layer region containing the above-mentioned p-type impurity and a layer region containing the above-mentioned n-type impurity are provided in the photoreceptive layer so as to be in direct contact to form a so-called p-n junction, and a depletion layer is formed. can be provided.

In the present invention, specific examples of the halogen atom (X) contained in the first Jljt (I) as necessary include fluorine, chlorine, bromine, and iodine, but particularly fluorine, chlorine, can be mentioned as suitable.

In the present invention, the first
In order to form layer (I), a vacuum deposition method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method is applied.

For example, in order to form the first layer (I) composed of a-5i (H, At the same time, a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (K) is introduced into a deposition chamber whose interior can be made to have a predetermined mixing ratio and gas flow rate. By generating a glow discharge in the deposition chamber and forming a plasma atmosphere of these gases,
a-3i on the surface of the support that has been installed in a predetermined position
A first (7) layer (1) composed of (H,X) is formed.

In addition, when forming by the spar two-talling method, a target made of Si or 5i07, or a mixture thereof, is formed in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases. When sputtering, a gas for introducing hydrogen atoms (I) and H/halogen atoms (X) may be introduced into the deposition chamber for sputtering.

In the present invention, the following are effective starting materials for the raw material gas used to form the first layer (I).

First, the starting materials that will become the raw material gas for supplying Si are as follows:
SiH4, Si2H6, 5i3HB, Si4H16
Silicon hydrides (silanes), which can be easily gasified or in a non-volatile state, can be used effectively, in particular:
S in terms of ease of handling layer creation work, good Si supply efficiency, etc.
Preferred examples include iH4 and Si2H6.

Effective starting materials that serve as raw material gas for supplying Si include:
In addition to the silicon hydride mentioned above, silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example, SiF4゜5i2F 6 , 5
Preferred examples include silicon halides such as iG14 and SiBr4, and furthermore, SiH2F
2.5iH21z, SiH2CI2, 5iHCI3,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents, such as halogen-substituted silicon hydride 1 such as 5iH2Br2 and 5iHBr3, can also be cited as effective starting materials for forming the first layer (1). can.

Even when using a silicon compound containing these halogen atoms (X), the halogen atoms (X) can be added to the first layer (I) together with Si by appropriately selecting the layer forming conditions as described above. can be introduced.

In the present invention, effective starting materials that serve as raw material gas for introducing halogen atoms (X) used to form the first layer (I) include, in addition to the above, for example, fluorine,
Chlorine, bromine, iodine, etc./\logenkas, CIF,
ClF3, BrF, BrF3, BrF5, HF3
Examples include interhalogen compounds such as , IFy, ICI, and IBr, and hydrogen halides such as HF, MCI, HBr, and old.

In the present invention, when providing a layer region (C) containing carbon atoms in a desired layer region constituting the first layer (I), the above-mentioned starting material is used to form the first layer region (C). When forming the layer (I), a starting material for introducing carbon atoms may be used in combination while controlling the amount thereof, and the starting material may be contained in the formed layer.

The carbon atoms contained in the layer (I) of $1 are the carbon atoms contained in the first layer (
It may be contained in the entire area of I) without any scratches, or it may be contained only in one layer area.

In addition, the distribution state of carbon atoms C (C) is 1L:1')
The layer (1,) may be uniform or non-uniform in the layer thickness direction.

In the present invention, when the purpose is to improve photosensitivity and dark resistance, the layer region (CI) containing carbon atoms provided in the first layer (I) is I) is provided so as to occupy the entire layer area, and is connected to the substrate and further to the second layer (I).
In order to strengthen the adhesion with I), it is provided so as to occupy the substrate or the second layer (II) or the end layer regions on both sides.

In this way, the layer region (CI) provided in the first layer (I)
) The content of carbon atoms in the layer (CI) is determined based on the characteristics required for the layer region (CI) itself to achieve the above-mentioned purpose, the characteristics required at the contact interface with the support, or the characteristics required for the layer Regarding organic relationships such as the characteristics of other layer regions provided in direct contact with the layer region (CI) and the characteristics required at the contact interface between the layer region (CI) and other layer regions. , can be selected as appropriate.

The amount of carbon atoms contained in the layer region (CI) is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001-50 at.
omic%, more preferably 0.002 to 40 atoms
ic%, preferably 0.003-30 atomic%.

When applying the glow discharge method to form the layer region (CI), carbon atoms are further introduced into the starting materials selected as desired from among the starting materials for forming the first layer (I). starting materials are added. As the starting material for introducing carbon atoms, it is possible to use almost any gaseous substance having at least a carbon atom as a constituent atom or a gasified substance that can be gasified.

The combinations of raw material gases used include (a) a raw material gas containing silicon atoms (Si), a raw material gas containing carbon atoms (G), and optionally hydrogen atoms (H) and/or or halogen atom (X)
(b) Silicon atoms (Si) and hydrogen atoms (H
) and a halogen atom (X)
(c) A raw material gas containing silicon atoms (Si) and a raw material gas containing carbon atoms (C) at a desired mixing ratio. , a raw material gas whose constituent atoms are carbon atoms (G) and hydrogen atoms (H) are mixed at a desired mixing ratio; (d) a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are silicon atoms ( Examples of combinations include mixing and using a raw material gas containing three atoms, Si), carbon atoms (C), and hydrogen atoms (l()) at a desired mixing ratio.

Carbon atoms (
C) Starting materials that can be effectively used as raw material gas for supply include saturated hydrocarbons having 1 to 5 carbon atoms, 1 having C as a constituent atom, or C and H as constituent atoms, and 2 -5 ethylene hydrocarbons, C2-4 acetylene hydrocarbons, and the like.

These include methane as a saturated hydrocarbon;
Ethylene hydrocarbons include ethylene propylene, butene-1, butene-2, isobutylene, pentene, etc.; acetylene hydrocarbons include acetylene, methylacetylene, butyne, and the like.

In addition to these, Si(CH3)4.5i (also C2H)4 is used as a raw material gas containing Si, C, and H as constituent atoms.
etc. can be given.

In the present invention, 1. In order to further enhance the effect obtained with carbon atoms, in addition to carbon atoms, oxygen atoms and/or nitrogen atoms can be contained in the layer region (C). .

Examples of source gases for introducing oxygen atoms into the layer region (CI) include oxygen (0□), ozone (03), -nitrogen oxide (NO), nitrogen dioxide (NO2), and -nitrogen dioxide (N20). , nitrogen sesquioxide (N203), nitrogen tetroxide (N204), nitrogen sesquioxide (N20S), nitrogen trioxide (N03), constituent atoms of silicon atom (Si), oxygen atom (0), and hydrogen atom (H) For example, disiloxane (H3SiO8iH3), trisiloxane (H3Si
Examples include lower siloxanes such as OSiH205iH3).

Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) into the layer region (CI) include those in which N is a constituent atom, or N and H are constituent atoms. For example, nitrogen (N2), ammonia (NH3
), hydrazine (H2NNH2), hydrogen azide (HN
3) Gaseous or gasifiable nitrogen such as ammonium azide (NH4Ng), nitrogen compounds such as nitrides and azides. In addition to this,
In addition to introducing a nitrogen atom (N), a halogen atom (X) can also be introduced, so mention may be made of /\nitrogen compounds such as nitrogen trifluoride (F3N) and nitrogen tetrafluoride (F4N2). Can be done.

When forming the first layer (I) containing carbon atoms by a sputtering method, single crystal or polycrystal S
This can be carried out by sputtering an i-wafer and/or a C-wafer, or a wafer containing a mixture of Si and C, in various gas atmospheres.

For example, when using a Si wafer as a target, a raw material gas for introducing carbon atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and the material gas is added to the deposition chamber for sputtering. The Si wafer may be sputtered by introducing these gases to form a gas plasma of these gases.

Alternatively, if Si and C are used as separate targets, or when Si and C are used as a mixed target, an atmosphere of diluted gas as a snow ivy gas may be used. or at least a hydrogen atom (
A layer region containing carbon atoms (C
A first layer (I) provided with I) can be formed.

Note that, as the gas for introducing carbon atoms, those listed as the gas for introducing carbon atoms in the glow discharge method described above can also be used as the gas for sputtering.

In order to structurally introduce a substance (C) that controls conductivity into the layer region constituting the first layer (I), for example, a group II atom or a group V atom, a The starting material for introducing group (2) atoms or the starting material for introducing group V atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the first layer (I). As the starting material for the introduction of Group (1) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

Specifically, starting materials for the introduction of Group Ⅰ atoms include B2H6 and B4 for the introduction of boron atoms.
Hlo, BS B9・Bs Hll, Bb Hl
o, boron hydride such as 8G'H12・B6H14,
Examples include boron halides such as BF3, 8013, and BBr3. In addition to this, AlCl3. GaG13, Ga(CH3)3,
Examples include InCl3, Tl11;13, and the like.

As a starting material for introducing a group V atom, PH3 is effectively used in the present invention for introducing a phosphorus atom.
, P2H, etc., phosphorus hydride, P)+41.

PF3, PF, , PCl3, PCB5, PB
Examples include phosphorus halides such as r3, PBr3, and PI3. In addition, AsH3, AsF3, AsCl3,
AsBr3, AsF5, SbH3, SbF3, SbF
5, SM:B3, 5bC15, BiI3. BiCl
3, B1Br3, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, the content of the substance (C) that controls conductivity contained in the first layer (I) depends on the conductivity properties required for the first layer (I) or the layer (I). It is appropriately selected based on organic relationships such as the characteristics of other layers provided in direct contact with I) and the characteristics of the contact interface between the layer and the other layer.

In the present invention, the content of the substance controlling conductivity contained in the first layer (I) is preferably 0.00
Desirably, the range is 1-5X 104104ato ppm, more preferably 0.5-IX 104104ato ppm, optimally 1-5X 103103ato ppm.

In the present invention, the amount of hydrogen atoms (I), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (HlX) that may be present in the first layer (I) is preferably 1 to 40 ato+*ic%, more preferably 5 to
It is desirable to set it to 30 atomic%.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) that may be contained in the first layer (I), for example, the support temperature, hydrogen atoms ()l) and halogen atoms ( X)
What is necessary is to control the amount of the starting material used to contain the material introduced into the deposition system, the discharge power, etc.

The layer thickness of the first layer (I) of the present invention is such that the first layer (I) mainly functions as an adhesion layer between the support and the second layer (II), or it acts as an adhesion layer and charge transport layer. It is appropriately determined depending on whether it functions as a layer or not.

In the former case, preferably 100OA to 50 units, more preferably 2000A to 30 units, optimally 2000A
-101AI+ is desirable. In the latter case, it is preferably 1-100 u, more preferably 1-80 u, most preferably 2-50 u.

In the photoconductive member of the present invention, the first layer (I) 103
A second layer (II) 104 is formed on top. First layer (
I) and the second layer (II) are each mainly composed of an amorphous material having a common constituent atom, silicon atoms, so that chemical stability is maintained at the laminated interface. Sufficiently secured.

In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the second layer (II) is non-uniform in the layer thickness direction, but the distribution state is non-uniform in the layer thickness direction. It is desirable that the distribution be uniform in parallel in-plane directions.

By forming the second layer (II) in such a layered structure, it has excellent photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively long wavelengths, including the visible light region. A photoconductive member is formed.

In addition, the distribution state of germanium atoms in the second layer (II) is such that germanium atoms are continuously distributed in the entire region, and the distribution concentration C of germanium atoms in the layer thickness direction is the first
The distribution decreases from the boundary with the first layer (I) to the third layer (m), and the distribution decreases from the boundary with the first layer (I) to the third layer (III). A layer structure in which the distribution increases toward the boundary between the two, or a layer structure that has the characteristics of both are allowed.

2 to 13 show typical examples of the distribution state of germanium atoms contained in the second layer (II) of the photoconductive member of the present invention in the layer thickness direction.

In FIGS. 2 to 13, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the second! (II), tB is the position of the interface between the first layer (CI) and the second layer (If), and t□ is the layer thickness of the second layer (U) and the third i (I
Indicates the position of the interface with [[), that is, the second layer (II) containing germanium atoms is
Layer formation occurs toward the □ side.

FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the second layer (II) in the layer thickness direction.

In the example shown in FIG. 2, from the interface position 1B with the first layer (I) where the second layer (II) containing germanium atoms is formed to the position Ll, there is a distribution of germanium atoms. It is contained in the second layer (II) with the concentration C taking a constant value of 01, and gradually continues from the position L1 to the interface with the third layer (m) from the concentration C2. has been reduced to

At one boundary surface, the distribution concentration C of germanium atoms is C3.

In the example shown in Figure 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from position 1B to position 1, and once reaches C5 at position 1. It forms a distribution state like this.

In the case of Fig. 4, the distribution concentration C of germanium atoms is kept at a constant value C6 from position tB to position L2, and gradually and continuously decreases between position t2 and position 1. , Mtr, the distribution concentration C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of Fig. 5, the distribution concentration C of germanium atoms is continuously and gradually reduced from the concentration C8 from position tB to position 1, and becomes substantially zero at position t□. .

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is at position 1. Between position 13 and 13, the density is a constant value C9, and at position 13, the density is C10. Position t3 and position 1. In between, the distribution density C is linearly decreased from position t3 to position 1.

In the example shown in No. 71, the distribution C is once located, and from position L4 it takes a constant value of concentration c, and from position t4 to position 1, it is a linear function from concentration C12 to concentration CI3. It is said that the distribution state decreases to .

In the example shown in FIG. 8, from position iil tB to position Mt
Until □, the distribution concentration C of germanium atoms is the concentration C
It decreases linearly from I4 to substantially zero.

In FIG. 9, the distribution concentration C of germanium atoms decreases linearly from the concentration CI5 to the concentration CI6 from the position tB to the position its, and between the position tilts and the position An example is shown in which the concentration CIG is set to a constant value.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is at the concentration CI7 at the position LB, and it decreases slowly from this concentration CI7 until reaching the position t6, and then near the position L6. At position t6, the concentration is rapidly decreased to Cl1l at position t6.

Between position t6 and position t7, the concentration is decreased rapidly at first, then slowly and gradually decreased to reach CI9 at position L7, and between position t7 and position t8, it is extremely slowly decreased. The concentration is gradually decreased to reach the concentration C20 at position t8. Between position t8 and position t,
The concentration is decreased from C20 to substantially zero according to a curve shaped as shown in the figure.

In the example shown in FIG. 11, the germanium concentration C2□ is constant from position tB to position t9, and from position t9 to position 1
The germanium concentration C is kept constant at C21 up to B.

In the example shown in FIG. 12, the germanium concentration is substantially zero at position 1B and the germanium concentration is C at position t1.
23, increasing along the curve shown in the figure.

In FIG. 13, the germanium concentration is substantially zero at position tB and at position 1. The germanium concentration increases from L to concentration C24 at position t1° according to the curve shown in the figure.
From tso to position 1. The germanium concentration remains constant at C24 up to C24.

In addition, the germanium concentration distribution shown in FIGS. 2 to 13 shows a distribution in which the germanium concentration is high near the interface with the first layer (I) from FIG.
Although FIG. 1 to FIG. 13 show a distribution in which the germanium concentration is high near the interface with the third layer (III), a germanium concentration distribution may be obtained by combining these.

As described above with reference to FIGS. 2 to 13, some typical examples of the distribution state of germanium atoms contained in the second layer (■) in the layer thickness direction, in the present invention, , near the interface with the first layer (I) and/or the third layer (m)
In the vicinity of the interface with the first layer (I), there is a part with a high distribution concentration C of germanium atoms, and in the center of the second layer (II), the distribution concentration C is higher than that with the first layer (I). The second layer (II) is provided with a germanium atom distribution state that has a considerably lower portion near the interface and near the interface with the third layer (m).

The second layer (II) constituting the photoreceptive layer constituting the photoconductive member in the present invention is preferably the first layer as described above.
It is desirable to have a localized region (A) containing germanium atoms at a relatively high concentration near the interface with the layer (I) and/or near the interface with the third layer (m).

In the present invention, the localized region (A) is
To explain using the symbols shown in the figure, boundary surface position 1. Alternatively, it is desirable to provide the area within 5 scales from one knife.

In the present invention, the localized region (A) is located at the interface position t.
It may be the entire layer region (Lo) up to 5u thick from B or 1T, or it may be a part of the layer region (Lr).

Whether the localized region (A) is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the layer to be formed.

The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration C aX of germanium atoms is preferably 1000 atomic ppm or more with respect to silicon atoms, more preferably 5000 atomic ppm or more, optimally IX
It is desirable that the layer be formed in such a manner that it can have a distribution state of 104 to 30 ppm or more.

That is, in the present invention, the second layer (II) containing germanium atoms has a thickness within 5 μm from the first layer (I) side or the free surface of the second layer (n) ( t
It is preferable that the maximum value C ax of the distribution concentration exists in a layer region of 5-thickness from B).

In the present invention, the content of germanium atoms contained in the second layer (n) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1. ~9.5X 105105ato ppm,
More preferably 100~8X10 Satomic p
pm, optimally 500-7X 105105ato p
It is desirable to set it as pm.

In the photoconductive member of the present invention, high photosensitivity and high dark resistance are achieved, and furthermore, the first layer (I) and the second layer (II) or the second layer (n) and the third layer (m) or between the first layer (I), second layer (II) and third layer (II).
For the purpose of improving the adhesion with I), it is desirable that the second layer (■) contain carbon atoms.

The carbon atoms contained in the second layer (n) are
It may be contained in the entire area of IT) without any scratches, or it may be contained only in one layer area.

Further, the carbon atom distribution state C (C) may be uniform or non-uniform in the layer thickness direction of the second layer.

In the present invention, the carbon atom-containing layer region (c■) provided in the second layer (II) is (II) When provided so as to occupy the entire layer area and aiming to strengthen the adhesion with the first layer (I) and/or with the third layer (m), the first layer ( I) and/or the end layer region on the third layer (m) side.

In this way, the layer region (c■) provided in the second layer (■)
) is determined based on the characteristics required for the layer region (C■) itself, the first layer ('I) and the third layer (III) in order to achieve the above-mentioned purpose. ) or the properties required at the contact interface with the first layer (I)
It can be appropriately selected depending on the organic relationship with the characteristics of the third layer (I[I) layer, etc.

The amount of carbon atoms contained in the layer region (CII) is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001 to 50.
ato+mic$, more preferably 0.002-40a
tomic$, optimally 0.003-30 atomic
It is preferable to set it as c$.

In the photoconductive member of the present invention, when the first layer (I) is thin, the second layer (I) containing germanium atoms is used.
In (II), by locally providing a layer region (PN) containing a substance (C) that controls conductivity on the first layer (I) side, the layer region (PN) can be It can function as a charge injection blocking layer.

That is, the content of the substance (C) that controls conductivity in the layer region (PN) containing the substance (C) is preferably 3.
0ato■ic pp shoes or more, preferably 50at
os+ic ppm or more, optimally 100100ato
ppm or more, for example, when the contained substance (C) is the above-mentioned p-type impurity, when the free surface of the photoreceptive layer is charged to Φ polarity, the photoreceptor layer is removed from the support side. Injection of electrons into the photoreceptor layer can be effectively prevented, and when the contained substance (C) is the n-type impurity, the free surface of the photoreceptive layer can be charged to e-polarity. When holes are received, injection of holes from the support side into the photoreceptive layer can be effectively prevented.

In the above case, in the layer region (ZII) of the second layer (II) excluding the layer region (PN), there is a layer region (ZII) that controls the conductivity contained in the layer region (PM). substance C
A substance (C) that governs conductivity different from the polarity of G) may be contained, or a substance (C) that governs conductivity of the same polarity may be contained in the layer region (PM) in an amount greater than It may be contained in an even smaller amount.

In such a case, the content of the substance (C) that controls the conductivity contained in the layer region (Z■) depends on the polarity and content of the substance (C) contained in the layer region (PN). It is determined as appropriate depending on the amount.

Preferably 0.001 to 1001000ato ppt
a, more preferably 0.05 to 500 atomic p
p+w, optimally 0.1-200 atomic ppm
It is desirable that this is done.

In the present invention, the layer region (■) provided in the second layer (■)
PN) and the layer region (zn) contain the same kind of substance (C) that controls conductivity, the layer region (zn)
The content of the substance (G) that controls conductivity contained in the material is preferably 30 atomic ppm or less. In addition to the above-mentioned case, in the present invention, a layer region containing a substance (C) controlling conductivity having one polarity and a conductivity controlling substance (C) having one polarity is included in the second layer (II). It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing a substance (C) that controls conductivity. That is, for example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the second layer (II) so as to be in direct contact with each other to form a so-called p-n junction. Thus, a depletion layer can be provided.

In the present invention, specific examples of the halogen atom (X) contained in the second layer (II) if necessary include fluorine, chlorine, bromine, and iodine, but especially fluorine, Chlorine may be mentioned as suitable.

In the present invention, in order to form the second layer (II) composed of a-3iGs (H, Deposition method is applied.

For example, by glow discharge method, a-3iGe(H,X)
In order to form the second layer (■) made up of
A desired gas pressure state is maintained in the deposition chamber where the internal pressure can be reduced for the source gas for supply and, if necessary, the source gas for introducing hydrogen atoms (H) and/or the source gas for introducing halogen atoms (X). is introduced into the deposition chamber to generate a glow discharge in the deposition chamber, and the first ffi' (
A second layer composed of a-SiGe (H, (II) is formed.

In addition, when forming by sputtering method, for example, A
In an atmosphere of an inert gas such as r, He, or a mixed gas based on these residues, a target composed of eight plates, two targets consisting of the target and a target composed of Ge, or a target composed of Si and Using a target mixed with Ge, raw material gas for supplying CE diluted with dilution residues such as Ar and He and hydrogen atoms (
)l) Raw material gas and/or halogen atom (X) for introduction
A raw material gas for introduction is introduced into a deposition chamber for sputtering to form a desired gas plasma atmosphere, and the target is You can do it by sputtering.

In the case of the ion plate ink method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in the evaporation port as evaporation sources, and the evaporation sources are heated using the resistance heating method or the electron beam method. Sputtering can be carried out in the same manner as sputtering, except that the evaporated material is heated and evaporated by (EB method) or the like and the flying evaporated material is passed through a predetermined gas plasma atmosphere.

In the present invention, the following are effective starting materials for the raw material gas used to form the second layer (II).

First, the starting materials that will become the raw material gas for supplying Si are as follows:
SiH+, S! Gaseous or gasifiable silicon hydrides (silanes) such as 2H6, S+3HB, 5iaH1°, etc. are mentioned as those which are effectively used, and in particular,
SiH4 and Si2H6 are preferred in terms of ease of layer creation work and good Si supply efficiency. The starting material that becomes the raw material waste for supplying Ge is G.
e H4, Ge2H6, Ge3HB, Gl! 4HIO
1Ge5Ht2, Ge6H14, Ge7H16, GeB
Germanium hydride in a gaseous state or that can be gasified, such as Hto, GecJ (2°), can be effectively used. In particular, GeH4 , Ge7H6, and Ge3HB are preferred.

In the present invention, many l\\ halogen compounds can be mentioned as effective starting materials that serve as raw material gases for introducing halogen atoms (X) used to form the second layer (II). For example, halogen compounds in a gaseous state or capable of being gasified, such as /\halogen gas, /\halides, interhalogen compounds, /\halogen-substituted silane derivatives, are preferably mentioned. Furthermore, silicon hydride which is in a gaseous state or which contains silicon atoms and halogen atoms as constituent elements or which contains % halogen atoms can also be mentioned as one that can be effectively used.

In the present invention, the halogen compounds preferably used to form the second layer (II) are specifically:
Halogen gas such as fluorine, chlorine, bromine, iodine, CIF
, ClF3, BrF , BrF3, BrF5, I
F3, IF71. [1, IBr etc./\interlogen compounds can be mentioned.

Silicon compounds containing a halogen atom (X), so-called /
Preferred examples include silicon halides such as .

When forming the second layer (II) of the photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom (X), Si is used together with the raw material gas for supplying Ge. A second layer composed of a-5iGe (H, of! (II) can be formed.

According to the glow discharge method, the second one containing a halogen atom (X)
When forming the layer (II), basically, for example, S
Silicon halide, which serves as a raw material gas for i supply, germanium hydride, which serves as a raw material gas for Ge supply, Ar,
He and other scum are introduced at a predetermined mixing ratio and scum flow rate into the deposition chamber where the second layer (11) is formed, and a glow discharge is generated to generate plasma of these scum. By forming an atmosphere, the second layer (■) can be formed on the support on which the first layer (I) is formed on its large surface. Further, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is further mixed with these gases to form the second layer (II). Good too. In addition, each gas can be used not only individually but also in multiples at a predetermined mixing ratio.

In either the sputtering method or the ion blasting method, in order to introduce halogen atoms (x) into the formed layer, a gas of the above-mentioned halide or a silicon compound containing halogen atoms is introduced into the deposition chamber. However, a plasma atmosphere of the gas may be formed.

In addition, when introducing hydrogen atoms, a gas for introducing hydrogen atoms, such as H2, or the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering, and a plasma atmosphere of the gas is introduced. All you have to do is form it.

In the present invention, the above-mentioned halides or silicon compounds containing halogen atoms are effectively used as the raw material gas for introducing halogen atoms when forming the second layer (II). , HF, HGI, HBr
, hydrogen halides such as HI, SiH2F2.5iH
2I2.5iH2G12.5iHG13.5iH2Br
2, SiH2Br, 5it (halogen-substituted silicon hydride such as Br3, and GeHF3, GeHBr3, G
eH3F, GeHCl3, GeH2C12, Ge)
+3c1. GeHBr3. GeH2C12, GeHB
Halides containing hydrogen atoms as one of their constituent elements, such as r3 rumanium, GeF4, GeG14, GeBy4
, Ge14, GeF2. G-ecI2, GeB
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents, such as germanium halides such as r2, Ge12, etc., can also be mentioned as effective starting materials for forming the second layer (II). .

Among these substances, halides containing hydrogen atoms are
When forming the second layer (II), hydrogen atoms, which are extremely effective in controlling electrical or photoconductive properties, are also introduced into the layer at the same time as the halogen source r- is introduced into the layer. In some cases, it is used as a suitable raw material for introducing /\\rogen atoms.

In order to structurally introduce the hydrogen element f- into the second layer (II), in addition to the above, H2, SiH4, Si2H6,
5i3HB, 5i4H+. Ge
or with germanium or germanium compounds for supplying GetIn, Ge2H6, Ge3HB
, ce4)+10, Ge5H12, Gl! 68I4,
It can also be carried out by causing germanium hydride such as Ge7H16, Ge5H12, Ge5H12 and silicon or a silicon compound for supplying Si to coexist in the deposition chamber to generate radiation.

In a preferred example of the present invention, hydrogen atoms (H) that may be contained in the second layer (11) of the photoconductive member to be formed
The amount of /\the amount of halogen atoms ('X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 0.
01-40 atomic%, more preferably 0.05-3
0ato+sic%, optimally 0.1-25atomi
It is desirable to set it to c%.

Hydrogen atoms (H
) and/or to control the amount of halogen atoms (X),
For example, support temperature, hydrogen atom (H) or halogen atom (X
), the amount of the starting material introduced into the deposition system, the discharge power, etc. may be controlled.

In the second layer (11), a substance (C) that controls conductivity,
For example, in order to structurally introduce a group Ⅰ atom or a group V atom, in the same way as in the case of explaining the method for forming the first layer (I), the method for introducing a group The starting material or the starting material for introducing group V atoms may be introduced in gaseous state into the deposition chamber together with other starting materials for forming the second layer (II).

The layer thickness of the second layer (II) in the photoconductive member of the present invention is such that when the second layer (II) is mainly used as a photocarrier generation layer, the thickness of the second layer (II) is determined by It is determined appropriately considering the absorption coefficient of the layer (n) of No. 2, preferably 100OA to 50μ, more preferably 10
It is desirable to set it to 0OA -30 scales, optimally +000A to 20μ.

In addition, when the second layer (II) is mainly used as a layer for generating and transporting photocarriers, the second layer (II) is appropriately determined as desired so that photocarriers are efficiently transported, and is preferably a layer for generating and transporting photocarriers. -100μ, more preferably 1~
It is desirable that it be 80 mm, most preferably 2 to 50 IIJ11.

In the present invention, in order to provide a layer region (ell) containing carbon atoms in the second layer (ff), carbon atoms are In the same manner as for forming the layer region containing carbon atoms in the first layer (I), except that the starting material for introduction is used together with the starting material for forming the second layer (II) described above. It is sufficient if the amount thereof is controlled to be contained in the layer to be formed.

In the present invention, the first layer (I) and the second layer (II
), a layer region containing carbon atoms (C)
is provided in at least one of these layers, the distribution concentration C (C) of carbon atoms contained in the layer region (C) is changed in the layer thickness direction to obtain a desired teno distribution shape g(de) in the layer thickness direction.
In the case of the glow discharge method, in order to obtain the desired change rate curve, the flow rate of a gas consisting of a starting material for introducing carbon atoms whose distribution concentration C (C) is to be changed is changed as appropriate in accordance with a desired rate of change curve. It is possible to apply a method of forming these layers by introducing them into a deposition chamber while

In the case of sputtering, when using a mixed target of Si and Si3N4 as a sputtering target, for example, the mixing ratio of Si and Si3N4 is changed in advance in the layer thickness direction of the target. By setting the thickness of the layer, it is possible to obtain a desired distribution state (depth profile) of carbon atoms in the layer thickness direction.

The third layer (III) 105 formed on the second layer (II) 104 of the photoconductive member of the present invention has a free surface,
It is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, and durability. Second! (II) and the third layer (m) are each mainly composed of an amorphous material having a common constituent atom, silicon atoms, and therefore have chemical stability at the laminated interface. is sufficiently secured.

The third layer (■) in the present invention is silicon atoms (Sυ
and an amorphous material containing an oxygen atom (0) and, if necessary, a hydrogen atom (H) and/or a halogen atom (X) (hereinafter a-(Six o, -x)y) (
)l, X)+-7, provided that 0 < x, y < 1
).

The third layer (III) composed of a-(SiXol-X)y (H, Implemented by law etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. A third layer (m) in which the conditions for manufacturing the conductive member are relatively easy to control and in which oxygen atoms and halogen atoms are formed together with silicon atoms.
The glow discharge method or the sputtering method is preferably employed because of the advantages such as ease of introduction into the interior. Further, the third layer (m) may be formed by using a glow discharge method and a sputtering method in the same apparatus system.

To form the third layer (m) by the glow discharge method,
a-(Slx O+ -x)y CH,X) 1-
The raw material gas for forming y is mixed with a diluent gas at a predetermined mixing ratio if necessary, and introduced into the deposition chamber for vacuum deposition where the support on which the second layer (II) is formed is installed. , the introduced gas is turned into gas plasma by causing a glow discharge, and a-
(Six ol-X)y (H, Xl+-y) may be deposited.

In the present invention, a-(Six o, -x)y (
As the raw material residue for forming H, Most of the gaseous substances contained therein or the gasified substances that can be gasified may be used.

Si, 0. When using a raw material gas having Si as a constituent atom as one of H and X, for example, a raw material gas having Si as a constituent atom, a raw material gas having 0 as a constituent atom,
Source gas containing H as a constituent atom and/or X as necessary
or a raw material gas containing Si as constituent atoms at a desired mixing ratio, or a raw material gas containing Si as constituent atoms and a raw material gas containing 0 and H and/or 0 and Alternatively, a raw material gas containing Si as constituent atoms may be mixed at a desired mixing ratio, or a raw material gas containing Si, 0, and H as constituent atoms or Si , 0, and X as constituent atoms are mixed at a desired mixing ratio.

Alternatively, for reliability, a raw material gas containing Si and H as constituent atoms and a raw material gas containing 0 as constituent atoms may be mixed and used, or a raw material gas containing Sl and X as constituent atoms may be used. and raw material waste having 0 as a constituent atom may be used in combination.

In the present invention, preferred halogen atoms (X) that may be contained in the third layer (III) are F, C:
1, Br, and I, with F and CI being particularly desirable.

In the present invention, the starting material serving as the raw material residue for forming the third layer (III) is Si,! :S i H4, Si2H6, 5i3HB, 5i4 whose constituent atoms are H
Gaseous or gasifiable silicon hydride (such as H1°)
Silanes) can be effectively used, and SiH4 and Si2H6 are particularly preferred from the viewpoint of ease of layer creation and good Si supply efficiency.

If these starting materials are used, S can be added in the third layer (m) to be formed by appropriately selecting the layer forming conditions.
H may also be introduced along with i.

Effective starting materials that serve as raw material gas for supplying Si include:
In addition to the above-mentioned silicon hydride, silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example, SiF4.5i2F 6 , 5
Silicon halides such as iCI4 and SiBr4 can be mentioned as preferred, and furthermore, Si
H2F2.5iH2I2, SiH2012, 5iHC
Halogen-substituted silicon hydrides such as 13,5iH2Br2.5iHBr, etc., in gaseous state or capable of being gasified,
Halides containing hydrogen atoms as one of their constituents can also be mentioned as effective starting materials for forming the third layer (m).

Even when using silicon compounds containing these halogen atoms (X), the halogen atoms (X) can be included together with Si in the third layer (III) formed by appropriately selecting the layer forming conditions as described above. can be introduced.

In the present invention, effective starting materials that serve as raw material gas for introducing halogen atoms (X) used to form the first layer (I) include, in addition to the above, for example, fluorine,
Halogen gas such as chlorine, bromine, iodine, CIF, Cl
F3, BrF, 13rF3, BrF5IF5,
Interhalogen compounds such as IF7, ICI, IBr, etc.
Examples include hydrogen halides such as HF, HC:I, HBr, and old.

In the present invention, starting materials that are effectively used as a raw material gas for supplying oxygen atoms (0) used to form the third layer (III) include those having 0 as a constituent atom, or 0 and H as constituent atoms, for example oxygen (O2)
, ozone (03), ' -nitrogen oxide (NO), nitrogen dioxide (NO2), nitrogen oxide (N20), nitrogen sesquioxide (N203), nitrogen tetroxide (N,,04), nitrogen sesquioxide (N20S) , nitrogen trioxide (NO3), silicon atoms (Si), oxygen atoms (0), and hydrogen atoms (I()), such as disiloxane (H3SiOSiH
3), Trisiloxa 7 (H35iOSiH205iH
3) etc. (7) Lower siloxanes and the like can be mentioned.

These third layer (III) forming substances contain silicon atoms, oxygen atoms, and optionally halogen atoms and/or hydrogen atoms in a predetermined composition ratio in the third M (III) to be formed. In the formation of the third layer (m), it is selected and used as desired.

To form the third layer (m) by sputtering, for example, the following method can be adopted.

The first method is to process Si in an atmosphere of an inert gas such as At or He or a mixed gas based on these gases.
When sputtering a target made up of It is sufficient to introduce it into the deposition chamber where the process is carried out.

In the second method, as a target for sputtering, a target made of Si, a target made of Si and a target made of 5i02, or a target made of Si and 8102 is used. By using the target, oxygen atoms (0) can be introduced into the third layer (In). At this time, if the aforementioned raw material gas for introducing oxygen atoms (0) is also used, the amount of oxygen atoms (0) introduced into the third layer (m) can be controlled as desired by controlling the flow rate. It is easy to control.

As a material serving as a raw material gas for introducing 0.8 and obtain.

In the present invention, so-called dilute scum, such as He, Me, A, r, etc., are suitable as the diluting gas used when forming the third layer (m) by a glow discharge method or a sputtering method. It can be mentioned as follows.

The third layer (m) in the present invention is carefully formed so as to provide the desired properties.

In other words, a substance whose constituent atoms are Si, 0, H and/or Semiconductor property.

In the present invention, a-(Sixo
, -X)y (H,X)sy so that sy is formed,
The selection of the production conditions is made strictly according to desire. For example, when providing the third layer (III) with the main purpose of improving electrical withstand voltage, a-(Six ol -x
)y (H,

In addition, when a third layer (m) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and the resistance to irradiated light is reduced. The amorphous material has a certain degree of sensitivity.
−(Six O+ −x )y (HlXL-y is created.

On the surface of the second layer (II) a-(stx O, -X
When forming the third layer (m) consisting of )y (H5 In the present invention, a-(StxO
It is desirable that the temperature of the support during layer formation be strictly controlled so that + -x )y (H,X) 1-y can be formed as desired.

In the present invention, the formation of the third layer (m) is carried out by selecting an optimal range as appropriate according to the method of forming the third layer (m) in order to effectively achieve the desired purpose. but preferably 20 to 400°C1, more preferably 50 to 350°C
The temperature is preferably 100 to 300°C. Glow discharge method and sputtering method are used to form the third layer (m) because delicate control of the composition ratio of atoms that make up the layer is relatively easy compared to other methods. is advantageous, but when forming the second layer by these layer forming methods, the discharge power during layer formation is created in the same manner as the support temperature described above. y
It can be cited as one of the important factors that influence the characteristics of (H,

a-(Six O+ -x)y (H,X) having the characteristics to effectively achieve the purpose of the present invention
The discharge power conditions for effectively producing ty with good productivity are preferably 10 to 300 W, more preferably 20 to 250 W, and optimally 50 to 200 W.

The gas pressure in the deposition chamber is preferably 0.01"l.
Torr, preferably about 0.1-0.5 Torr.

In the present invention, the desirable numerical ranges of the support temperature and discharge power for creating the third layer (III) include the values in the above ranges, but these layer creation factors can be determined independently. The desired characteristics a-(Six o, -X)y()l,X)+-
Preferably, the optimum value of each layer creation factor is determined based on the mutual organic relationship so that the third layer (m) consisting of y is formed.

The amount of oxygen atoms contained in the third layer (m) in the photoconductive member of the present invention is the same as the conditions for creating the third layer (m).
This is one of the important factors for forming the third layer (m) that provides the desired properties that achieve the object of the present invention.

The amount of oxygen atoms contained in the third layer (m) in the present invention is determined as desired depending on the characteristics of the amorphous material constituting the third layer (III). .

That is, the general formula a-(Stx O', -11)y
The amorphous material shown in (H,
a < 1), an amorphous material composed of silicon atoms, oxygen atoms, and hydrogen atoms (hereinafter referred to as a-(Sib O+ −
b) Write as e H+-e. However, 0 < b, c
<1), an amorphous material composed of silicon atoms, oxygen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter a-(Sino, -d)s (H,X)s-
It is written as e. However, it is classified as 0 < d, e < 1).

In the present invention, the third layer (m) is a-silo I-
When composed of a, the amount of oxygen atoms contained in the third layer (III) is preferably 8, preferably 0.33 to 0.899.
1119, more preferably 0.5 to 0.98, optimally 0.6 to 0.8.

On the other hand, in the present invention, the third layer (m) is a-C5ib
O+ -b)c H+-e, the third
The amount of oxygen atoms contained in the layer (m) is such that b is preferably 0.33 to 0.99999, more preferably 0.5 to 0.
．． 98, optimally 0.6-0.9, C preferably 0.98, optimally 0.6-0.9, C preferably 0.
Desirably, it is between 6 and 0.98, more preferably between 0.85 and 0.88, most preferably between 0.7 and 0295.

The third layer (III) is a-(Sin o, -a)
e (When composed of H, 0.5 to 0.99, optimally 0.8 to G, 9, e, preferably 0.8 to 0.89, more preferably 0.82 to 0.
98, most preferably 0.85 to 0.98.

Further, the amount of hydrogen atoms (H) is preferably 90a with respect to the sum (H+X) of halogen atoms (X) and hydrogen atoms (H).
atomic% or less, more preferably 80 atomic%
Hereinafter, it is optimally desirable to set it to 70 atomic% or less.

The numerical range of the layer thickness of the third layer (m) in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose.

' Also, the layer thickness of the third layer (III) is the same as that of the third layer (III).
III) The amount of oxygen atoms contained in the first layer (I)
The relationship with the layer thickness of the second layer (II) also needs to be determined as desired based on the organic relationship depending on the characteristics required for each layer. In addition, it is desirable to consider the economical aspects including productivity and mass production.

The thickness of the third layer (m) in the present invention is preferably 0.003 to 30 scales, more preferably 0.004 to 2 scales.
It is desirable that the scale be 0u, optimally 0.005 to 10 scales.

The support 101 used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A1. Cr,
No, Au, Nb, Ta, V, Ti, P
Examples include metals such as T, 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.

In other words, for example, if it is glass, N1G is applied to the surface of the glass.
r, AI, Cr, No, Au, Ir, Nd, T
a, V, Ti, Pt, In2O3, 5n02, I
Conductivity is imparted by providing a thin film made of TO (In203 + 5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr,
A1. Ag, Pb, Zn, Ni, Au, Or,
Mo, Ir, Nb, Ta, V, Ti, Pt
Conductivity is imparted to the surface by providing a thin film of metal such as by vacuum evaporation, electron beam evaporation, sputtering, etc., or by terminating the surface with the metal.

The shape of the support is determined as desired, but for example, if the photoconductive member 100 of FIG. It is desirable to have a belt shape or a cylindrical shape. 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 a case, the number of scales is usually 10 scales or more in view of manufacturing and handling of the support, as well as mechanical strength.

Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be described.

FIG. 20 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method.

Gas cylinders 1102 to 110B in the figure are filled with raw material gas for forming the photoconductive layer of the photoconductive member of the present invention. For example, 1102 is SiH4 gas diluted with He. (Purity 11L999%, hereinafter S
1103 is a He diluted GeF4 gas (purity 119.1199%, hereinafter abbreviated as GeF4/He gas) cylinder, 1104 is H
82H diluted with e gas (M degree 911.9H%, hereinafter abbreviated as B2 H6/He gas) cylinder, 1105 is C2) Ll gas (purity 99.911%) cylinder, 110
6 is a He gas (purity 911.911%) cylinder.

Although not shown in the drawings, it is possible to add cylinders of desired gas types in addition to these as needed.

In order to flow these gases into the reaction chamber 1toi, each valve 1122 to 112 of the gas cylinder 1102 to 110B is
8 and leak valve +135 are closed, and also inlet valves 1112-111B, outlet valves 1117-1121 and auxiliary valves 1132.113
Make sure that valve 3 is open, then open main valve 1 first.
134 is opened to exhaust the inside of the reaction chamber +101 and each gas pipe. Next, the reading of vacuum gauge 1138 is about 5X 10'6t
The auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed with the priority that has become orr.

First, an example of forming the first layer (I) on the cylindrical substrate 1137 will be described.
H6/He gas, C2H4 gas from gas pump 1105, open valves 1122.1124.1125, adjust the pressure of outlet pressure gauge 1127.1129.1130 to IKg/cm2, and inflow valve 1112.1.
Gradually open valves 114 and 1115 to allow the water to flow into the rollers 1107, 1108 and 1110, respectively.Subsequently, the outflow valves 1117 and 1119
．． 1120 and auxiliary valve 1132 are gradually opened to allow each gas to flow into the reaction chamber 1101.

At this time, the outflow valve 1117.11113.1120 is adjusted so that the ratio of the 5iH47He gas flow rate, the C2H4 gas flow rate, and the 82 H6/He gas flow rate becomes the desired value, and the pressure inside the reaction chamber becomes the desired value. Adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136. After confirming that the temperature of the base cylinder 1137 is set to a predetermined temperature of 50 to 400°C by the heating heater 1138, the electric power [1140] is set to the desired power to generate a glow discharge in the reaction chamber 1101. to coat the first layer (I) on the base cylinder 1137.
) to form. Further, during layer formation, the base cylinder 1137 is rotated at a constant speed by a motor 1138 in order to ensure uniform layer formation. All the gas operation system valves used last are closed, and the reaction chamber 1101 is once evacuated to high vacuum.

Next, an example of the case where the second layer (II) is formed on the first layer (I) formed in this way is shown in which the reading of the vacuum gauge 1138 is approximately 5×10°” torr. Repeat the same operation as in case 2.

That is, SiH4/He gas from gas pump 1102, GeF4/He gas from gas pump 1103, 82 H6/He gas from gas pump 1104, and C2H4 gas from gas pump 1105 through valve 1122.112.
3. Open each of 1124 and 1125 and check the pressure of outlet pressure gauge 1127, 1128, 1128, 1130 in IKg.
/ Adjust to arm2, inflow pulp 1112.111
3.1114.1115 are gradually opened to allow flow into mass flow controllers 1107.1108, +109, +110, respectively. Subsequently, outflow valve 1117.
1118.1119.1120 and auxiliary pulp 1132
are gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, SiH4/He gas flow rate and GeF4
/ He gas flow rate and 82 H6 / He gas flow rate and C2
Outflow pulp +1 so that the ratio with H4 gas becomes the desired value.
Adjust 17.1118.1119.1120 and also
Vacuum so that the pressure inside the reaction chamber reaches the desired value;
Adjust the opening of the main valve 1134 while checking the reading of 3s. After confirming that the temperature of the base cylinder 1137 is set to a predetermined temperature of 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. Then, the second layer (II) is formed on the base cylinder 1137 in the same manner as in the case of forming the first layer (I).

Next, when forming the third layer (I[[) on the second layer (II) formed in this way, all the gas operating system valves used are is closed, the reaction chamber 1101 is once evacuated to a high vacuum, and when the reading on the vacuum gauge 1136 becomes approximately 5X 10' torr, in the same manner as above, for example, SiH4 is injected from the gas pump 1102.
/He gas and NO gas are supplied from the gas pump 1106 to generate glow discharge and form the third layer (m). The amount of oxygen atoms in the third layer (III) is controlled by adjusting the NO gas supply flow rate.

Examples will be described below.

Example 1 Using the photoconductive member manufacturing apparatus shown in FIG. 20, a photoreceptive layer was formed on an AI cylinder according to the manufacturing conditions shown in Table 1 by the glow discharge decomposition method detailed above. Each sample of an image forming member for electrophotography (sample NG, 1-1-1
~1B-10-8 (860 pieces in total) were created.

Figures 14A and 14B show the distribution state of boron atoms contained in the layer region consisting of the first layer (I) and second layer (■1) in the photoreceptive layer in each sample. The distribution of atoms is shown in FIG. 15, and the distribution of germanium atoms contained in the second layer (■) is shown in FIG. 16.

The distribution state of boron atoms, carbon atoms, and germanium atoms in each sample is determined by the sample number (H
6).

That is, the distribution state of boron atoms and carbon atoms is indicated by the numbers 1-1-1ft-10 as shown in Table 3, and the distribution state of germanium atoms is indicated by the numbers 1-1-1ft-10 for each sample as shown in Figure 16. l-1-1 The numbers 1 to 6 corresponding to the numbers at the end of the species distribution status (501 to 506) are shown in Table 3.
It was added to the end of the number of ff-10.

Such distribution of boron atoms, carbon atoms, and germanium atoms can be achieved by automatically controlling the opening/closing state of the corresponding pulp according to a predetermined gas flow rate change curve.
/ Formed by adjusting the HB waste flow rate.

Each sample of the image forming member obtained in this way is individually set in a charging exposure experiment apparatus; 5. Corona charging was performed for 0.3 seconds using OKV, and a light image was immediately irradiated.

The optical image was created using a tungsten lamp light source with a 0.2 lu
A light amount of x@sec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the photoconductive member surface by cascading an e-chargeable developer (including toner and carrier) over the photoconductive member surface. 5. Toner image on the surface of the photoconductive member. When the image was transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Next, replace the light source with a tungsten lamp using an 810n
Using an m-GaAs semiconductor laser (10 mW),
When the image quality of the toner transfer image was evaluated under the same toner image forming conditions as above except that an electrostatic image was formed, a clear, high-quality image with good gradation reproducibility was obtained.

Example 2 Example 1 was carried out using the manufacturing apparatus shown in FIG. 20, except that the manufacturing conditions for the cylindrical AI substrate were as shown in Table 2.
Samples of image forming members for electrophotography (a total of 432 samples of samples 21-1-1 to 2B-9-8) were prepared in the same manner as described above.

The first layer (I
) and the second layer (II), the distribution state of boron atoms contained in the layer region is shown in Fig. 17, and the distribution state of carbon atoms is shown in Fig. 18. FIG. 18 shows the distribution of germanium atoms.

The distribution state of boron atoms, carbon atoms, and germanium atoms in each sample was expressed by the sample number (#li) assigned to each sample in the same manner as in Example 1.

That is, the distribution state of boron atoms and carbon atoms is shown by numbers 21-1 to 28-9 as shown in Table 4, and the distribution state of germanium atoms is shown in numbers 21-1 to 28-9 for each sample as shown in Figure 19. Numbers 1 to 6 corresponding to the numbers at the end of species distribution pattern 8 (601 to 606) are shown in Table 4. 1-1 to 16
-What year is at the end of the number 10?

Using each sample of the image forming member thus obtained, the image quality of the toner transfer image was evaluated in the same manner as in Example 1. A quality image was obtained.

Example 3 Samples 5-5-2 and 14 of Example 1 were prepared using the manufacturing apparatus shown in FIG. 20, except that the conditions for forming the third layer (m) were as shown in Table 5. -10-5 and Sample 25-3-4 of Example 2 were prepared under the same conditions and procedures as the electrophotographic imaging members (Sample A
I6.5-5-2-1 to 5-5-2-8.14-10-
5-1 to 14-10-5-8, 25-3-4-1 to 2
A total of 24 samples (5-3-4-8) were prepared.

Using each of the image forming members thus obtained, image quality was evaluated under the same conditions as in Example 1, and durability through repeated and continuous use was evaluated.

The evaluation results for each of these samples are shown in Table 6.

Example 4 The third layer (m) was prepared by sputtering, and the target area ratio between the silicon wafer and the 5i02 wafer was variously changed during its formation, so that the silicon atoms and oxygen in the third layer (In) were A photoreceptive layer was formed on a cylindrical AI substrate in the same manner as Sample A1118-9-4 of Example 1 except that the content ratio of atoms was changed, and an image forming member for electrophotography (sample sample A1118-9-4) was formed. 8-9-4-1 to 8-9-4-
7) were produced.

Using each of the image forming members thus obtained, the image forming, developing, and cleaning steps similar to those in Example 1 were repeated approximately 50,000 times, and then image quality was evaluated.
Table evaluation results were obtained.

Example 5 The same procedure was carried out except that when forming the third layer (III), the flow rate ratio of SiH4 gas and NO gas was changed and the content ratio of silicon atoms and oxygen atoms in the third layer (III) was changed. Example 1
A light-receiving layer was formed on a cylindrical AI substrate in exactly the same manner as Sample 8-f3-4 to produce image forming members for electrophotography (Sample 8-9-4-11 to 5-9-5). A total of 7 pieces (a-x7) were produced, respectively.

Using each of the image forming members thus obtained, the same image forming, developing, and cleaning steps as in Example 1 were repeated approximately 50,000 times, and then image quality was evaluated.
Table evaluation results were obtained.

Example 6 When forming the third layer (m), the content ratio of silicon atoms and oxygen atoms in the third layer (m) was changed by changing the flow rate ratio of SiH4 gas, SiF4 dregs, and NO gas. Except for this, a photoreceptive layer was formed on a cylindrical AI substrate in exactly the same manner as Sample AI6.8-9-4 of Example 1 to obtain an electrophotographic image forming member (Sample M68-9-4-21). ~8-9-
4-27) were produced, respectively.

Using each of the image forming members thus obtained, the same image forming, developing, and cleaning steps as in Example 1 were repeated approximately 50,000 times, and then image quality was evaluated.
Table evaluation results were obtained.

Example 7 A light-receiving layer was formed on a cylindrical AI substrate in the same manner as sample MfL8-9-4 of Example 1 except that the thickness of the third layer (m) was changed. Image forming members for electrophotography (a total of four samples, Samples 8-8-4-31 to 8-9-4-34) were each produced.

Using each of the image forming members thus obtained, the image forming, developing, and cleaning steps similar to those in Example 1 were repeated approximately 50,000 times, and then image quality was evaluated.
Table 0 evaluation results were obtained.

Common layer forming conditions in the above-mentioned non-examples are shown below.

Support temperature When forming the first layer and third layer: Approximately 250°C When forming the second layer: Approximately 200°C Discharge frequency: 13.58 MHz Reaction chamber internal pressure during reaction: 0.3 Torr Table 10

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing the layer structure for explaining the structure of the photoconductive member of the present invention, and FIGS. 2 to 13 respectively show germanium in the second layer (II) of the present invention. Schematic diagrams for showing the distribution state of atoms, Figures 14A and 14
Figure B is a diagram showing the distribution state of boron atoms in the photoreceptive layer of the photoconductive member created in Example 1 of the present invention, and Figure 15 is a diagram created in Example 1 of the present invention. A diagram showing the distribution state of carbon atoms in the photoreceptive layer of the photoconductive member,
FIG. 16 is a schematic diagram showing the distribution state of germanium atoms in the second layer (II) of the photoconductive member produced in Example 1 of the present invention, and FIG. FIG. 18 is a diagram showing the distribution state of boron atoms in the photoreceptive layer of the photoconductive member prepared in Example 2, and FIG. FIG. 18, a diagram showing the distribution state of carbon atoms in the layer, shows the second layer (II) of the photoconductive member prepared in Example 2 of the present invention.
FIG. 20 is a schematic diagram showing the distribution state of germanium atoms in ), and FIG. 20 is a diagram showing an apparatus for manufacturing a photoconductive member by the glow discharge decomposition method. 100: Photoconductive member 101: Support 102: Light receiving amount 103: First layer 104: Second layer 105: Third layer 1101: Reaction chambers 1102 to 1108: Gas cylinders 1107 to 1111 + mass flow controller 1112
~111111: Inflow valves 1117-112 Outflow valves 1122-1126: Valves 1127-113'l Pressure regulator + 132: Auxiliary valve 1133: Main valve +
134: Gate valve 1135: Leak valve 11
36: Vacuum gauge 1137: Base cylinder 1138:
Heater 1139: Motor +140: High frequency power supply (matching box) Fig. 1□C Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6 Fig. 7 Fig. C Fig. 8 Fig. 9 Fig. 1O Fig. (301) (302) (303) (304) (a
tomic pp+++) No. (305) (306) (307) (308) 17
Diagram (401) (402) (Smell 03) (4014)
(405) 18th (406) (407) (408) (409) (6
01) (602) (603) (++m) Gel manila M) content distribution concentration (atomi
, c Z) No. (60) (605) (606) Figure 19

Claims (5)

[Claims] (1) In a photoconductive member having a support for a photoconductive member and a photoreceptive layer provided on the support and having photoconductivity, the photoreceptor layer is formed of silicon from the support side. a first layer (I) composed of an amorphous material containing atoms;
A second layer (II) made of an amorphous material containing silicon atoms and germanium atoms, and a third layer (m) made of an amorphous material containing silicon atoms and oxygen atoms. The germanium atoms contained in the second layer (II) are distributed non-uniformly in the layer thickness direction of the layer, and Layer (I
A photoconductive member characterized in that at least one of I) contains a carbon atom. (2) The photoconductive member according to claim 1, wherein at least one of the first layer (I) and the second layer (■) contains hydrogen atoms and/or halogen atoms. (3) The photoconductive member according to claim 1 or 2, wherein at least one of the first layer (I) and the second layer (II) contains a substance that controls conductivity. . (4) The photoconductive member according to claim 3, wherein the substance that controls conductivity is an atom belonging to Group Ⅰ of the periodic table. (5) The photoconductive member according to claim 3, wherein the substance that controls conductivity is an atom belonging to Group V of the periodic table.