JPS60140356A - Photoconductive member - Google Patents

Abstract

PURPOSE:To stabilize electrical, optical and other characteristics by providing a photoreceptive layer consisting of an amorphous material contg. Si atoms, amorphous material layer contg. Si atoms and Ge atoms and amorphous material layer contg. Si atoms and O atoms on a base. CONSTITUTION:A photoreceptive layer 102 constituted of the 1st layer 103 consisting of an amorphous material contg. Si atoms, the 2nd layer 104 consisting of an amorphous material contg. Si atoms and Ge atoms and the 3rd layer 105 consisting of an amorphous material contg. Si atoms and O atoms and having photoconductivity is provided on a base 101 for a photoconductive member 100 to manufacture a photoconductive member. Carbon atoms are required to be incorporated into at least either of the 1st layer and the 2nd layer in this case. It is preferable to incorporate hydrogen atoms or halogen atoms into at least either of the 1st layer and the 2nd layer.

Description

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

[Prior Art] A highly sensitive photoconductive material 1 for forming a photoconductive layer in a solid-state imaging device, or an electrophotographic image forming member in the image forming field or a document reading device.

It has a high signal-to-noise ratio [photoelectricity fIf, (Ip)/dark current (Id)], has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, and has a desired dark resistance value. The solid-state imaging device 4 is 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 given time.

Particularly in the case of an electrophotographic image forming member that is installed in 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 point of view, amorphous silicon (hereinafter referred to as a-3i) is a photoconductive material that has recently attracted attention.
The fjS2855718 publication describes an application to an electrophotographic image forming member, and DE 28'33411 describes an application to a photoelectric conversion reader.

However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and temperature resistance. The reality is that there are problems that need to be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires comprehensive improvement of characteristics.

For example, when applied to an image forming member for electrophotography J″L,
In the past, when attempting to simultaneously increase the sensitivity of the tip of the tube and increase the -118 resistance, it was often observed that residual potential remained during use, and this type of photoconductive member could be repeatedly used if used repeatedly for a long time. There have been many disadvantages, such as accumulation of fatigue due to this, resulting in so-called ghost phenomenon, which causes afterimages, and gradual decline in responsiveness when used repeatedly at high speeds.

Furthermore, a-9i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. Furthermore, there is still room for improvement in that when a commonly used halogen lamp or fluorescent lamp is used as a light source, it is not possible to effectively use light on the longer wavelength side. 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 "blurring" in images. 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 forming a photoconductive layer using an a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms,
and boron atoms, phosphorus atoms, etc. to control the electrical conduction type, or other atoms to improve other properties.
Each of these constituent atoms is contained in the photoconductive layer, but depending on the manner in which these constituent atoms are contained, problems may arise in the electrical or photoconductive properties of the formed layer.

That is, for example, sufficient image moisture 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 may be generated from the support side in dark areas. In many cases, problems arise due to insufficient blocking of the charge on the injector.

Therefore, while efforts are being made to improve the properties of the a-9i 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 (Sl) as its matrix, especially silicon atoms (Si) as its matrix, with either hydrogen atoms ()l) or halogen atoms (X) An amorphous material containing at least one of the above, i.e., so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon (hereinafter referred to generically as a-9i(H,X)), and silicon atoms. (
Si) and germanium atoms (Ge) as a matrix, especially amorphous materials with these atoms as a matrix and hydrogen atoms (H)
or an amorphous material containing at least one of halogen atoms (x), that is, so-called 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, when compared with conventional photoconductive materials, it has 71 ffs in all respects, and has particularly excellent characteristics as a photoconductive material for electronic photography, and has excellent properties on the long wavelength side. Absorption spectrum at 4. This is based on the discovery that it has excellent ν properties.

[Objective of the Invention] The present invention is an all-environment type in which electrical, optical, and photoconductive properties are always stable and are hardly affected by the usage environment, and has excellent photosensitivity on the long wavelength side. It has excellent light fatigue resistance and does not deteriorate even after repeated use.
The main objective is to provide a photoconductive member in which no or very little residual amount is 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 that when applied as an image forming member for electrophotography, (1) normal electrophotography can be applied very effectively to the band-E processing for electrostatic image formation. It is an object of the present invention to provide a photoconductive member having sufficient charge retention ability and excellent electrophotographic characteristics.

Still another object of the present invention is a photoconductive member for electrophotography that can easily obtain high-quality images with high density, clear halftones, and high resolution, and without image defects or image deletion. The goal is to provide the following.

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 soft 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 (m) made of an amorphous material containing silicon atoms and oxygen atoms, and at least one of the first layer (I) and the wS2 layer (II). , a photoconductive member characterized by containing carbon atoms.

The distribution of germanium atoms in the second layer (II) is uniform in the layer thickness direction and in a plane parallel to the surface of the support. Hydrogen atoms and/or halogen atoms are preferably contained in at least one of the first layer (I) and the second layer (1). Also,
Preferably, at least one of the first layer (I) and the second layer (II) 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, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it has high sensitivity.

It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high image Wjf, bright halftones, and high resolution. can.

Furthermore, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, especially when used with semiconductor lasers.

Excellent photo-resistance and fast photoresponse.

[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 has a photoreceptive layer 102 having sufficient volume resistance and photoconductivity on a support 101 for the photoconductive member. Photoreceptive layer 102
is the first layer consisting of a-9i(H,X) from the support side.
Layer (I) 103, a-9iGe()1. X) second layer (11) 104, a-SiO()l, X
), the third layer (m) 105 is composed of:

Photoconductivity may be imparted to either the first layer (I) or the second layer (11), but in any case, the layer to which incident light reaches has photoconductivity. needs to be designed.

Moreover, in this case, the first layer (I) and the second layer (II
) both have photoconductivity for the desired light.
It is desirable to design the layer as a layer that is capable of generating a sufficient amount of photocarriers.

In the photoconductive member of the present invention, high photosensitivity and high 11r
In order to improve the adhesion between the support and the photoreceptive layer or between the layers constituting the photoreceptive layer, the first layer (I) and the second layer ( II) at least one of them contains a carbon atom.

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.

The carbon atoms contained in at least one of the first layer (I) and the second layer (II) 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 wSl layer (I) and the second
The carbon atom-containing layer region (C) provided in at least one of the layers (II) is not suitable for these layers when the main purpose is to improve photosensitivity and dark resistance. It is provided so as to occupy the entire layer area. In addition, when the purpose is to strengthen the adhesion of a desired adhesion surface among the adhesion surfaces between the support and the first H(I) and the adhesion surfaces between each layer constituting the light-receiving layer, , for example, the support and the first layer (
1), if you want to strengthen the adhesion with the layer (I) of the tjIjl layer,
If you want to strengthen the adhesion between the first layer (I) and the second layer (II), the layer interface between the first layer (I) and the second layer (II) and the area near the layer interface can be !■) and the third layer (II
If the purpose is to strengthen the adhesion with the second layer (II), try to strengthen the adhesion a1, such as by providing it so as to occupy the end layer area on the third layer (m) side of the second layer (II). It is provided so as to occupy the layer interface and the area near the layer interface.

In the former case, the content of carbon atoms contained in the layer region (C) is relatively low in order to maintain high photosensitivity, and in the latter case, in order to strengthen the adhesion between the layers. It is desirable to have a relatively large amount. In addition, in order to achieve the former and latter objectives at the same time, it is necessary to distribute the layer in a relatively large amount on the support side and at a relatively low concentration in the layer region on the free surface side of the photoreceptive layer. What is necessary is to form region (C).

Furthermore, if the purpose is to prevent charge from entering the support or the first layer (I) and increase the apparent dark resistance, carbon may be added to the support side of the first layer (I). It is desirable that the atoms be distributed or distributed to a high degree of S at the interface and/or near the interface between the first layer (I) and the second layer (II).

In addition, in the present invention, the layer region (C) as shown in ]2.
is not limited to only one layer region (C), and a plurality of layer regions (C) may be provided in the photoreceptive layer depending on the above-mentioned purpose.

In the present invention, the content of carbon atoms contained in the layer region (C) provided in at least one of the layer (I) and the second layer (rr) of ff5l is as follows. The characteristics required of the layer region (C) itself to achieve the above objectives, and furthermore, when the layer region (C) is provided in direct contact with the support, the properties required at the contact interface with the support. The required characteristics, or if another layer region is provided in direct contact with the layer region (C), the characteristics of the other layer region and the contact 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 interface.

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

In the photoconductive member of the present invention, at least one of the layer (I) and the second layer (II) of ft51 contains a substance (C) that controls conductivity. The conductivity can be controlled as desired. The substance (C) has a first layer (I) and a second layer (II).
In at least one of the above, the content may be distributed uniformly or non-uniformly in the layer thickness direction. Further, in the layer region (PN) 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 thickness of the second layer (II) is made thicker than that of the first layer (I), so that the second layer (II) mainly functions as a charge generation layer and a charge transport layer. When used in the t31 layer (I
), the distribution is such that it increases on the support side! It is desirable to use a substance that controls transmission (C).
) is the second layer (II), the first layer (I) and ft5
It is desirable to have a distribution state in which the amount of silica is concentrated at or near the interface with layer (II) of layer 2 (II).

Examples of the substance (C) that controls conductivity include so-called impurities in the semiconductor field. Mention may be made of type impurities and n-type impurities that provide n-type conductivity properties. Specifically, the p-type impurities include atoms belonging to Group ■ of the periodic table (Group ■ atoms);
For example, there are B, AI, Ga, In, TI''S-, and B and Ga are particularly preferably used.As the n5 impurity, atoms belonging to Group V of the Periodic Table (Group V atoms) are used.
, for example, P 2 , As, Sb, Bil, etc., and P 2 and As are particularly preferably used.

In the present invention, the substance controlling conductivity (/C) contained in the layer region (PN) containing the substance controlling conductivity (G) provided in the photoreceptive layer is The content is
The conductivity properties required for the layer region (PN), or when the layer region (PM) is provided in direct contact with the support, the relationship with the properties at the contact interface with the support, etc. It can be selected as appropriate depending on the organic relationship. In addition, in the layer region (PM), a substance that governs the conductivity is added, taking into consideration the characteristics of other layer regions provided in contact with α and the characteristics of the contact interface with the other layer regions. (C) content,
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 10' atomic ppm, more preferably 0.5-LX 10' atomic ppm
pm, optimally 1-5X 103ato+a1c p
It is desirable that it be pIll.

In the present invention, the content of the substance (C) that controls conductivity in the layer region (PM) is preferably 30 atoms.
ic ppm or more, more preferably 50 atomic
ppm or more] 2. Optimally 100100ato ppm
By doing the above, 1, for example, the substance (C) is
In the case of type impurities, when the free surface of the photoreceptive layer is subjected to polar charging treatment, injection of electrons from the support side into the photoreceptor layer can be effectively prevented, and -force , when the substance (C) is the n-type impurity, when the free surface of the photoreceptive layer is charged to e polarity, the injection of holes from the support side into the photoreceptor layer is effected. can be prevented.

In the above case, the layer region (Z) excluding the layer region (PN) has a polarity different from the polarity of the substance (C) that controls conductivity contained in the layer region (PN). A substance (C) controlling conductivity of the same polarity may be contained in the layer region (PM
) is much smaller than the amount contained in 9. It may also be contained.

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
1-1000 atomic ppm, more preferably 0
．． 05~500atoi+ic ppm, @0 for suitability
．． It is desirable to set it as 1-200aLomic ppm.

In the present invention, when the layer region (PM) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the one layer region (Z) is preferably 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 in the photoreceptive layer and a conductivity having the other polarity are included. It is also possible to provide a so-called depletion layer in the contact region by providing a layer region containing a dominating substance (C) so as to be in direct contact with the layer 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 layer (I) if necessary include fluorine, chlorine, bromine, and iodine, but especially fluorine, Chlorine may be mentioned as being suitable.

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

For example, in order to form the first layer (I) composed of a-9i (H, Tono(ni, hydrogen atom()l) introduction raw material scraps and/
Or No. 5 for introducing halogen atoms (X): (Neil gas is placed in a deposition chamber whose interior can be depressurized at a predetermined ratio and gas flow rate, and then introduced into the deposition chamber. By generating a glow discharge and forming a plasma atmosphere of these gases, a first layer composed of a-Si(H,X) ( Form I).

Also, when forming by sputtering method.

For example, ^[, Si or 5i02 in an atmosphere of an inert gas such as He or a mixed gas based on these gases.
．． Alternatively, when sputtering a target layer I made of a mixture of these, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) may be introduced into the deposition chamber for sputtering.

In the final IJI, the starting material is the raw material gas used to form the first layer (I).

The following are valid:

First, the starting materials that will become the raw material scraps for supplying S1 are as follows:
S i H4,5i2H6,5i3H(1,5i4H1
Silicon hydrides (silanes) in a gaseous state such as No. 6 or which can be turned into scum can be effectively used, and Si Preferred examples include H4 and Si2H6.

Effective starting materials that serve as raw material scraps 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, SiF.

Preferred examples include silicon halides such as 5i2F 6 , 5iC14, and S+Brn, and further include 5iH7F7.5iH212, 5i87C12,
Halogen-substituted unhydrated silicon 1 such as 5IHC13°SiH2Br2 and 5iHBr3 can be in a gaseous state or can be gasified. Halides containing hydrogen atoms as one of their constituents can also be mentioned as effective starting materials for forming the first layer (I).

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

In the present invention, in addition to the above-mentioned materials, for example, fluorine, , J15, halogen gas such as bromine, iodine, CIF
, ClF3, BrF , BrF3, BrF5, IF3
Examples include interhalogen compounds such as , IF7, 101, IBr, and hydrogen halides such as IF, )ICI, HBr, and Hl.

In the present invention, when providing a layer region (G) 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 (G). 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 first layer (I) are
It may be contained in the entire area of I) without any scratches, or it may be contained only in one layer area.

Further, the distribution state C (C) of carbon atoms is the same as that in the first layer (I).
may be uniform or non-uniform in the layer thickness direction.

In the present invention; the carbon atom-containing layer region ('cr) provided in the first layer (I) is composed of photosensitive melon and IM?
When improving resistance on a 1-1 basis, the first layer (I)
When it is provided so as to occupy the entire layer area and to enhance the adhesion with the substrate and further with the second layer (II),
It is provided to occupy the end layer area of the substrate or the second layer (II) or both sides.

In this way, the layer region (cB
The content of carbon atoms in the layer region depends 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 region (CI) at the contact interface with the support. In organic relationships such as the characteristics of other layer regions provided in direct contact with (CHI) and the characteristics required at the contact interface between layer region (CI) and other layer regions, It can be selected as appropriate.

The shape of the 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 0.001-50a.
tomic%, more preferably 0.002 to 40ato
mic%, preferably 0.003 to 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 combination of raw material scraps to be used is (a) a raw material gas containing silicon atoms (Sl) as constituent atoms, a raw material gas containing carbon atoms (C) as constituent atoms, and hydrogen atoms (H) and/or as necessary. or halogen atom (X)
(b) Silicon atoms (Sl) and hydrogen atoms (H
) and a halogen atom (X)
(c) A raw material gas containing silicon atoms (Sl) as constituent atoms; a raw material gas containing carbon atoms (C) as constituent atoms; and a raw material gas containing carbon atoms (C) in a desired mixing ratio. and a raw material gas whose constituent atoms are carbon atoms (C) and hydrogen atoms (l) are mixed at a desired mixing ratio. (d) Raw material gas whose constituent atoms are silicon atoms (Sl) and silicon Atom (Si), carbon atom (C) and hydrogen B;
Combinations such as mixing and using raw material scraps having three atoms as constituent atoms with child (l()) at a desired mixing ratio can be mentioned.

Carbon atoms (
C) C is a constituent atom of the starting material that is effectively used as the raw material gas for supply.

Alternatively, C and H are constituent atoms, for example, carbon number is 1 to
5 saturated hydrocarbons, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like.

These include methane as a saturated hydrocarbon;
Examples of ethylene hydrocarbons include ethane, propane, n-butane, and pentane; examples of ethylene hydrocarbons include ethylene propylene, butene-1, butene-2, imbutylene, and pentene; examples of acetylene hydrocarbons include acetylene, methylacetylene, butyne, and the like.

In addition to these, Si (CH3)4.5i (C2Hs
)n, etc.

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 (02), ozone (03), -nitrogen oxide (NO), nitrogen dioxide (NO2), -nitrogen dioxide (N20), Nitrogen sesquioxide (N203), nitrogen tetroxide (N204), nitrogen sesquioxide (N20S), nitrogen trioxide (N03), silicon atom (Si), oxygen atom (0), and hydrogen atom (H) as constituent atoms For example, disiloxane (N3SiO9iH3), disiloxane (N3S
Examples include lower siloxanes such as ITS 1H20S 1H3).

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 (N)1
3), hydrazine (82NNH2), hydrogen acyde (H
N3), ammonium aceide (NH4N3)?
(7) Nitrogen in the form of scum or which can be gasified;
Mention may be made of nitrogen compounds such as nitrides and azides. In addition, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (
Examples include halogenated nitrogen compounds such as nitrogen tetrafluoride (F3N) and nitrogen tetrafluoride (F4N2).

When forming the first layer (I) containing carbon atoms by a sputtering method, single crystal or polycrystal S
This may be carried out by sputtering an i-wafer and/or a C-wafer-1 or a wafer containing a mixture of Si and C in various gas atmospheres using the targets.

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

Alternatively, when using Sl and C as separate targets, or when using Si and C as a mixed target, it is possible to use a diluting gas atmosphere as a spunter gas. 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 (CI), for example, a group Ⅰ atom or a group V atom, during the formation of one layer.

The starting material for use in Part II or the starting material for use in Part V 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 such m-th release, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

Specifically, as a starting material for use in the first part (1), for introducing a boron atom.

B2H6・O4HIo, Bs N9・BSH eyes・
Examples include boron hydrides such as B6HIO, B6HI2, and 86H14, and boron halides such as BF3, BC:I3, and BBr3. In addition to this, other materials used in Part 1: AlCl3, GaCl3, Ga(
Examples include CH3)3, InCl3, TlCl3, and the like.

In the present invention, PH3 is effectively used as a starting material for the introduction of phosphorus atoms in Part V Atsushi Chihiro.
, P2O, etc., phosphorus hydride, P)1.1, PF3,
PFs, PCl3, PCI5, PB3, PBr3,
Examples include phosphorus halides such as PI3. In addition, A
sH3, AsF3, AsCl3, AsBr3,
AsF5, SbH3, SbF3.5bFS, 5bC13
, SM:ls, BiH3, BiCl3, B1B
r3 and the like can also be mentioned as effective starting materials for use in Part V Atsushi Chihiro.

In the present invention, the content of the substance (C) controlling the conductivity contained in the first layer C1,) is the same as that of the layer (II) of the f51.
), or the characteristics of other layers provided in direct contact with the layer (I), or the relationship with the characteristics of the contact interface between the layer (I) and other organic relationships. The ball is selected appropriately.

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

In the present invention, the amount of hydrogen atoms (H) that may be contained in the layer (I) of il, the amount of /\rogen atoms (X), or the sum of the amounts of hydrogen atoms and /\roken atoms ( ) IIX) is
Preferably l-41-40ato%, more preferably 5
It is desirable that the content be 30 atomic%.

Hydrogen atoms ()l) that may be contained in the first layer (I)
And/or to control the amount of halogen atom (X), for example, the support temperature, hydrogen atom (H) and/\\halogen atom (X
), the amount of the starting material introduced into the deposition system, the discharge power, etc. may be controlled.

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

In the case of 1111 people, preferably 1000 to 50 pieces, more preferably 2000 to 30 pieces, optimally 200 pieces.
It is desirable that the number of tiles is 0A-10. In the latter case, the number of scales is preferably 1 to 100 u, more preferably 1 to 80 scales, and optimally 2 to 50 scales.

In the photoconductive member of the present invention, the first layer (I) 103
Second, a second layer (II) 104 containing silicon atoms and germanium atoms is formed.

Since the first layer (I) and the second layer (II) are each mainly composed of an amorphous material having a common constituent atom, silicon atoms, chemical sufficient stability is ensured.

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 (II) and the third layer (m) or between the first layer (I), the second W# (II), and the third layer (m).
) preferably contains nitrogen atoms.

The nitrogen atoms contained in the second layer (II) may be contained in the entire area of the second layer (II) without any scratches, or may be contained only in one layer area.

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

In the present invention, the nitrogen atom-containing layer region (N11) provided in the second layer (II) is not included in the second layer (II) when the purpose is to improve photosensitivity and dark resistance. H) Provided to occupy the entire layer area and with the first JH (I),
and/or to strengthen the adhesion with the third layer (Ill), the first layer (I) and/or the third layer (m
) is provided so as to occupy the end layer area on the side.

In this way, the layer region (N) provided in the second layer (n)
The content of nitrogen atoms contained in il) depends on the characteristics required of the layer region (N11) itself, the first layer (1) and the third layer (m) in order to achieve the above-mentioned purpose. properties required at the contact interface with the first layer (I)
or the third layer (m) can be appropriately selected depending on the organic relationship with the characteristics of Fyi.

The amount of nitrogen atoms contained in the layer region (NII) is determined as desired depending on the characteristics required of the photoconductive member to be formed, but is preferably.

0.001-50 atomicX, more preferably 0
．． 002-40atomrcL Optimally 0.003~
30 a, tomicl is preferable.

In the photoconductive member of the present invention, when the first layer (1) is thin, the second layer (II) containing germanium atoms contains a substance (C) that controls conductivity. ) can be made to function as a so-called charge injection blocking layer by locally extending the layer region (PN) containing a layer (PN) on the first layer (, I) side.

That is, the content of the substance (C) that controls conductivity in the layer region (PN) containing the substance (C) is preferably 3.
0 atomic ppm or more, more preferably 50 at
omic ppm or more, optimally 100100at
o ppm or more, for example, if the contained substance CC) is the above p-type impurity, when the free surface of the photoreceptive layer is subjected to the polar charging treatment, 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 (Zll) of ft52 W(II) excluding the layer region (PN), there is a layer region (Zll) that controls the conductivity contained in the layer region (PN). A substance (C) that governs conductivity different from the polarity of the substance (C) may be contained, or the amount of a substance (C) that governs conductivity of the same polarity contained in the layer region (PN). It may be contained in a much smaller amount.

In such a case, the content of the substance (C) controlling the conductivity contained in the layer region (ZII) depends on the polarity and content of the substance (C) contained in the first layer region (PN). Although it is determined as appropriate depending on the amount, preferably 0.
001-1000 atomic ppm, more preferably 0.05-500 atomic ppm, optimally 0
- Desirably 1 to 200 atomic ppm.

In the present invention, when the layer region (PM) and the layer region (Zll) provided in the second layer (II) contain the same kind of substance (C) that controls conductivity, the layer region (
the substance (C) that controls the conductivity contained in zrr)
The content is preferably 30 atomic ppm
The following is desirable. 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, in the second layer (II), the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided so as to be in direct contact with each other. forming a p-n junction,
A depletion layer can be provided.

In 1JI, the content of germanium atoms contained in the second layer (II) is 1. Although the content of germanium atoms contained in the second layer (II) is determined as desired so as to effectively achieve the object of the present invention, silicon atoms Preferably for the sum of 1 to 9.
Desirably, the amount is 5X 10' atomic ppm, more preferably 100-8X 10S105ato ppm, optimally 500-7X 10'' atomic ppm.

In the present invention, specific examples of the halogen atom (X) contained in the second layer (!■) 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-9iGe (H, A vacuum deposition method is applied.

For example, by glow discharge method, a-5iGe(H,X)
In order to form the second layer (II), basically, a raw material gas such as Si, which can supply silicon atoms (Sl), and G, which can supply germanium atoms (Ge), are used.
e Source gas for supply and hydrogen atoms ()l) as necessary
A raw material gas for introduction and/or a raw material gas for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be depressurized at a predetermined mixing ratio and gas flow rate, and a gummy gas is introduced into the deposition chamber. By causing electrical dispersion and forming a plasma atmosphere of these gases, a-3iGe (H, The second layer (I
I).

In addition, when forming by sputtering method, for example, A
A target made of Si, two targets made of Si and a target made of Ge, or a target made of Si and Ge in an atmosphere of an inert gas such as T, He, or a mixed gas based on these residues. Using a target mixed with , a source gas for supplying Ge diluted with a diluent gas such as Ar or )le as necessary, a source gas for introducing hydrogen atoms (H) and / Alternatively, a raw material gas for introducing halogen atoms (X) may be introduced into a deposition chamber for sputtering, a desired gas plasma atmosphere may be formed, and the target may be sputtered.

In the case of the ion blating 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 these evaporation sources are used by resistance heating method or 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 that serve as raw material residues used to form the second layer (11).

First, the starting materials that will become the raw material gas for supplying Si are as follows:
SiH4, 5i2H6, 5i31 (B, Sii+H
Silicon hydride in a gaseous state or gasifiable such as lo
Silanes) can be effectively used as raw material gases for mGe supply, with SiH4 and Si2H6 being particularly preferred in terms of ease of layer creation work and good S1 supply efficiency. As a starting material, G
eH4, Ge7H6, Ge3HB, Ge4H1゜, G
e5H+2, Ge6H14, Ge7H16, Ge6Ht
GeH4, Ge2H6, Ge3HB is preferred.

In the present invention, many halogen compounds can be cited as effective starting materials that serve as raw material gases for introducing halogen atoms (X) used to form the second layer (■!). Preferred examples include halogen compounds in a scum state or that can be gasified, such as halogen scum, saponified halides, interhalogen compounds, and halogen-substituted silane derivatives.Furthermore, halogen compounds containing silicon atoms and halogen atoms as constituent elements are preferably mentioned. Silicon hydrides containing gaseous or gasifiable halogen atoms may also be used with advantage.

In the present invention, the second! Specifically, halogen compounds suitably used for forming 1) include halogen residues such as fluorine, chlorine, bromine, and iodine, CIF, C
IF3, BrF, BrF3, BrF5, IF3,
Examples include interhalogen compounds such as 1F7, 1CI, and IBr.

Specifically, silicon compounds containing a halogen atom ('X), so-called silane derivatives substituted with a halogen atom, include SiF4.5i2F 6 , 5iC14, SiBr4
Preferred examples include silicon halides such as the following.

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, A layer (II) can be formed.

According to the glow discharge method, the second one containing a halogen atom (X)
When forming a calendar (n) of, for example, Si
/\silicon halogenide, which will be the raw material gas for supply, and germanium hydride, which will be the raw material gas for Ge supply, A ", H
A gas such as e is introduced at a predetermined mixing ratio and gas flow rate into a deposition chamber where the second layer (If) is formed, and a glow discharge is generated to generate plasma of these dregs. By forming an atmosphere, a layer (H) of ft52 can be formed on the support on which the first layer (I) is formed. In addition, in order to more easily control the introduction ratio of hydrogen atoms, hydrogen scum or a silicon compound gas containing hydrogen atoms may be added to the desired Mtm.
They may be combined to form the second layer (II). Moreover, each gas may be used not only as a single species but also as a plurality of them at a predetermined mixing ratio.

In both the sputtering method and the ion blasting method, in order to introduce I\halogen atoms (X) into the formed layer, a gas of the above-mentioned l\halogenide or silicon compound containing halogen atoms is deposited. What is necessary is to introduce the waste into the chamber and form a plasma atmosphere of the residue.

In addition, when introducing hydrogen atoms, a gas for introducing hydrogen atoms, such as H2, or the above-mentioned silanes and/or germanium hydride, etc., is introduced into the deposition chamber for sputtering, and the 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 nitrogen gas for introducing halogen atoms when forming the second layer (II). , In addition, HF, I[l,
HBr, HI, etc. (7) Hydrogen halide, SiH
2F2, 5N421+, 5iH2C17, 5iHC
13, 5i) 12Br2, SiH2Br, 5iHB
Halogen-substituted silicon hydrides such as r3, and GeHF3
, GeHCl3, GeH3F, GeHCl3,
Halides containing hydrogen atoms as one of their constituent elements, such as germanium hydrogenated halides such as GeH2Cl7, GeHCl3, GeHI3, GeH212, and GeH3I, GeF4. GeC1a,
GeBr4, Ge14, GeF4, GeC12, G
eBr2, GeI2, etc. (7) Germanium halides, etc., which are in a cassate state or can be cassified, and have a hydrogen atom as one of their constituents are also effective ff5.
2 as a starting material for the formation of layer (II).

- Among these substances, halides containing hydrogen atoms are extremely effective for controlling electrical or photoconductive properties at the same time as introducing halogen atoms into the second layer (II) when forming the second layer (II). Since hydrogen atoms can also be introduced, it is used as a suitable raw material for introducing halogen atoms in the present invention.

In order to structurally introduce hydrogen atoms into the second layer (II), in addition to J2, H2 or SiH4,5i2H (,
, 5i3HB, 5i4Hro etc.
with germanium or germanium compounds for supplying e, or with G e H4, Ge2H6, Ge3H
13, Ge4H+o.

Ge5H12, Ge6H14, Ge71-116,
It can also be carried out by causing germanium hydride such as Ge3H13 and silicon to coexist in the deposition chamber with silicon or a silicon compound for supplying Si, and causing a discharge.

In a preferred example of the present invention, hydrogen atoms (H
), 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 0.05-30a
atomic%, preferably 0.1-25 atomic%.

Hydrogen atoms that may be contained in the layer (II)' of WS2 (
To control the amount of I() and/or halogen atoms (X), for example, the temperature of the support, the deposition system of the starting material used to contain the hydrogen atoms (I) and the halogen atoms (X) What is necessary is to control the amount introduced into the battery, the discharge power, etc.

In the second layer (II), 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), when forming the first layer, the above-mentioned method ② The starting material used or the starting material used for the V release process can be introduced in gaseous form into the deposition chamber together with the other starting materials for forming the second layer 1).

The layer thickness of the second layer (n) 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 second layer (n) is It is determined as appropriate in consideration of the absorption coefficient of layer (II), preferably 100 OA to 50 OA, more preferably 1000 OA to 30 OA, most preferably 1OO
It is desirable that the number of tiles is oA~20. In addition, the second layer (
When II) is mainly used as a layer for generating and transporting photocarriers, it is appropriately determined depending on the needs so that photocarriers can be transported efficiently, and preferably 1.
~100u, more preferably 1~80u, optimally 2~
It is desirable that the thickness be 50μ.

In the present invention, in order to provide the layer region (CII) containing carbon atoms in the second layer (II), carbon atoms must be introduced during the formation of the second layer (II) as described above. The layer region containing carbon atoms is formed in the same manner as for forming the layer region containing carbon atoms in the first layer (I), except that the starting materials for forming the second layer (II) are used together with the starting materials 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 coated.

In the present invention, when forming the layer (I) and the second layer (II) of f:iSl, a layer region (C) containing carbon atoms is provided in at least one of these layers. ,
The distribution concentration C (C
) in the layer thickness direction to obtain a desired depth profile in the layer thickness direction, in the case of the glow discharge method, the distribution concentration C (C) must be changed in order to obtain the desired depth profile. It is possible to apply a method of forming these layers by introducing a gas consisting of a starting material into the deposition chamber while changing its flow rate appropriately according to a desired rate of change curve.

In the case of sputtering, for example, when a mixture of Sl and Si3N is used as the tarcerate for sputtering, the mixing ratio of Si and Si3N4 is changed in advance in the thickness direction of the tarcerate. By doing so, a desired carbon atom distribution in the layer thickness direction of 7g (depth profile) can be obtained.

The third layer (m) io5 formed on the second layer (11) 104 of the photoconductive member of the present invention has a free surface and is mainly characterized by its temperature resistance, continuous repeated use characteristics, and electrical breakdown voltage. This is provided to achieve the objectives of the present invention in terms of performance, use environment characteristics, and durability. The second layer ('II) and the third layer (m) are each mainly composed of an amorphous material having a common constituent atom, silicon atoms, so that at the laminated interface, Sufficient chemical stability is ensured.

The third layer (m) in the present invention consists of silicon atoms (Si
), oxygen atom (0), and optionally hydrogen atom ()I)
and/or a material whose main component is amorphous containing a halogen atom (X) (hereinafter a-(Six O+ -x)y
() I, X) + - A, however, 0 < x, !
<1).

a-(Si, 0.-x), (H,X) 1-,
The third layer (m) is formed by a glow discharge method, a sputtering method, an ion implantation method,
This is carried out by ion blating method, electron beam method, 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. The third layer (which is relatively easy to control the conditions for producing the conductive member and which contains oxygen atoms and halogen atoms together with silicon atoms)
m) The claw discharge method or the sputtering method is preferably employed because of the advantages such as ease of introduction into the material. 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-(Six O+ -x)y (H,X) +-y
The raw material gas for formation 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. Then, the introduced gas is turned into gas plasma by causing a glow discharge, and a-(Stxo, -X)y (H,X)ry is deposited on the second layer (II) on the support. All you have to do is deposit it.

In the present invention, a-(StxO+-x)y(H, XL
b for -v formation: (As the raw material, silicon atoms (S
i) A gasified substance containing a scum-like substance containing at least one of a sulfur atom (0), a hydrogen atom (H), and a halogen atom (X) as a constituent atom or a substance that can be gasified Most can be used.

When using a JJI gas containing Si as one of Si, 0, H, and X, for example,
A desired mixing ratio of a raw material gas containing Si as a constituent atom, a raw material gas containing 0 as a constituent atom, and a raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent IO & atom as necessary Alternatively, a raw material gas containing Sl as a constituent atom and a raw material gas containing 0 and H as constituent atoms and/or a raw material gas containing 0 and X as constituent atoms at a desired mixing ratio. Mixed use or alternatively Si
B'xC raw material gas with constituent atoms and three of Si, 0 and H;
There is an example in which a raw material gas having three constituent atoms is mixed at a desired mixing ratio and used.

Alternatively, as a thin shape, a raw material gas consisting of Sl and H; You may mix and use the raw material gas which has 0 as a constituent atom, and the raw material gas which has 0 as a constituent atom.

In the present invention, suitable halogen atoms (X) that may be contained in the third layer (m) are F, C1,
Br, IT, and F and CI are particularly desirable.

In the present invention, the starting material serving as the raw material gas for forming the third layer (m) is S containing Si and H as constituent atoms.
Gaseous or cassifiable silicon hydrides (silanes) such as i H4, 5i7H6, 5i3HB, and 5i4H1° can be used effectively, especially for ease of handling in layer creation work and improvement of Si supply efficiency. S in terms of quality etc.
Preferred examples include iH4 and Si2H6.

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 containing a halogen atom (X), a surface compound, a so-called halogen atom-substituted silane derivative, specifically, for example, SiF4.5i7F 6 ,
Preferred examples include silicon halides such as S+CI4.5rBr, I, and moreover, SiH
2F2.5iH212, 5iH2C1□, 5i) ICh
, SiH2Br2, halogen-substituted silicon hydrides such as 5iHBr, and other gaseous or halogenated halides containing a hydrogen atom as one of the constituent elements, such as gaseous 71, are also effective starting materials for forming the third layer (m). It can be mentioned as.

Even when using silicon compounds containing these halogen atoms (X), the halogen atoms (× ) can be introduced.

In the present invention, effective starting materials that serve as the 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, C
IF3, BrF, BrF3, BrF51F3.1F
Interhalogen compounds such as 7, 1CI, and IBr.

Examples include hydrogen halides such as HF, HC:l, )lBr, and Hl.

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 (m) include those having 0 as a constituent atom; Or O and H are constituent atoms, for example oxygen (02),
Oson (C3), -nitric oxide (NO), nitrogen dioxide (8
02),=,nitric oxide (N20), nitric oxide (N20),
203), nitrogen tetroxide (N204), l: nitrogen oxide (
N20S), nitrogen trioxide (NO3), silicon atoms (
Si), oxygen atom (0), and hydrogen atom (H) as constituent atoms, for example, disiloxane (H3SiOSiH3),
Examples include lower siloxanes such as trisiloxane (H3SiOSiH20SiH3).

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

In order to form the third N(m) by the sputtering method, the following method can be adopted, for example.

The first method is to use a raw material gas for introducing oxygen atoms (0) when sputtering a target composed of 81 in an atmosphere of an inert gas such as Ar or He or a mixed gas containing these gases. , optionally hydrogen atoms (
H) It may be introduced into a deposition chamber in which sputtering is performed together with a raw material gas for introduction and/or for introduction of halogen atoms (X).

In addition, in the second method, as a sputtering target, a target made of Sl, a target made of Sl and a target made of 5i02, or a target made of Si and 5i02 is used. By using , oxygen atoms (0) can be introduced into the third layer (■). At this time, if the raw material waste for introducing oxygen atoms (0) described above 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.

0, H, and
) Forming substances can also be used as effective substances in the case of sputtering methods.

In the present invention, as the diluting gas used when forming the third layer (m) by the claw discharge method or the sputtering method, so-called box dregs, such as He, Ne, Ar, etc., are preferably mentioned. be able to.

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

In other words, substances whose constituent atoms are Si, 0, H and/or In the present invention, a- (Six o, 4)y (H,
X) The selection of the formation conditions is made strictly as desired so that ly is formed. For example, the third! (
m) with the main purpose of improving electrical voltage resistance, a-(Sillo, -X)y (H,X)
ry is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, if a third layer (m) is provided for the main purpose of improving the characteristics of continuous use and the environment of use, the degree of electrical insulation described above will be relaxed to some extent, and the degree of electrical insulation will be reduced to a certain extent with respect to the irradiated light. As an amorphous material with a sensitivity of
(Six o, -X)y 1-y (in Hl) is created.

On the surface of the second layer (II) a-(StXO,-1
1) When forming the third layer (m) consisting of y (l(, In the present invention, a-(Si, 1
It is desirable that the temperature of the support during layer formation be tightly controlled so that O1-x)y(H,X)l-v can be formed as desired.

In the present invention, the formation of the third layer (III) 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. However,
Preferably 20-400°C, more preferably 50-35°C
The formation of the third layer (II[), which is preferably at 0°C, optimally at 100-300''C, requires delicate control of the composition ratio of the atoms that make up the layer compared to other methods. Glow discharge method and sputter link method are advantageous due to their relative ease, but when forming the second layer using these layer forming methods, the above-mentioned support temperature and Similarly, the discharge power during layer formation is created a−(S+xO+ −X
)y (H,

a-(Six O+ -x)y ()1. X
) The discharge power conditions for effectively creating ry with high 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 to I
Torr, preferably about 0.1 to 0.5 Torr.

In the present invention, the above-mentioned values are listed as the preferable numerical ranges for the support temperature and discharge power for creating the third layer (m), but these layer creation factors can be determined independently. a of the desired characteristic, rather than one that can be determined separately.
The optimal value of each layer creation factor is determined based on the mutual organic relationship so that the third layer (■) consisting of -(S record 0+ -x )y (HlX)+-7 is formed. desirable.

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

That is, the general formula a-(StXo, -X)y (H
,
From then on.

It is written as a-5iaOI-a. However, 0 < a < 1)
, an amorphous material composed of silicon atoms, oxygen atoms, and hydrogen atoms (hereinafter, a-'(Sjbo, -b)e
It is written as Hl-e. however.

0 < b, c < 1), an amorphous material composed of silicon atoms, oxygen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter a-(Sia o, -, i) e
(H,X) written as ra, provided that 0 < d,
e < 1).

In the present invention, the third W (m) is a-5ilo 1
- When composed of @, the amount of oxygen atoms contained in the third layer (III, ) is such that a is preferably 0.33 to 0
,．． 99999, more preferably 0.5 to 0.99, optimally 0.6 to 0-9.

On the other hand, in the present invention, the third layer (m) is a-(Si,
, o, -b) c H+-0, the amount of oxygen atoms contained in the third layer (III) is such that b is preferably 0.33 to 0.9111199, more preferably 0. .5 to 0.88, optimally 0.6 to O, S, C, preferably 0.8 to 0.99, more preferably 0.85 to 0.
98, optimally 0.7 to 0.95.

4 The third layer (m) is a-(Sia o, +l).

When composed of (H,X)+-0, the MS3 layer (
As for the content of oxygen atoms contained in m), d is preferably 0.33 to 8.999119, more preferably 0.5 to 0.91+, and optimally 0.6 to 0. .8, e is preferably 0.8 to 0.99, more preferably 0.82 to 0
．． 99, optimally 0.85 to 0.88.

Further, the amount of hydrogen atoms (H) is preferably 9° atomic% or less, more preferably 80 atomic% or less, based on the sum ()I+X) of halogen atoms (X) and hydrogen atoms (H).
% or less, preferably 70 atomic% or less.

The numerical range of the layer thickness of the third layer (III) in the present invention is one of the important factors for effectively achieving the object of the present invention. To effectively achieve the objectives of the present invention,
It can be determined as desired depending on the intended purpose.

In addition, the layer thickness of the third layer (m) is determined by the amount of oxygen atoms contained in the third layer (m) and the layer thickness of the first layer (1) and the second layer (II). The relationship between the two layers 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 tiles, more preferably 0.004 to 2
0u, optimally 0.005-10. It is desirable that this is the case.

The support 101 used in the present invention includes t4
It may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, and A! ,Or,
No, Au, Wb, 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.

That is, for example, if it is glass, NiC is applied to the surface of the glass.
r, A1. Cr, No, Au, Ir, lid, T
a, V, Ti, Pt, In2O3, 5n02, I
Conductivity is imparted by providing a thin film made of In2O3+ 5n02, etc., or if it is a synthetic resin film such as polyester film, N1cr
, A1. Ag, 'Pb, Zn, old, Au, Cr
, Mo, Ir, Wb, 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 laminating the surface with the metal.

The shape of the support body is determined depending on the need, but for example, the shape of the support body is determined as desired. If the photoconductive member 100 of :i is used as an electrophotographic image forming member, in the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape, and the thickness of the support can be adjusted as desired. However, if flexibility is required as a photoconductive member, the thickness of the photoconductive member is determined as appropriate so that the photoconductive member can be formed as thinly as possible within a range that can sufficiently exhibit its function as a support. be done. However, in such cases, in manufacturing and handling of the support,
Furthermore, from the point of view of mechanical strength, etc., it is usually set to IOμ or more.

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

FIG. 2 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method.

In the gas cylinders 11Q2 to ttoe in the figure, raw material gas for forming the photoconductive layer of the photoconductive member of the present invention is sealed.
Diluted SiH4 gas (purity! 99.999%, hereinafter abbreviated as SiH4/He gas) cylinder, 1103
GeF4 gas diluted with Hete (purity 98.989%)
, hereinafter abbreviated as GeF4/)Ie cassette) cylinder, 11
04 is B10.04 diluted with He. Gas (purity 911.9
89%, hereinafter abbreviated as B2 H6/He gas) cylinder,
+105 is C2H4 gas (purity ss, ss%) cylinder,
1106 is a He gas (purity 99..!19%) cylinder.

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

To flow these gases into the reaction chamber 1101.

Gas Pombe 1102~! Confirm that each of the valves 1122 to port 2B and the leak valve 1135 of 106 are closed, and also check that the inflow valves 1112 to 111θ, the outflow valves 1117 to 1121, and the auxiliary valves 1132.11
Make sure that 33 is open, and then open the main valve first! 134 is opened to exhaust the reaction chamber 1101 and each gas pipe. 6. Next, the reading on the vacuum gauge 1136 is approximately 5X 10"
When it becomes torr, auxiliary valve 1132.1133
and close the outflow valves 1117-1121.

First, an example of forming the first layer (I) on the cylindrical substrate 1137 is shown.
)16/)He gas, C2 from gas pump 1105
Open the He gas valves 1122, 1124, and 1125, respectively, and check the outlet pressure gauges 1127, 1129, and 113.
0 pressure to IKg/c intestine 2, inflow valve 1112
．． 1114. Gradually open +115 and mass flow controller 110? , 1108, and 111G, respectively. Subsequently the outflow valve 1117.1119.1
120 and auxiliary valve +132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101.

At this time, the outflow valve 111 is adjusted so that the ratio of S iH4/He gas flow rate, C2H4 gas flow rate, and 82H6/He gas flow rate becomes a desired value. , li 1119.1120
I! ! ! Then, while checking the reading on the vacuum gauge 1138, adjust the main valve 11 so that the pressure inside the reaction chamber reaches the desired value.
Adjust the aperture of 34. and the base cylinder 1137
After confirming that the temperature of
140 to a desired power to generate a glow discharge in the reaction chamber 1101, the first
Form layer (I). In addition, during layer formation, a base cylinder 1137 is used to ensure uniform formation of one layer.
is rotated at a constant speed by a motor 1139. Close all the gas operation system valves used last, reaction chamber 1!
O1 is once evacuated to high vacuum.

Next, to show an example of forming the second layer (II) on the first layer (L) formed in this way, when the reading of the vacuum gauge 1136 becomes approximately 5X 10' torr, Repeat the same operations as above.

That is, S+H4/He gas from the gas pump 1102, GeF4/He gas from the gas pump 1103, B2 H6/)le gas from the gas cylinder 1104, and C2H4 gas from the gas cylinder 1105 through the valve 1122.1.
123, 1124, and 1125, respectively, and check the pressure on the outlet pressure gauges 1127, 1128, 1129, and 1130.
Adjust to Kg/c+a2, inlet valve 1112.111
3. Gradually open 1114 and ux5 to flow into the mass controllers 1107, 1108, 1108, and 1110, respectively. Subsequently, the outflow valve 1117, l
118.111s, 1120, and the auxiliary valve 1132 are gradually opened to allow the respective dregs to flow into the reaction chamber 1101. At this time, SiH4/He gas flow rate and GeF4/
He waste flow rate and B2 H6/ He waste flow rate and C7H
Outflow valve +1 so that the ratio with 4 swords is 9I
17.1118, +1119.1120, and vacuum gauge 113 so that the pressure in one reaction chamber reaches the desired value.
Adjust the opening of the main valve 1134 while checking the reading of 6. 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 syringe 1137 in the same manner as in the case of forming the first layer (I).

Next, the second layer (II) formed in this way.
- When forming the layer (III) of ¥Jj3 on
When the reading of 313 becomes approximately 5X 10” torr,
In the same manner as in the above case, for example, SiH4/He scum is supplied from the gas cylinder 1102 and NO scum is supplied from the gas cylinder 1108 to generate glow discharge and form the third layer (III
) is formed into a roux. The amount of oxygen atoms in the third layer (III) is N
Controlled by adjusting the O gas supply meteor.

Examples will be described below.

Example 1 Using the photoconductive member manufacturing apparatus shown in FIG. 2, a photoreceptive layer was formed on a cylinder made of ^I according to the manufacturing conditions shown in Table 1 by the glow radiation decomposition method described in detail above. Each sample of an image forming member for electrophotography (Samples 1-1 to 16-10)
)It was created.

Figures fjS3A and 3B show the distribution state of boron atoms contained in the layer region consisting of the first layer CI) and the second layer (II) in the photoreceptive layer in each sample, and further show the distribution of carbon atoms. The distribution state is shown in Figure 4.

Such a distribution of boron atoms and carbon atoms can be achieved by automatically controlling the opening/closing states of the corresponding valves according to a predetermined gas flow rate change curve.6. H6 and N
It was formed by adjusting the gas flow rate of H3. The distribution of boron atoms and carbon atoms in each sample is shown in Table 3.

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 e see was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the photoconductive member surface by cascading a θ-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 co-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 a GaAs-based semiconductor laser (loin) of
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 high quality image with good one-tone reproducibility was obtained.

Example 2 Using the manufacturing apparatus shown in FIG. 2, an electrophotographic image forming member was produced on a shilling-shaped At substrate in the same manner as in Example 1 except that the manufacturing conditions shown in Table 2 were changed. Each sample (sample 21
-1 to 2B-9) were produced.

The first layer (I
) and the second layer (II) are shown in FIG. 5, and the distribution of carbon atoms is shown in Pt56. The distribution of boron atoms and carbon atoms in each sample is shown in Table 4.

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 Each of Example 1 was performed using the manufacturing apparatus shown in FIG. 2, except that the conditions for creating the third layer (m) were as shown in Table 5.
Samples 5-5 and 14-10 as well as the sample of Example 2,
16. Electrophotographic imaging members (sample positives 5-5-1 to 5-5
-8, 14-10-1-14-10-8, 25-3
-1 to 25-3-8) were prepared, respectively.

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

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

Example 4 The third layer (III) was manufactured by a sputtering method, and the target area ratio of the silicon wafer and the 5i02 wafer was variously changed during the formation.
A photoreceptive layer was formed on a cylindrical AI substrate in the same manner as Sample 8-9 in Example 1, except that the content ratio of silicon atoms and oxygen atoms in [l) was changed, and electrophotography was performed. Image forming members (a total of 7 pieces, sample notifications 8-8-1 to B-9-7) were prepared.

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 When forming the third layer (III), SiH4 gas and NOO
20 on a cylindrical A1 substrate in exactly the same manner as Sample A3-8 of Example 1, except that the content ratio of silicon atoms and oxygen atoms in the m3 layer (m) was changed by changing the flow rate ratio. A photoreceptive layer was formed on the sample to prepare image forming members for electrophotography (a total of 7 samples Nos. 8-9-11 to 8-9-17).

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), 5i) 14 gas and SiF4
The third layer (III) was formed by changing the flow rate ratio of gas and NO scum.
A cylindrical AI-made specimen was prepared in exactly the same manner as Sample Sui 8-9 of Example 1, except that the content ratio of silicon atoms and oxygen atoms was changed. Photographic image forming members (samples! 7 ILs of 8-9-21 to 8-9-27) were prepared.

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 shilling-shaped A1 substrate in the same manner as Sample 8-8 of Example 1 except that the layer thickness of the third R (m) was changed. Image forming members for electrophotography (samples, a total of four pieces /L8-9-31 to 8-9-34) were prepared.

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 embodiments are shown below.

When forming the first and third layers of support body melon: Approximately 250°C When forming the second layer: Approximately 200°C Discharge frequency: 13.58 MHz Reaction chamber pressure during reaction: 0.3 Torr Table 10

[Brief explanation of drawings]

Fig. 1 is a diagram schematically showing the layer structure for explaining the structure of the photoconductive member of the present invention, Fig. 2 is a diagram showing an apparatus for manufacturing a photoconductive member by glow discharge decomposition method, and Fig. 3A. and FIG. 3B is a diagram showing the distribution state of boron atoms in the photoreceptive layer of the photoconductive member prepared in Example 1 of the present invention,
FIG. 4 is a diagram showing the distribution state of carbon atoms in the photoreceptive layer of the photoconductive member prepared in Example 1 of the present invention;
FIG. 5 is a diagram showing the distribution state of boron atoms in the photoreceptive layer of the photoconductive member prepared in Example 2 of the present invention;
FIG. 6 is a diagram showing the distribution of IR atoms in the photoreceptive layer of the photoconductive member produced in Example 2 of the present invention. 100: Photoconductive member 101: Support 102: Photoreceptor #103: First layer 104: Second layer 105: Third layer +101: Reaction chambers 1102-1108: Gas cylinders 1107-till: Mass flow controller 1] 12
~11+8: Inflow valve 1117~+12]: Outflow valve 1122~1128, /Help 1127~1131: Pressure regulator 1132: Ni auxiliary valve 1133: Main valve 11
34: Kate valve 1135/leak valve 1ia
e: Vacuum gauge 1137: Base cylinder 1138:
Heater 113! It: Motor +140: High frequency power supply (matching box) Patent applicant Canon Co., Ltd. (301) (302) (303) (304) (a
(305) (306) (307) (308) Figure 5

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 photoconductive properties, the photoreceptor layer is formed 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. (!I) and a third layer (m) made of an amorphous material containing silicon atoms and oxygen atoms, the first layer (I) and the second layer (1
A photoconductive member characterized in that at least one of 1) contains carbon atoms. (2) The first layer (I) and the second layer (II')
2. The photoconductive member according to claim 1, wherein at least one of the photoconductive members contains a hydrogen atom and/or a halogen atom. (3) Layer (I) and second layer (II) of tf'sl
3. The photoconductive member according to claim 1, wherein at least one of the photoconductive members 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.