JPS59197044A - Photoconductive member - Google Patents

Abstract

PURPOSE:To increase the sensitivity in the whole visible light region by forming the 1st layer of a specified amorphous material, the 2nd photoconductive layer contg. Si, and the 3rd layer of an amorphous material contg. Si and C on a support. CONSTITUTION:The 1st layered region 103 made of an amorphous material contg. GexSi1-x (0.95<x<=1) and the 2nd layered region 104 showing photoconductivity and made of an amorphous material contg. Si are formed on a support 101 for a photoconductive member. Ge contained in the amorphous material of the region 103 is distributed uniformly and continuously in the direction of the thickness and in the plane direction parallel to the surface of the support 101. The 3rd layered region 106 made of an amorphous material contg. Si and C or further contg. H and halogen is then laminated on the region 104. The preferred thickness of the region 103 is 30Angstrom -50mum, that of the region 104 is 0.5-9mum, and the preferred total thickness of the regions 103, 104 is 1-100mum. The preferred thickness of the region 106 is 0.003-30mum.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.). As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/dark current (Id)], has absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and is non-polluting to the human body during use. The solid-state imaging device is required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member that is incorporated into an electrophotographic apparatus used on a business machine in an office, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

In addition, a photoconductive member having a photoconductive layer composed of conventional a-8i has good electrical, optical, and photoconductive properties such as dark resistance value, photosensitivity, and photoresponsiveness, as well as moisture resistance, etc. The reality is that there is a need for further improvement in terms of the use environment characteristics of Niji, and the stability over time of Niji, which requires comprehensive improvement of the characteristics.

For example, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases, the reflectance of the support itself to the light transmitted through the photoconductive layer will decrease. When it is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of 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 a-8i material, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the light guide layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties or electrical withstand voltage of the formed layer.

That is, for example, the lifetime of the photocarriers generated by light irradiation in the formed light guide layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in the dark area, or There may be image defects commonly called "white spots" on the image that has been transferred to the transfer paper, which are thought to be caused by a localized phenomenon of radiation destruction, or, for example, due to cleaning.
When using a blade, it seems to be caused by the friction, which is commonly known as "
A so-called image defect called "white stripe" occurred. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs.

Therefore, while efforts are being made to improve the properties of the a-8i material itself, it is necessary to take measures to solve the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above-mentioned points, and has the applicability and applicability of a-8i as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from various viewpoints, aS'
In particular, an amorphous material having a silicon atom as its base material and containing at least either 0 hydrogen atoms or a halogen atom (3), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as [a-8i(H2N)] is used as a generic notation for these, and the layer structure of a photoconductive member having a photoreceptive layer exhibiting photoconductivity is specified as explained hereinafter. The photoconductive materials designed and manufactured under this system not only have extremely superior properties in practical use, but also exceed conventional photoconductive materials in every respect, especially when used in electrophotography. This is based on the discovery that it has extremely excellent properties as a photoconductive member and that it has excellent absorption spectrum properties on the long wavelength side.

An 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 in particular, and has fast photoresponse.

Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance.

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

Yet another object of the present invention is high photosensitivity.

It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics.

Still another object of the present invention is to easily obtain high-quality images with no image defects or image blurring, high density, clear halftones, and high resolution during long-term use. An object of the present invention is to provide a photoconductive member for electrophotography that can be used in electrophotography.

A photoconductive member that achieves the object of the present invention includes a support for the photoconductive member and an amorphous material [hereinafter a-Ge, (Si , i(H.

X)]; a second layer region composed of an amorphous material containing silicon atoms and exhibiting photoconductivity; and an amorphous material containing silicon atoms and carbon atoms. The third layer region is characterized by having a light-receiving layer having a layered structure provided in order from the support side.

The photoconductive member of the present invention can solve all of the above-mentioned problems and has extremely excellent mechanical and optical properties.

Shows photoconductive properties, electrical pressure resistance, and usage environment properties.

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

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

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

FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention.

A photoconductive member 100 shown in FIG. 1 has a photoreceptive layer 102 on a support 101 for the photoconductive member, and the photoreceptive layer 102 has a free surface 105 on one end surface. .

The photoreceptive layer 102 has a first layer region ((3103 and a -8i (
H, X, ) third layer region (M) 106 are laminated in this order. The germanium atoms contained in the first layer region (G) 103 are
It is contained in the first layer region (G) 103 so as to be continuously and uniformly distributed in the thickness direction of the layer 103 and in the in-plane direction parallel to the surface of the support.

Second layer region (S) provided on the first layer region (G)
It does not contain germanium atoms, and by forming a light-receiving layer with such a layered structure, it can absorb light of all wavelengths from relatively short wavelengths to relatively short wavelengths, including the visible light region. It can be used as a photoconductive member that has excellent photosensitivity compared to other materials.

In addition, the distribution state of germanium atoms in the first layer region CG) is such that germanium atoms are continuously distributed in the entire layer region, so when a semiconductor laser or the like is used, the second layer region CG)
The first layer region (G) can substantially completely absorb light on the long wavelength side, which is almost completely absorbed in the layer region (S) of the first layer, thereby eliminating interference due to reflection from the support surface. It can be prevented.

The content of silicon atoms contained in the first layer region (G) [NS1/(NS1 + NG8): NA is A in the layer
The total number of atoms] can be determined as desired so as to effectively achieve the object of the present invention, but is preferably 5 X 104 atomic ppH or less, more preferably I X 104 atomic ppH or less, an optimal number. It is desirable to have an atomic content of less than IXIO3 atomic ppm. That is, a GexStl-x
The value of X in (H,X) is preferably 0.
It is desirable that 95<X≦1, more preferably 0.99<x≦1, most preferably 0.999<X≦1.

The layer thicknesses of the first layer region (G) and the second layer region (S) are:
One of the important factors for effectively achieving the purpose of the present invention
Therefore, it is desirable that sufficient care be taken in the design of the photoconductive member to ensure that the photoconductive member formed has sufficient desired properties.

The layer thickness TB of the first layer region (G) is preferably 30λ
~50μ, more preferably 4 (1~40μ, optimally 50λ~30μ). The layer thickness T of the second layer region (S) is preferably 05~
90μ, preferably 1 to 80μ, optimally 2 to 50μ
It is preferable that it be μ.

Based on the mutual organic relationship between the layer thickness TB of the first layer region (G) and the properties of the second layer region (8), it is determined as desired when layering the photoconductive member. It is desirable that

In the photoconductive member of the present invention, the numerical range of (TB+T) is preferably 1-100μ, more preferably 1-80μ, most preferably 2-50μ.

In a more preferred embodiment of the present invention, the above-mentioned layer thickness TB and layer thickness T are appropriately selected to satisfy the relationship TB/T≦1. It is desirable that

In selecting the numerical values of the layer thickness TB and the layer thickness T in the above case, more preferably TB/T≦09, optimally T
It is desirable that the values of layer thickness TB and layer thickness T be determined so that the relationship B/T≦0.8 is satisfied.

The layer thickness TB of the first layer region (G) is desirably quite thin, preferably 30μ or less, more preferably 25μ or less, and most preferably 20μ or less. .

If necessary, the first layer region (G) constituting the photoreceptive layer
Specifically, the halogen atoms (X) contained in the second layer region (S) and the third layer region (S) include fluorine,
Examples include chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the present invention, a-G'exS'+-x (H+
) (0,95〈X≦1) first layer region (
G) is formed by, for example, a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method.

For example, by glow discharge method, a-GexSi,
,, To form the first layer region (G) composed of x (H, A raw material gas for supplying S1 that can supply gas and silicon atoms (Sl);
If necessary, a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be made to have a reduced pressure. a -GexSi, - on the surface of a predetermined support which has been placed in a predetermined position in advance.
A layer consisting of X (H,X) may be formed.

When x = l, the S1 supply gas may be excluded from the aforementioned source gases.

In addition, when forming by sputtering method, for example, Ar
In an atmosphere of an inert gas such as He, or a mixed gas based on these gases, one target made of porcelain or two targets made of this target and Si are used. Alternatively, using a mixed target of Si and Ge, the raw material gas for supplying Ge diluted with a diluent gas such as He, Ar, etc., as necessary, can be converted into -hydrogen atoms 0 or 0. A gas for introducing the halogen atoms (3) 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 germanium or single-crystal germanium, and if necessary polycrystalline silicon or single-crystalline silicon are used as evaporation sources in a evaporation boat, and this evaporation source is used in the resistance heating method or This can be carried out in the same manner as in the case of sputtering, except that the evaporated material is heated and evaporated by an electron beam method (18B method) or the like and the flying evaporated material is passed through a desired gas plasma atmosphere.

Substances that can be combined with the raw material gas for S1 supply used in the present invention include SiH4, Si, I(6, Si
,H,.

Silicon hydride (silanes) in a gaseous state or that can be gasified, such as Si, H, and O, can be effectively used, especially because of their ease of handling during layer creation work, good Si supply efficiency, etc. From this point of view, SiH4, Si, and H6 are preferred.

GeH is a substance that can be used as the raw material gas for supplying Ge.
,,Ge2H6,Ge,H8,Ge,H,. , Ge,
H,,,Ge,H,4,Ge,H,,.

GeaH+a+Ge, H2o, and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, and in particular, ease of handling during layer creation work, G
eGeH4, Ge2H, etc. in terms of good supply efficiency, etc.

Ge3H8 is preferred.

Effective raw material gases for introducing halogen atoms used in the present invention are preferably gaseous or gasifiable halogen compounds such as many halogen compounds, interhalogen compounds, and silane derivatives substituted with halogen. Can be mentioned.

Further, silicon hydride compounds containing halogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective in the present invention. Specifically, halogen compounds that can be suitably used in the invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CJF, CI! F.

BrF, , BrF, , IF, , IP, ,
Examples include 710 intergen compounds such as IC/ and IBr.

Specifically, as a silicon compound containing a halogen atom, so-called a silane derivative substituted with a halogen atom, for example, 8
Preferred examples include silicon halides such as iF4.8i2F6.5icz, SiBr4, and the like.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying 8i together with a raw material gas for supplying Ge. a-GeXS containing halogen atoms on a desired support without using silicone gas
When creating the first layer region (G) containing no-rogen atoms according to the 0 glow discharge method that can form the first layer region (G) consisting of 'l-x, basically, For example, silicon hydride, which is the raw material gas for supplying Si, germanium hydride, which is the raw material gas for Ge supply, and Ar, H
2. Introducing a gas such as He into the deposition chamber where the first layer region (G) is to be formed at a predetermined mixing ratio and gas flow rate;
The first layer region (G) can be formed on a desired support by generating a glow discharge and forming a plasma atmosphere of these gases, but it is possible to control the introduction ratio of hydrogen atoms. In order to make it even easier, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer. There is no problem even if a plurality of types are mixed and used at a predetermined mixing ratio.

K, which introduces 7-halogen atoms into the layer formed in both the sputtering method and the ion-blating method, involves introducing a gas of the above-mentioned 7-halogen compound or a silicon compound containing the above-mentioned halogen atoms into the deposition chamber. It is sufficient if a plasma atmosphere of the gas is formed by introducing the gas into the atmosphere.

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as H2, or the above-mentioned silanes or/
Gases such as germanium hydride and the like may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gases.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl! .

Hydrogen halides such as HBr, HI, S1H2F,
, 8 iguchi,■,.

S 1H2Cz2. S 1Hcz, , S 1H2
Br, , S 1HBr3 and other halogens, substituted silicon hydrides, and GeHF1. GeH2F, , GeHl
lF.

GeHCl5'+ GeH,Cz, , 'GeH,
CI! , GeI(Br8. (EeH2Br2.G
eH8Br.

GeHI3. Hydrogenation of GeH2I, GeH3I, etc.] - halogen atoms having hydrogen atoms as one of their constituents, such as germanium rogenide, GeF4. GeCl! 4
, ()eBr4. GeI, .

GeF2. GeCJ2. GeBr2. The first layer region (G
) can be mentioned as a starting material for the formation.

Among these substances, chlorides containing hydrogen atoms are
When forming the first layer region (G), hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer. used as raw material.

'In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, H2, or SiH, Si2H6
゜Germanium or germanium compound for supplying Ge to silicon hydride such as Si, H6, 5i4H, (, etc.),
Or GeH, Ge2H6, Ge3H, Ge4H
,. , Ge, Hl, , Ge, H, .

This can also be done by causing a discharge by coexisting germanium hydride such as Ge7H, 6, Ge8H, 8, Ge, H2°, etc. and silicon or a silicone compound for supplying 81 in the deposition chamber. 0 In a preferred example of the present invention, the amount of hydrogen atoms (14) or the amount of hydrogen atoms (X) or hydrogen atoms contained in the first layer region (G) of the photoconductive member to be formed is 710
The amount of genomic atoms (1-1+X) is preferably 0.01-40 atomic%, more preferably 0.0
5-3 Q atomic%, optimally 0°1-25a
It is desirable to set it to tomic%.

Hydrogen atoms (T) contained in the first layer region (G)
or/and to control the fate of the rogen atom (X),
For example, it may be possible to control the support temperature reaction, the amount of the starting material used to incorporate hydrogen atoms (H) or halogen atoms (X) into the deposition system, the discharge force, etc. .

In the present invention, in order to form the second layer region (S) composed of a-8i(H,X), the starting material (I) for forming the first layer region (G) described above is used. inside 1), Ge
A case where the first layer region (G) is formed using the starting material excluding the starting material that becomes the raw material gas for supply [starting material for forming the second layer region (S) (■)] , can be carried out according to similar methods and conditions.

That is, in the present invention, to form the second layer region (S) composed of a-8i (H, It is made by a vacuum deposition method. For example, a-8i(H
, Introducing a raw material gas for introducing (H) and/or for introducing halogen atoms (X) into a deposition chamber whose interior can be reduced in pressure,
A glow discharge is generated in the deposition chamber, and a -8i (H,
It is sufficient to form a layer consisting of X). In addition, when forming by a sputtering method, hydrogen atoms (H ) or/and norogen atom (X
) The gas for introduction may be introduced into the deposition chamber for sputtering.

In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the second layer region (S) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (H+X) is preferably 1 to 40 atoms
ic%, more preferably 5-3 Q atomic%, optimally 5-25 atomic%.

A starting material for structurally introducing a substance (C) for controlling conduction properties, such as an atom of Group I or Group V of the periodic table, into the second layer region (S) constituting the photoreceptive layer. Or Chapter V
The starting material for introducing group atoms is introduced in a gaseous state into the deposition chamber in a second
It may be introduced together with other starting materials for forming the layer region (S). As the starting material for introducing the group (I) atoms, it is desirable to use 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 introducing such a group III atom, B2 is used for introducing a boron atom.
H,・B4H1O・B,H,,B5H1l,B6HI
Boron hydride such as O, B6H12, B6HI4, BF,
, BCJ, , BBr, etc. (7) Boron halides and the like. In addition, C133 in )s, ()eC1
! 3*Ge(CH3)3 +InC/3, Tl
C15 etc. can also be mentioned.

In the present invention, effective starting materials for the introduction of Group Ⅰ atoms include PH3,
, P2H, etc., phosphorus hydride, PH4I, PF, etc.

PFa, PCts, pci! , , PBr,
, PBr, , PI3 and other phosphorus halides. In addition, AsH,, Asfan, ks'cl*+A
s13r3. AsF, , 8bH3, SbF3.
SbF, , 5bC1s, 5bCJv l5iH
,,5iCJ3. B1Br3 and the like can also be mentioned as effective starting materials for introducing Group V atoms.

In the photoconductive member 100 shown in FIG. 1, a third layer region (M) is formed on the second layer region (S) 104.
106 has a free surface and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability.

Further, in the present invention, each of the amorphous materials constituting the second layer region (S) 104 and the third layer region (M) 104 has a common constituent element of silicon atoms. As a result, sufficient acid leakage occurs at the laminated interface to ensure chemical stability.

The third layer region (iJ) in the present invention includes silicon atoms (Si), carbon atoms (C), and hydrogen atoms (
H) or/and a halogen atom (3) (hereinafter referred to as ra(SjxC+-x)y(H9X)+
-yJ. However, it is composed of % o<xs y<1).

a (SLX(-1-X) y (H,X)
Formation of the third layer region (M) consisting of 1-y
This is accomplished by a glow discharge method, a sputtering method, an electron beam method, or the like. These manufacturing methods are based on manufacturing conditions,
It is selected and adopted as appropriate depending on factors such as the level of equipment capital investment, manufacturing scale, and the desired characteristics of the photoconductive member to be manufactured. The glow discharge method or the sputtering method is preferred because of its advantages such as relatively easy control and easy introduction of carbon atoms and halogen atoms together with silicon atoms into the third layer region (M) to be produced. Suitably adopted.

Furthermore, in the present invention, a glow discharge method and a sputtering method are used together in the same system to form the third layer region (M).
may be formed.

When forming the third layer region (,M) by the glow discharge method, the raw material gas for forming a (S'xC1-x)y (H,X)+-y is mixed with a diluting gas as needed. The mixture is mixed at a fixed mixing ratio and introduced into a vacuum deposition chamber where the support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, thereby removing the gas already formed on the support. On a certain second layer region (S) K a-(8i)(C1-)O
It is sufficient to deposit y'(H,X)+-y.

In the present invention, a-(8ixC,-x)y(H,X
), -.

The raw material gas for formation includes silicon atoms (Si), carbon atoms (C), hydrogen atoms (H), and nitrogen atoms (3
Most of the gaseous substances or gasified substances containing at least one of the atoms listed in ) can be used.

When using a raw material gas containing Sl as one of 8i, C, H, and X, for example, a raw material gas containing Si and a raw material gas containing C, as necessary. Accordingly, a raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing 8i as a constituent atom and a raw material gas containing C and H may be used. A raw material gas containing constituent atoms and/or a raw material gas containing C and X as constituent atoms are also mixed at a desired mixing ratio, or a raw material gas containing Si as constituent atoms,
8i, a raw material gas containing three constituent atoms of C and H, or
A raw material gas containing Si, C, and X as constituent atoms can be used in combination.

Separately, C is added to the raw material gas containing Si and H as constituent atoms.
A raw material gas containing Si and X as constituent atoms may be mixed and used, or a raw material gas containing C as constituent atoms may be mixed and used with a raw material gas containing Si and X as constituent atoms.

In the present invention, the preferred halogen atomic diagrams contained in the third layer region (M) are F, CI! .

Br, I, especially F', CI! is desirable.

In the present invention, materials that can be used effectively to form the third layer region (Δ()) include those that are in a gaseous state at room temperature and normal pressure or that are easily gasified. The substances obtained can be listed.

In the present invention, the gases effectively used as raw material gases for forming the third layer region (M) are the s-cliff and the Ht'm-form.
jX Child f Toru 80 (4-S"2H6-s'-Ha
, 81. H.

Silicon hydride gas such as silanes (Si/ane), C
and H as constituent atoms, for example, hydrogen tetrahydride having 1 to 1 carbon atoms,
Acetylene hydrocarbons having 2 to 3 carbon atoms, simple halogens,
Hydrogen halides, interhalogen compounds, silicon halides,
Examples include halogen-substituted silicon hydride and silicon hydride. Specifically, methane (CH
4), ethane (C2H6), propane (C5Hs), n
-butay (n-C4H1O), penta7 (CsH+t
), -r-f L/ Examples of ethylene (C2H4), propylene (C,H,), butene-1
(C,H,), butene-2 (C4H8), isobutylene (C4H8), pentene (C6HI o ), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (CsH4), butyne (C4Ha), and simple halogens. Examples include halogen gases such as fluorine, chlorine, bromine, and iodine, and -4FH as hydrogen halide.

HI, HC/, HBr, and interhalogen compounds include BrF, CI! F, CI! Fs,
ClF5, BrF, , BrF, , IP,
, IF', .

Ice, IBr, silicon halide and 8i
F4, 812F6 tSiCgsBr, 5iC1
! tBr2.5iC41'Br, , 5iCz8I
, 8iBr, s as a halogen-substituted silicon hydride
S I H2F2.

SiH, Ce, , 5iHCz, , 8iHsCI
! , 5iH3Br, 8iH,Br, .

5iHBr3, as silicon hydride, SiH4,8i
2H8゜8i, H, o etc. 7 (SiJane)
and so on.

In addition to these, CF4. CCI, , CBr4. C
HF, , C) (2F, .

CHsF, CHsCJ, CI(, Br, C
HsI, halogen-substituted paraffinic hydrocarbons such as CtH5Cl, fluorinated sulfur compounds such as sp, sp6, S
i(CHs)4. Alkyl silicides such as Si(C2H3)4, SI C7(CHs)s, 81C1
Silane derivatives such as halogen-containing alkyl silicides such as 2(C14g)2,5IC1s C8 can also be mentioned as effective.

These third layer region (M) forming substances have a predetermined composition ratio of 1 silicon atom in the third layer region (M) to be formed.
, carbon atoms, halogen atoms, and optionally hydrogen atoms are selected and used as desired when forming the third layer region (M).

For example, S can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and can form a layer with desired characteristics.
i (CHs)i and 8iHCz as containing a halogen atom, , 5iH1C&, 5iCl!
a-(SiXC+-x)y(C A third layer region (M) consisting of /+H)ly can be formed.

In order to form the third layer () by sputtering, a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is targeted, and these are spun as necessary. This may be performed by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements.

For example, if a Si wafer is used as a target, raw material gases for introducing C, H or/and X are diluted as necessary and introduced into a sputtering deposition chamber, and these gases The Si wafer may be sputtered by forming plasma.

In addition, by using a single target containing Si and C as separate targets for Sl and C, it is possible to use a mixed target of Si and C in a gas atmosphere containing hydrogen atoms and/or halogen atoms as needed. The material used as the source gas for the introduction of oC, 'H and It can also be used as an effective substance in legal cases.

In the present invention, the diluent gas used when forming the third layer region (M) by the glow discharge method or the spuck-ring method includes so-called rare gases such as He, Ne,
Suitable examples include Ar and the like.

The third layer region (M) in the present invention is carefully formed so as to provide the required characteristics as desired.

In other words, a substance whose constituent atoms are 8i, C, and H or/and X as necessary can have a structure ranging from crystalline to amorphous depending on its preparation conditions, and in terms of electrical properties,
In the present invention, a-( S'
xC+-x)y (H+
x)y (H9X), -y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, when the third layer region (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 degree of electrical insulation is reduced to a certain extent with respect to the irradiated light. As an amorphous material with a sensitivity of a
(8'xC+-x)y(H,X)+-a is created.

a (S'x"t-x)y on the surface of the second layer region (S)
A third layer region (M) consisting of a (S+XC1'x)y(H,X), -a is formed on the surface of the third layer region (M) consisting of (H, In this case, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer, and in the present invention, a-(SixCt-x)y It is desirable that the temperature of the support during layer formation be strictly controlled so that (H,X)+-y can be formed as desired.

In the present invention, the formation of the third layer region N) is performed by selecting an appropriate range in accordance with the method of forming the third layer region (M) in order to effectively achieve the desired purpose. is executed, but
Preferably 20-400°C, more preferably 50-3
The temperature is desirably 50°C, most preferably 100-300°C. In forming the third layer region (M), delicate control of the composition ratio of the atoms ``-'' constituting the layer and control of the layer thickness are relatively easy compared to other methods. It is advantageous to employ a glow discharge method or a sputtering method, but when forming the third layer region (M) using these layer forming methods, the temperature during layer formation as well as the support temperature described above must be adjusted. Discharge power is created a
-(8'xC1-x)y(H,X)ty is one of the important factors that influences the characteristics of ty.

a having the characteristics that enable the object of the present invention to be achieved;
”” xC□−x)y (H,X) The discharge power conditions for effectively creating ly with good productivity are as follows:
Preferably 10-300W, more preferably 20-250W
W, preferably 50 to 200 W.

The gas pressure in the deposition chamber is preferably O,Ol-I To
rr, more preferably about 0.1 to 0.5 Torr.

In the present invention, the desired numerical ranges of the support temperature and discharge power for forming the third layer region (M) include the values in the above-mentioned ranges, but these layer forming factors are independent of each other. They are not determined separately, but are mutually and organically related so that a third layer region small I) consisting of a-(SxXC,-x)y(H,X)-y with desired characteristics is formed. It is desirable that the optimum value of each layer creation factor be determined based on the properties of the layers.

The amount of carbon atoms contained in the third layer region in the photoconductive member of the present invention is the same as the conditions for creating the third layer region.
It is an important factor in the formation of the third layer region (M) that achieves the desired properties that achieve the objectives of the invention.

The amount of carbon atoms contained in the third layer region (M) in the present invention can be determined as desired depending on the type and characteristics of the amorphous material constituting the third layer region (M). It can be determined by

That is, the general formula a-(SjxCx -x)y(H,
) l-3' can be roughly divided into amorphous materials composed of silicon atoms and carbon atoms (hereinafter referred to as
It is written as "a-8iaC1-a". However, 0(a(1),
An amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as r a (SibC+-b)cH+-c
It is written as j. However, 0<bb C<1)% An amorphous material (hereinafter referred to as ra-(Si, IC+
-d) e(H, written as X'5-eJ. However, O<d,
It is classified as e(1).

In the present invention, the third layer region CM) is a-8iaC
, -a, the amount of carbon atoms contained in the third layer region (M) is preferably lX10 to 90ato
miC%, preferably 1-80 atomic X
, most preferably 10 to 75 atomic%, preferably 0.2 to 0.99, most preferably 0.25 to 0.9.

In the present invention, the third layer region (2) is a-(Si1)
When composed of C14,)cH,-o, the amount of carbon atoms contained in the third monolayer region (M) is preferably 1×
1O-3 to 90 atomic%, more preferably 1 to 1g□ atomic%, optimally IO-80
It is desirable to set it to atomic%. The content of hydrogen atoms is preferably 1 to 40 atoms
ic%, more preferably 2 to 35 atomic%, optimally 5 to 30 atomic%, and the photoconductive member formed when the hydrogen content is in these ranges is practically It can be fully applied as an excellent product.

Optimally 0.15-0.9, C usually 0.6-0.99
, preferably 0.65-0.98, optimally ido, 7-0
．． 95 is desirable. .

The third layer region (M) is a-(SjdCt-d)e(H
, X)te, the third layer region (M
) Preferably, the content of six carbon atoms contained in
m Niha 1~90 atomic%, optimally l O~8
It is desirable to set it to 0'atomic%.

The content of halogen atoms is preferably 1 to 20
It is desirable that the halogen atom content be in atomic%, and photoconductive members prepared when the halogen atom content is within these ranges can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 19
atomic X or less, more preferably 13 atoms
It is desirable that it be less than ic%.

That is, the previous a (Sidc, -d)e(H+ x)
If it is expressed as d and e in I-e, d is preferably 0.
．． 1-0.99999, more preferably 0.1-0.99
, optimally 0.15-0.9, e usually 0.8-0.
99, preferably 0.82 to 0.99, optimally 0.85
It is desirable that it be ~0.98.

The number range of the layer thickness of the third layer region (ht) in the present invention is one of the important factors for effectively achieving the object of the present invention.

It can be determined as desired depending on the intended purpose so as to effectively achieve the purpose of the present invention.

Further, the layer thickness of the third layer region (IJ) depends on the amount of carbon atoms contained in the layer (M) and the layer thicknesses of the first layer region (G) and the second layer region (S). It is desirable that the relationship between the two layers be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region.

In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production.

The layer thickness of the third layer region (LM) in the present invention is as follows:
Preferably 0.003 to 30 μ, more preferably 0.00
It is desirable that the thickness be 4 to 20μ, most preferably 0.05 to 10μ.

The support used in the present invention may be either electrically conductive or electrically insulating. Examples of the conductive support include NiCr stainless steel and fart.

Cr, No, Au, NblTa,
Examples include metals such as VITi, Pt, Pd, and alloys thereof.

Polyester is used as an electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass.

Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is preferably provided on the other side of the conductive treatment. If so, on its surface, NI Cr IAtr Cr # llo I
A11l r It + Nb * Ta + '/
+ Tl p Pt p N g In2O51SnO
Conductivity can be imparted by providing a thin film consisting of 1*tTo (In20m 15nCh), etc., or Df if a synthetic resin film such as a polyester film
.

NtCr, Aj, Noig, P, b, 'An+Nir entry u
, Or, lo, Ir, Nb, TarV, Ti,
Conductivity is imparted to the surface by providing a thin film of metal such as Pt on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support may be any shape such as cylindrical, belt-like, or plate-like, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. In the case of continuous high-speed copying, it is desirable to use an endless belt 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 cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ 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 example of a photoconductive member manufacturing apparatus.

Gas cylinders 202 to 206 in the figure are sealed with raw material gases for forming the photoconductive member of the present invention.
in4 gas (99.999% purity.

Hereinafter, it will be abbreviated as SiH4/He. ) cylinder, 203 is li
GeH1 gas (purity 99.999%, hereinafter abbreviated as aaH4/Ha) diluted with
205 is a Lie gas (purity 99.999%) cylinder, 206 is H, gas (
(purity 99.999%) cylinder.

To allow these gases to flow into the reaction chamber 201, make sure that the valves 222 to 226 of the gas cylinders 202 to 206 and the leak pulp 235 are closed. ~221. After confirming that the auxiliary knobs 232 and 233 are open, first open the main pulp 234 to exhaust the reaction chamber 201 and each gas pipe. Next, when the reading on the vacuum gauge 236 reaches approximately 5 x 10"torr, turn the auxiliary knob 23
2,233, close the outflow valves 217-221.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 237, 5i) (1
/ [Ia gas, GaHa/He from gas cylinder 203
Open the gas pulp 222, 223 and check the outlet pressure gauge 2.
Adjust the pressure of 27.228 to 1 k417CrrL2,
The inlet pulps 212 and 213 are gradually opened and allowed to flow into the 5-mass flow controllers 207 and 208, respectively. Subsequently outflow) <Lube 217, 218, auxiliary pulp 23
2 is gradually opened to allow the gas to flow into each reaction chamber 201. At this time, 5iI (4/Ila gas flow rate and GeH4
Adjust the outflow valves 217 and 218 so that the dead force 5 is at the desired level with the gas flow rate, and while watching the reading on the vacuum gauge 236 so that the pressure inside the reaction chamber 201 reaches the desired value. Adjust the opening of the main knob 234. Then, the temperature of the base body 237 is raised to 50 to 4
After confirming that the temperature is set within the range of 00'0, the power supply 240 is set to the desired power and the reaction chamber 201 is turned on.
germanium atoms are contained in the layer formed by generating a glow discharge within the layer.

The glow discharge is maintained for a desired time as described above to form a first layer region (Q) on the substrate 237 to a desired layer thickness. In the
Substantially no germanium atoms are formed on the first layer region (q) by maintaining the glow discharge for the desired time following similar conditions and procedures, except for completely closing the effluent pulp 218 and changing the discharge conditions as necessary. It is possible to form a second layer region (S) that does not contain any oxides.

In order to contain a substance that controls conductivity in the second layer region (S), when forming the second layer region (Sl, for example, B2
Gases such as H4 and PHs may be added to the gas introduced into the deposition chamber 201.

The first layer region (Q
To form a third layer region on the second layer region (0), connect a CJL gas cylinder to the gas line that is not used when forming the third layer region (hI), This is accomplished by diluting each of the 3iH4 gas, C, and H4 gases with He, etc., as necessary, using the same valve operation as in the formation, and generating glow discharge according to desired conditions.

In order to contain halogen atoms in the third layer region (product), for example, add 5IF4 gas) (4 gas, or add SiH gas to this and add SiH gas to this and add halogen atoms to the third layer region (
It is achieved by forming (goods).

The amount of carbon atoms contained in the third layer region can be determined, for example, by changing the flow rate ratio of SiH4 gas and CJL gas introduced into the reaction chamber 201 by glow discharge, or by sputtering. In the case of forming a layer using a ring, the target can be formed as desired by changing the sputter area ratio of the silicon wafer and graphite powder, or by changing the mixing ratio of silicon powder and graphite powder and forming the target. can be controlled. The amount of halogen atoms (3) contained in the third layer region is determined by adjusting the flow rate when the raw material gas for introducing halogen atoms, such as SiF, is introduced into the reaction chamber 201. Ru.

Further, during layer formation, it is desirable that the base body 237 be rotated at a constant speed by a motor 239 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 2, layers were formed on a cylindrical adhesive substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member.

The image forming member thus obtained is installed in a charging exposure experiment device.E) 5. Corona charging was performed for 0.31 m using OKV, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light amount of 2 lux-see was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the image forming member by cascading a charged developer (including toner and carrier) over the surface of the image forming member. The toner image on the imaging member is set at θ5. When the image was transferred onto transfer paper using OKV's double charging, a clear, high-density image with excellent resolution and good tone reproducibility was obtained.

Example 2 Layer formation was performed using the manufacturing apparatus shown in FIG. 2 in the same manner as in Example 1 except that the conditions shown in Table 2 were used to obtain an electrophotographic image forming member.

With respect to the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, except that the charging polarity and the charging polarity of the developer were reversed. A clearer image quality was obtained.

Example 3 Layer formation was performed using the manufacturing apparatus shown in FIG. 2 in the same manner as in Example 1 except that the conditions shown in Table 3 were used to obtain an electrophotographic image forming member.

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

Example 4 In Example 1, GIIHI/He gas and 5iH
An electrophotographic image forming member was produced in the same manner as in Example 3, except that the content of germanium atoms contained in the first layer was changed as shown in Table 4 by changing the gas flow rate ratio of 1/Ile gas. were created respectively.

Regarding the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1.
The results shown in the table were obtained.

Example 5 Electrophotographic image forming members were prepared in the same manner as in Example 3, except that the thickness of the first layer was changed as shown in Table 5. In fact, images were formed on transfer paper using the image forming members thus obtained under the same conditions and procedures as in Example 1, and the results shown in Table 5 were obtained.

Example 6 ・Cylinder-shaped M
A layer was formed on the substrate under the conditions shown in Table 6 to obtain an electrophotographic image forming member.

The image forming member thus obtained was placed in a charging exposure experiment apparatus and the image forming member was set at θ5. An electric current between 0.311 IC and 0.311 IC was performed using OKV, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 2 eux-tec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the image forming member by cascading a charged developer (including toner and carrier) over the surface of the image forming member. When the toner image on the image forming member was transferred onto a transfer paper by corona charging with C) s, o <v, a clear high density image with excellent resolution and good gradation reproducibility was obtained.

Example 7 In Example 1, the light source was replaced with a tungsten tube.
An electrophotograph was created under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using a 10 nm GaAs-based semiconductor laser (10 mW). When the image quality of the toner-transferred image was evaluated using the image forming member, it was found that a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

Example 8 As a result of the evaluation, the results shown in Table 10 were obtained.

Example 11 When forming the third layer region, SiH, gas, SiF4 gas,
Each of the image forming members was prepared in the same manner as in Example 1, except that the content ratio of silicon atoms and carbon atoms in the third layer region (b) was changed by changing the flow rate ratio of the CJL gas. Created. After repeating the image forming, developing, and cleaning steps as described in Example 1 approximately 50,000 times for each image forming member thus obtained, image evaluation was performed.
The results shown in Table 1 were obtained.

Example 12 Each of the imaging members was prepared in exactly the same manner as in Example 1, except that the layer thickness (in the third layer region) was changed. The process was repeated to obtain the results shown in Table 12.

Table (1) Excellent The common layer forming conditions in the examples of the present invention with O1 good or better are shown below.

Substrate temperature: germanium atom (Ge) containing layer ・・・・・・・・・・
Approximately 200°0 germanium atom (Ge)-free layer...
...About 250°C Discharge frequency: 13.56 MHz Reaction chamber pressure during reaction: 0.3 torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIG. 2 is an apparatus used for producing the photoconductive member of the present invention in Examples. FIG. 100...Photoconductive member 101...Support 102...-Photoreceptive layer Applicant Canon Corporation'! ”: Ryo agent Gi Marushima - Kidney! Pi row

Claims (1)

[Scope of Claims] (1) A support for a photoconductive member, and a Gex
A first layer region made of an amorphous material containing Sj s −X (0,95 (x≦1)) and a second layer region made of an amorphous material containing silicon atoms and exhibiting photoconductivity. a third layer comprising a layer region and an amorphous material containing silicon atoms and carbon atoms;
Layer region (2) The photoconductive member according to claim 1, wherein at least one of the first layer region, the second layer region, and the third layer region contains hydrogen atoms. . (3) The light according to claim 1 or 2, wherein a halogen atom is contained in at least one of the first layer region, the second layer region, and the third layer region. conductive member.