JPS5833256A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member for electrophotography, which is excellent in a charge holding function, has scarcely residual potential, stable in an electric characteristic even in a high humidity atomosphere, is high in sensitivity, has a high S/N ratio, is excellent in optical fatigue resistance and repetitive use property, has high density, generates a half tone clearly, and also is capable of stably obtaining a high resolution and high quality picture at all time. CONSTITUTION:A titled member is constituted of a supporting body 101, and an amorphous material containing a hydrogen atom or a halogen atom, and consisting of a silicon atom as its base body, and has an amorphous layer 103 showing photoconductivity and a barrier layer 102, and said amorhous layer 103 has a layer area containing an oxygen atom, distribution of the oxygen atom is unequal in the thickness direction of the layer, it is distributed more on the opposite surface side of the supporting body, and the layer is constituted so that its maximum distribution quantity Cmax is in the vicinity of a surface ts. In this way, excellent electric, optical and photoconductive characteristics and a use environmental characteristic are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a light guide that is sensitive to electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet light, visible light, infrared light, X-rays, r?/a, etc.). Regarding vLs material.

As a photoconductive material constituting a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, a protoscopic imaging device, etc., it has a high sensitivity and a photocurrent (Ip
)/dark current (Id)), have absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated with the wavelength of light, have fast photoresponsiveness, have a desired dark resistance value, and when used Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily dispose of afterimages within a predetermined time. In particular, in the case of electrophotographic image forming members incorporated into electrophotographic devices used in offices as business machines,
The non-polluting property during the above usage 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.
For example, DE 2746967 and DE 285.5718 describe its application as an electrophotographic image forming member, and JP-A-55-39404 describes its application to a photoelectric conversion/reading device. ing.

A photoconductive member composed of conventional A-8I and having a multilayer conductive layer has excellent electrical, optical, photoconductive properties such as dark resistance value, photosensitivity, and photoresponsiveness, as well as moisture resistance, etc. There are points that can be further improved in terms of environmental characteristics and stability over time, and practical solid-state imaging devices, reading devices, and electrophotographic images can be used in a wide range of applications. Forming member→
The reality is that it cannot be used effectively considering productivity and mass production.

For example, when applied to electrophotographic image forming members, it is often observed that residual potential remains during use.
When these types of photoconductive members are used repeatedly for a long period of time, fatigue accumulates due to repeated use, and there are many inconveniences such as the appearance of so-called ghost images, which result in the formation of a residual image. .

Furthermore, for example, according to many experiments conducted by the present inventors, a as a material constituting the photoconductive layer of an electrophotographic image forming member
-84 is the conventional 8e, , Od8.

OPO (organic photoconductive materials) such as ZnO, PVOz, and TNF have many advantages, but a single-layer structure consisting of a-8i that has characteristics suitable for use in conventional solar cells has many advantages. Even if the photoconductive layer of an electrophotographic image forming member having a photoconductive layer is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, making it difficult to apply ordinary electrophotographic methods. However, in a humid atmosphere, the above-mentioned tendency is remarkable, and in some cases, it may not be possible to retain the charged charge at all until the current stagnation time, so there are points that can be solved. It's clear.

Therefore, while efforts are being made to improve the properties of the a-8i material itself, when designing photoconductive members, the desired electrical, optical, and photoconductive properties as described above can be obtained, and high sensitivity and stable image quality can be achieved. It is necessary to devise ways to obtain the desired results.

The present invention has been made in view of the above points, and the adaptability 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 this perspective, we have developed an amorphous material (non-crystalline material) that uses silicon atoms as its base material and contains at least either a hydrogen atom (H) or a halogen atom (X). Amorphous silicon that exhibits photoconductivity and is composed of hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon (hereinafter a-8i (H, A photoconductive member manufactured with a specific layer structure as described below is not only usable for practical use, but also surpasses conventional photoconductive members in most respects. This is based on the discovery that it has extremely excellent properties, especially as a photoconductive member for electrophotography, in terms of photosensitivity and stabilization of image quality.

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

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

Another object of the present invention is to maintain charge during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as a scratch forming member for electrophotography. It is an object of the present invention to provide a photoconductive member tube having sufficient performance and excellent electrophotographic properties with almost no deterioration in its characteristics observed even in a humid atmosphere.

Another object of the present invention is to provide electrophotography with high density, clear 7%-7 tones, and high resolution, making it easy to consistently obtain high-quality images. An object of the present invention is to provide a photoconductive member.

The photoconductive member of the present invention includes a support for the photoconductive member and an amorphous material (a- an amorphous layer exhibiting photoconductivity and a barrier layer, the amorphous layer comprising:
It has a layer region containing oxygen atoms in at least a part thereof, and the distribution of oxygen atoms in the layer region is substantially uniform in a plane substantially parallel to the surface of the support, and the thickness of the layer is In a more preferred embodiment, it is non-uniform in the direction, and the oxygen atoms contained in the layer region are more distributed on the surface side opposite to the Tsumugi support. , the content of oxygen atoms in the entire layer region is 0.05
~30 atomic-, and the maximum distribution amount is present on the surface opposite to the layer region OS support or in the vicinity of the surface, and the value is 03 to 67 atomjcts.

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

In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on formation, and has stable electrical properties even in a humid atmosphere. It is highly sensitive, has a high 8N ratio, is extremely resistant to light fatigue, has excellent repeatability, and has high lightness.
It is possible to always stably obtain high-quality images with clear halftones and high resolution.Hereinafter, the photoconductive member of the present invention will be described in detail with reference to the drawings.

FIG. 1s1 is a schematic configuration diagram schematically shown to explain a typical configuration example of the photoconductive member of the present invention.

A photoconductive member 100 shown in FIG. 1 includes a barrier layer 102 provided as necessary on a support 101 for a photoconductive member, and a barrier layer 102 provided in direct contact with the barrier layer 102. The amorphous layer 103 has a layer region containing oxygen atoms in at least a part thereof, and the distribution of oxygen atoms in the layer region is similar to that of the support 1010. It is substantially uniform in a plane substantially parallel to the surface, and non-uniform in the thickness direction of the layer, so that the oxygen atoms contained in the layer region are on the surface side opposite to the support 101. The oxygen atom content O1 in the entire cough layer region is 0.05 to 30 atomic.
@, and the maximum distribution amount Omax exists on the surface opposite to the support 101 in the scissor layer region or very close to the surface, and 0unax is 0.3 to 67 mtonnt c
It is said to be d4.

The support 101 may be conductive or slightly insulating. As the conductive support, for example, Ni0r, x
Stainless Steel, Mu/, Or, Mo +Au +NJTa
, V, Ti, Pi, Pd, or alloys thereof.

Polyester is used as the 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. It is preferable that at least one surface of these electrically insulating supports is conductively treated with tCa, and another layer is provided on the conductively treated surface side.

For example, if it is glass, Ni0r is applied to its surface.

A4 *Or, Mo, Au, Ir, Nb*Ta, V
, Ti, Pt sPd*1, n, 0. ,8nO,+
Conductivity can be imparted by providing a thin film made of ITO (In, 0. +8 nO,) or the like, or if it is a synthetic resin film such as a polyester film, Ni0
r, A/, Ag, Pb, Zn*Ni, Au
.

A thin film of metal such as Or, Mo, Ir, Nb, Tm, V, Ti, Pt, etc. is formed on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal. conductivity is imparted to the The shape of the support body 101 may be cylindrical, belt-shaped, plate-shaped, etc.
It can be of any shape, and its shape is determined as desired; for example, if the photoconductive section of FIG. It is desirable to have an endless belt shape or a circle shape. The thickness of the support 101 is determined as appropriate so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the thickness of the support 101 may be determined so that it can sufficiently function as a support. It is made as thin as possible within the range. Heigo et al.
In such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc.

The barrier layer 102 is formed by forming the amorphous layer 10 from the support 101.
3. Effectively prevents the inflow of free carriers from the amorphous layer 103 side to the support body 101 side, and at the time of electromagnetic wave irradiation, the amorphous layer 103 is
It has a function of easily allowing photocarriers generated in the amorphous layer 103 and moving toward the support 101 to pass from the amorphous layer 103 side to the support 101 side.

The barrier layer 102 has the above-mentioned functions, but at the interface formed between the support 101 and the amorphous layer 103, the barrier layer 102 has the same function as the above-mentioned barrier layer 102. In the present invention, if the barrier layer 1 is sufficiently exhibited,
It is not necessary to provide 02i.

The barrier layer 102 has 7 licon atoms as its base material, and carbon atoms,
At least one type of atom selected from nitrogen atoms,
Amorphous materials containing at least either a hydrogen atom or a halogen atom as necessary are collectively referred to as a-
(8ix(0,N)>-x)y(H9X) Written as sy (however, 0<x<1.

Q<y<1 )> or an electrically insulating metal oxide or an electrically insulating organic compound.

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

Specifically, as a carbon-based amorphous material that can be effectively used as the amorphous material constituting the barrier layer 102, for example, a8ia0z-Hsa-(8mu bCt b)
cHx-c + a-(8t(101-d)eL-e
+a-(8ifOt-f)g(H+X)t-g-a 5ihNt-h+a-(8i
tNl-1)7H1-j, a-(SikNx-k)l
Xi-/+a (81mNn-rrl)n(H+X)t
Furthermore, among the above-mentioned amorphous materials, examples include amorphous materials containing two types of atoms, 0 and N, as constituent atoms (provided that O< a e b + C* d
* e + f + g + k + 1 + J +
kwltOn*El<Z).

These amorphous materials are used due to the characteristics required for the barrier layer 102 due to the optimized design of the layer structure and the ease of continuous production with the amorphous layer 103 stacked on the barrier layer 102. The most suitable one is selected accordingly. Especially from the characteristics point of view,
It is more preferable to select all carbon-based amorphous materials.

When the barrier layer 102 is made of the above amorphous material, the layer forming method may be a glow discharge method, a sputtering method, or an ion implantation/chision method.

This is accomplished by ion blating method, electron beam method, etc.

To form the barrier layer 102 by the glow discharge method, the raw material gas for forming the amorphous material is mixed with a dilution gas at a predetermined mixing ratio as needed, and the support 101 is installed. The introduced gas is introduced into a deposition chamber for vacuum deposition and turned into gas plasma by causing a glow discharge.
The amorphous material tube described above may be deposited on the support 101.

In the present invention, 8-vertical H4,8b whose constituent atoms are Sl and H is effectively used as a raw material gas for forming the barrier layer 102 made of a carbon-based amorphous material.
Hs * 8 k s Hs r 814 Hta
Silicon hydride gas such as silanes (8i1ane), C
and H as constituent atoms, for example, saturated hydrocarbons having 1 to 5 carbon atoms, and ethylene hydrocarbons having 2 to 5 carbon atoms.

Examples include acetylene hydrocarbons having 2 to 4 carbon atoms.

Specifically, the saturated hydrocarbons include methane (OH,),
Engineering <ctHm> + property (0@H1l)
, n-butane (n 04H16) + penta7 (0,
H,,) @ Ethylene hydrocarbons include ethylene (OtH*), globylene (OIH@), butene-1 (0*HA), butene-2 (0aHa), isobutylene (04H8), and pentene (OsHso).
, As the acetylene hydrocarbon, acetylene (0*H
t)-Methylacetylene (OIH4).

Butin (04H*) etc. are now mentioned.

As a raw material gas containing Si, C, and H as constituent atoms, a
Examples include o-furkyl silicides such as t(OHm)a and 8t(OtHs)a. In addition to these raw material gases, H
Of course, H1 is also effectively used as the raw material gas for introduction. Halogen atoms are introduced in the raw material gas for layer formation to configure the barrier layer 102 from a carbon-based amorphous material containing halogen atoms. Examples of raw material gases for use include simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides.

Specifically, the single halogen is fluorine.

Salt IA, bromine, hydrogen gas, hydrogen halides include FHeHI, HOz, HBr, interhalogen compounds include BrF, OtF, OzF,...
Ot￥, .

BrF5 *BrFB +Il'y + IF5 +
IOI, IBr, silicon halide: 8
iF4. sj, F', , sio/4+5iOl, Br
.

5tar, Br, , 5iOIBr, +8i0t, 1
5siBr41 As halogen-substituted silicon hydride, 8
iH,F, , 8 iH,C1@.

S IHO/81 S t HBOI + 8 sHg
Br * 81 HIBrfil 8 r )iB
rm + silicon hydride, SiB4. Si
,H,,S i,Hl.

Examples include silanes (8i1ane) such as 8i4H, and the like.

In addition to these, OOt, , OHF, , OH,F
, ,OH,F.

OH, O/, OH, Br, OH, I, 0. H,
Halogen-substituted paraffinic hydrocarbons such as Ol, 8F,
, 8F, etc., fluorinated sulfur compounds, 8t(OH3
), , 8t(OtHs)4゜and other alkyl silicides and s
sat (OH,)1 , s s o tt (OH,
)t, SiOt, OH, silane conductors such as halogen-containing alkyl silicides can also be mentioned as useful.

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

For example, 8i (OH,)4, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and form a barrier layer with desired characteristics, and 5iHO, which contains halogen atoms. /, , S 10/418iH,
By introducing O/, or 8iH, 0/, etc. in a gaseous state at a predetermined mixing ratio into the system for forming a barrier layer to generate a glow discharge, a-(8IfOt-f) g(
X+H) t -g Color disorder 11Nli't can be formed.

When employing the glow discharge method to form the barrier layer 102 with a nitrogen-based amorphous material, select the desired material from the materials listed above for forming the barrier layer, and add Then, the next raw material gas for introducing nitrogen atoms may be used. That is, a starting material that can be effectively used as a raw material gas for introducing nitrogen atoms to form the barrier layer 102 is nitrogen (Nt) having N as a constituent atom or N and H as constituent atoms, for example. , ammonia (NHm).

Hydrazine (H,NNH,), hydrogen azide (HNm)
Mention may be made of gaseous or oxidizable nitrogen, nitrogen products, and nitrogen compounds of the azide group, such as ammonium azide (NH4Ns). In addition, halogenated nitrogen compounds such as nitrogen trifluoride* (FsN> and nitrogen tetrafluoride (F4N) can be mentioned, since they can also introduce halogen atoms in addition to nitrogen atoms). .

As described above, when forming the barrier layer 102 by the glow discharge method, by selecting and using various starting materials for forming the barrier layer from among the materials on board, a desired structure having a desired solubility can be obtained. A barrier layer 102 can be formed of a material. Specifically, a good combination of starting materials when forming the barrier layer 1 (12'i by glow discharge method) is, for example, 8 I(OH,), , S 1Oz2
(OHs).

Single gas or 8iH4-NH, system, 8i 0
! , -NH4 system.

SiH4N! system, 8 i (OH,)4-8 i H
, system, Sio/, (OH5).

-8iH4 yarn and other mixed gases can be mentioned.

To form the barrier layer 102 made of a carbon-based amorphous material by sputtering, a single crystal or polycrystalline 8i wafer, a 0 wafer, or a wafer containing a mixture of 81 and C is used as a target. , this can be done by sputtering I4t'' in various gas atmospheres.

For example, if a Si wafer is used as a target, the source gas for introducing carbon atoms (0) and water bulk atoms (H) or halogen atoms (X) may be diluted with diluent gas as necessary. Then, introduce it into the deposition chamber for sputtering, and this is 4! It is possible to sputter a Si wafer by forming a gas plasma of the same gas.

Alternatively, a gas atmosphere containing at least water bulk atoms (H) or halogen atoms (X) can be created by using S and C as separate targets, or by using a single target mixed with 8i and Oo. This is done by sputtering inside.

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

To form the barrier layer 102t, which is made of an amorphous material based on Sl, by a sputtering method, a single crystal or polycrystalline 8i wafer or an S6 wafer is used.

Sputtering may be carried out using a wafer or a wafer containing a mixture of Si and N4 as a target in an atmosphere of these gases.

For example, if an 81 wafer is used as a target, a raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms, such as H8 and N2, or NH, is supplied with a diluting gas as necessary. If the Si wafer is diluted and introduced into a deposition chamber for sputtering, a gas plasma of these gases is formed and the Si wafer is sputtered.

Alternatively, it is possible to use a diluted gas atmosphere as a sputtering gas by using separate targets for Si, 8i, and N, or by using a single target formed by mixing St and 8iN. in or at least H atoms and/or
Alternatively, it can be performed by sputtering in a gas atmosphere containing X atoms.

Possible raw material gases for introducing N atoms include the raw material gas for introducing ON atoms into the starting material for forming a barrier layer, which is shown in the glow discharge example mentioned above, and is also effective in sputtering. can be used.

In the present invention, so-called rare gases such as He, N@, Ar, etc. can be cited as suitable diluent gases used when forming the barrier layer 102 by a glow discharge method or a sputtering method. I can do it.

When the barrier layer 102 is made of the above-mentioned amorphous material,
It is carefully shaped to provide the required properties as desired.

In other words, substances whose constituent atoms are at least one of C, H, and H and/or Physically, it exhibits properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention,
The preparation conditions are carefully selected so that a non-photoconductive amorphous material is formed.

The amorphous material constituting the barrier layer 102 has the function of injecting a 7-lead carrier from the support 101 side to the amorphous layer 103 side or from the amorphous layer 103 side to the support layer 101. and prevent " from occurring in the amorphous layer 103.
Since the generated photocarrier is easily allowed to move and pass to the support 101 side, it is formed as a book exhibiting electrically insulating behavior.

When the photocarriers generated in the amorphous layer 103 pass through the barrier layer 102, the mobility of the photocarriers passing through the barrier layer 102 is increased to such an extent that the photocarriers generated in the amorphous layer 103 pass through the barrier layer 102 smoothly.
The barrier layer 102 is formed to have a value of lty ).

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

That is, when forming the barrier layer 102 made of the amorphous material on the surface of the support 101, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. In the present invention, the temperature of the support when forming the support layer 102 at the time of layer formation is set at a barrier-
The barrier layer 102 is formed by appropriately selecting the optimum range in accordance with the formation method of the barrier layer 102, but in normal cases, the barrier layer 102 is formed at 20°C.
The temperature is preferably 50°C to 250°C, preferably 50°C to 250°C. To form the barrier layer 102, it is possible to continuously form the barrier layer 102 to the amorphous layer 103 and, if necessary, the third 1 m layer formed on the amorphous layer 103 in the same system. The glow discharge method and sputtering method are advantageous because it is relatively easy to finely control the composition ratio of atoms that make up each layer and control the layer thickness compared to other methods. However, with these layer formation methods, the barrier @1
02, the discharge power and gas pressure during layer formation, as well as the support temperature described above, are determined by the barrier Ij1 to be created.
This can be cited as an important factor that influences the characteristics of the layer 102.

The discharge power condition for effectively creating the barrier-102 with high productivity with the characteristics necessary to achieve the purpose is usually 1 to 300 W.

It is preferably 2 to 150W. Further, the gas pressure in the deposition chamber is usually 3 x 10' to 5 orr, preferably 8 x 104
It is desirable that the temperature is 0.5 to 0.5 Torr g.

The amount of carbon atoms, nitrogen atoms, hydrogen atoms, and halogen atoms contained in the barrier layer 102 is an important factor in forming a barrier layer with desired characteristics, similar to the conditions for forming the barrier layer 102.

When the barrier layer 102 is composed of a-st, cl-, the content of carbon atoms is usually 60% relative to silicon atoms.
~90 s+ornlc%, preferably 65-80 ato
mic-%9 70-75 atomic%1 for tolerance
．． The display shows 0.1 to 04. Preferably 0.2 to 0.35
゜Optimum value is 0.25~03, and heat (SlbCt-
b) In the case of cHt-C, the carbon atom-containing ring usually has 30 to 9 Q a (omic%, preferably 40
~9Qmtomlc 俤, optimally 50-80 itom
ic, the hydrogen atom content is usually 1 to 49
*to+nla%, preferably 2-35 atomic%
, optimally 5 to 30 atomic%, b and c, where b is usually 01 to 0.5. Preferably 0.1 to 0
．． 35. Optimally 0.15-0.3. c is usually 0.6
0-0.99. Preferably 0.65 to 0.98. The optimum value is 0.7 to 0.95, m (81aCt-a)eX
la or s-C81tC1r) g5-C31tC1r
), the carbon atom content 1 is usually 4
0 to 90 atomlc, preferably 50 to 90 ata
mlc%, Jl suitable 60-83s@omlc%,
The combined content of hydrogen atoms and hydrogen atoms is usually al~20 @tomic%, preferably 1~18 atoms 4), optimally 2~15
atomlc%, and when both hydrogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually 19
atosaic % or less, preferably 13 atomic
In the display of d, e, f, H, d,
f is usually 0.1 to 0.47. Preferably 0.1 to 0.
35. Optimally 0.15-0.3. e and g are usually 0.8 to 0.99. Preferably 0.82 to 0.99.
The optimum value is 0.85 to 0.98.

When the barrier layer 102 is made of a nitrogen-based amorphous material, first, in the case of Kasumi-'l1bNl-b, the content of nitrogen atoms is usually 43 to 60 atos to silicon atoms.
mic%, preferably 43'50 atomic%,
h is usually 0.40 to 0.57. Preferably 0
5 to 0.57.

When composed of a-(SiINl-1) 1Hx-j, the nitrogen atom content is usually 25 to 55 at
oImic%.

The content of hydrogen atoms is preferably 35 to 55 atomic%, preferably 5 to 30 atomic%, and when expressed as l and j, 1 is usually 0. .43-0.6. Preferably 0
．． 43-0.5°1 is usually 0.65-0.98.
It is preferably set to 07 to 0.95, and a −(SikN]−
k)/Xx-1 or a-(51mN1 m)n (H
+
~6 o 2tomic%, the content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 20
atomic%, preferably 2-15 atomic%
When both halogen atoms and hydrogen atoms are contained, the content of hydrogen atoms is usually 19 atomic% or less, preferably 13 atomic% or less, y,
4 +11. In the representation of n, k and l are usually 0.43
~0.60. Preferably 0.43 to 0.49, m, n force"
Usually 0.8-0.99. Preferably 0.85 to 0.98
It is said that

The electrically insulating metal oxides constituting the barrier layer 102 include Ti01, Cm@OB, Zr01, H
fO wealth, Ge01.

CmO, BeO, Pro@, YIOI, Cry03
．． To Llz, Mgo, xgo*mu1,0@.

Preferred examples include si03.MgO. The barrier layer 102 is formed by using two or more of these in combination.
It is also possible to form a

The barrier layer 102 made of an electrically insulating metal oxide is formed using a vacuum evaporation method, CVD (chemical vapor deposition), or chemical vapor deposition (CVD).
pour deposition) method, glow electrolysis method, sufu<tsutaring method, and ion implantation method.

This is accomplished by ion blating method, electron beam method, etc.

For example, to form the barrier layer 102 by a sputtering method, the starting material for forming the barrier layer, Ueno 1, is used as a target to perform IJ/Ging in a gas atmosphere for sputtering such as He, Ha, Ar, etc. You can do it by doing this.

When using the electron beam method, the starting material for forming the barrier layer may be placed in a vapor deposition boat and evaporated by irradiation with an electro/beam. and amorphous layer 1
The photocarriers generated in 03 move to the support 10.
Since it is intended to easily allow passage to one side, it is formed to exhibit electrically insulating behavior.

The numerical range of the layer thickness of the barrier layer 102 is one of the important factors for effectively achieving its purpose.

If the thickness of the barrier layer 1020 is too thin, the support 1
01 side toward the amorphous layer 103 side, or amorphous F
The function of preventing free carriers from flowing toward the side of the support body 101 from f4103flll becomes insufficient,
Moreover, if the thickness is more than enough, the probability that the photocarriers generated in the amorphous layer 103 will pass to the support body 101 side becomes extremely small, and therefore, in either case, the object of the present invention is not achieved. cannot be achieved effectively.

In view of the above points, the thickness of the barrier layer 1020 to effectively achieve the object of the present invention is usually 30 to 10
0OA, preferably 50-600 people.

In this @ song, how to effectively achieve this purpose, the amorphous layer 103 provided on the support 101 is composed of m-8i(' + x) having the semiconductor properties shown below, Oxygen atoms are doped in the layer thickness direction with a distribution as described below.

■pffls-84(H,X): Contains only acceptor. Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na).

(2) P-type - A type of si(H,

■ Day-type a St (H,X): Contains only the donor.

Or one that contains both a donor and an acceptor and has a high donor concentration (Nd).

(2) The n-type a-8i (H,

■ Straight type a-84 (H,! )-Na! Nd! O's or Na':: NdO's.

In the present invention, specific examples of the halogen atoms (X) contained in the amorphous layer 103 include fluorine, chlorine, bromine, and chlorine, with fluorine and chlorine being particularly preferred. I can list them.

In the photoconductive member 100 of the present invention, amorphous 11103
In some cases, the distribution is substantially uniform in a plane substantially parallel to the surface of the support 1010, non-uniform in the thickness direction of the layer, and on the surface side opposite to the support 101 (the first In the figure, a layer region containing oxygen atoms is formed such that oxygen atoms are distributed more on the free surface 104@) and the position of the maximum distribution t Cmax is on the surface or in the very vicinity thereof. .

2 to 5 show typical examples of the distribution of oxygen atoms contained in the amorphous layer 103 in the thickness direction of the amorphous layer 103. In FIG. 2 to FIG. 5, the vertical axis indicates the layer thickness t of the amorphous layer 103. 103 represents the interface position (lower surface), and tl represents the interface position (upper surface) of amorphous @103 on the free surface 104 side (W, which is the same position as the free surface 104 in Figure 1). , indicating that the layer thickness t increases from to to ts,
The horizontal axis shows the distribution amount C of oxygen atoms at any position in the layer direction of the amorphous layer 1030, and the increase in the distribution amount is shown in the direction of the arrow. This is a book that shows the maximum distribution amount of oxygen atoms in.

In the example shown in FIG. 2, the distribution state of oxygen atoms contained in the amorphous layer 103 extends from the lower surface position WILt to the upper surface position tB. The distribution tc increases monotonically and continuously, reaching the maximum distribution amount Crn□ at the position t1, and thereafter there is no fluctuation in the distribution tc until the surface position 1%, maintaining the value of C,□. . Regarding the second factor, near t0, it appears as if no acid or g atoms are contained at all, but below the detection limit of oxygen atoms, it is dangerous that oxygen atoms are contained. It is nicknamed because it is treated in the same way.

Therefore, in the present invention, the 7m region (for example, the layer region between t- and tl in FIG. 3) where the cage of oxygen atoms is shown as 0 contains no oxygen atoms at all, or Otherwise, it is treated as containing less than the detection limit. At present, at our technological level, the detection limit for oxygen atoms is 200 atoa+ic for silicon atoms.
It is PPm.

In the photoconductive member of the present invention, in order to obtain high photosensitivity and stable image quality characteristics, the distribution state of oxygen atoms is made of an amorphous layer such that the distribution amount increases as the position approaches the upper surface position t. 103 contains an oxygen atom.

When the amorphous @ 103 of the photoconductive member ioo prepared as shown in FIG. The free surface 104 can be provided with a significantly increased capacity to retain the charge applied to the free surface 104.

In this case, such a layer region serves as a so-called barrier layer.

In this way, in the vicinity of the free surface 104 of the amorphous layer 103, the content of oxygen atoms is extremely increased compared to other layer regions, and an upper barrier layer is formed in the amorphous layer 103. Although it is possible to
The upper barrier layer can also be formed using the same material as that constituting 1!102. The thickness of the upper barrier layer at this time is usually 30A to 5μ, preferably 50λ.
It is desirable that the value is ~2μ.

In the example shown in FIG. 3, the lower side t of the amorphous layer 103
・andt! The layer region between the layers contains no oxygen atoms at all or contains less than the detection limit, and the distribution amount of oxygen atoms changes linearly or - from the position tl to ts. Monotonically increasing functionally close to the following function,
At position t1, the maximum distribution amount Cm5x is reached. ts
In the layer region between and ts, oxygen atoms are uniformly contained with a maximum distribution of 1i Cross.

In the example shown in FIG. 4, the lower layer region (between t and t4) of the amorphous Fii 103 contains oxygen atoms evenly and uniformly with a constant amount CI, In the upper layer region (between ta and t30), oxygen atoms are contained in a uniformly distributed state with a maximum distribution amount Cmax, and in the lower layer region and the upper layer region, the distribution amount is discontinuous. It's becoming a target.

In the example shown in FIG. 5, oxygen atoms are contained at a constant p distribution amount C, from the lower surface position of the amorphous [1103] to the position tl, and the position i! The distribution amount of oxygen atoms gradually increases from f and li to position t6, and the distribution amount of oxygen atoms gradually increases from position □ to the upper surface position t.

The oxygen atoms are distributed in such a way that the distribution of oxygen atoms rapidly increases by t until reaching the upper surface position 1s, where the maximum distribution amount is C+a*X.

In the present invention, the maximum distribution of oxygen atoms tCrnax is
Normally, it can take the above-mentioned values, but preferably 0.5 to 67 atomic%, optimally 1.0 atomic%.
It is preferable to select from the range of '67 atomic%.

In the photoconductive member of the present invention, 1. oxygen atoms contained in the amorphous layer 103 are as described in n11.
The distribution of its content is uneven in the greasing direction, and the upper surface Wt or 1. The maximum distribution amount is in the vicinity of the upper surface position t, while the lower surface position t. According to a desired distribution state function, a distribution state in which the amount of distribution decreases in the direction of the layer thickness in the amorphous layer 103 is formed.
By being added to the amorphous layer 103, the intended purpose of the present invention is effectively achieved. The content of is also important for achieving the intended purpose of the present invention.

In the present invention, the value of the total amount of oxygen atoms contained in the amorphous layer 103 is usually in the range of [7], more preferably 0.05 to 20 atomic
4, 0.05 to 10 ato111ic for 171 letters
In the present invention, in order to form the amorphous 1m103 mainly composed of a-8i(t(,X)), for example, claw discharge method, sputtering method, Alternatively, it can be accomplished by a vacuum deposition method that utilizes a radiation phenomenon such as an ion grating method.

For example, in order to form amorphous 1- by the claw discharge method, the internal pressure of the raw material gas for water * atom introduction II and/or halogen atom introduction, together with the Si generation raw material gas that can generate Sr, must be reduced. A glow discharge is generated in the deposition chamber, and a -8i (H+ x
) may be formed. In order to introduce oxygen into the layer to be formed, it is preferable to introduce a raw material gas for introducing acid atoms into the deposition chamber at the time of forming the layer, in conjunction with the growth of the layer.

In addition, when forming by sputtering method, for example, Ar
When sputtering a target formed with 8i in an atmosphere of an inert gas such as , ms, or a mixed gas based on these gases, the hydrogen atoms are used as the parent gas and/or the gas for introducing halogen atoms is deposited for sputtering. You can introduce it into your room.

At this time, the method of introducing oxygen atoms into the amorphous layer 103 is to introduce a raw material gas for oxygen atoms into the deposition chamber at the time of layer formation, in conjunction with the growth of the layer, or, When forming the layer, sputtering may be carried out using a target for introducing oxygen atoms that has been provided in advance in the deposition chamber.

In the present invention, the Si generation raw material gas used when forming the amorphous layer 103 includes "[418I11@,
5t3H@1, 81411 (1 grade) Silicon hydride (silanes) in a gaseous state or that can be gasified is mentioned as one that can be effectively used, especially ease of handling during layer creation work, S1 generation efficiency fJiH4゜5i3)I
@ is preferred.

In the present invention, many halogen compounds are effective as raw material gases for introducing rodan atoms, such as halides, halides, and interhalogen compounds. Preferred examples include gaseous or gasifiable halogen compounds such as halogen-substituted silane derivatives.

Also effective in the present invention are silicon compounds containing silicon atoms and halogen atoms, which are in a gaseous state or contain gasifiable halogens.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine, and iodine.
f Gengas, BrF, CI? , ClF5+BrF
@, BrF3, IF7, IFF, rc
/, IBr, and other interhalogen compounds.

Examples of silane derivatives containing halogen atoms, so-called halogen-substituted silane derivatives include, for example, SiF
4, 5iIP@, SiC/4, SiBr4
Preferred silicon halides are as follows.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing halogen spores, silicon hydride gas as a raw material gas capable of producing Si is not used. In both cases, a-8 is placed on a predetermined support.
t: An amorphous layer consisting of X can be formed.

Amorphous layer 1 containing halogen atoms according to the glow discharge method
When creating 03, basically, silicon halide gas, which is the raw material gas for 84 generation, and gases such as Ar, Hl, I, etc. are mixed at a predetermined mixing ratio and gas flow rate to form an amorphous material. By introducing these gases into the deposition chamber where the layer is to be formed and generating a glow discharge to form a plasma atmosphere of these gases,
The amorphous layer 103 can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of silicon compound gas containing hydrogen atoms is further mixed with these gases to form a layer. You may do so.

Father, each gas can be used not only as a single species, but also in a mixture of multiple types at a predetermined mixing ratio.

Amorphous fi mainly consisting of m-8i (H,
In order to form 103, for example, in the case of a sputtering method, a target consisting of 81 is used and sputtered in a predetermined gas plasma atmosphere, and in the case of an ion blasting method, 1. Polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is heated and evaporated by a resistance heating method or an electron beam method (KB method), etc., and the flying evaporates are evaporated into a predetermined gas plasma atmosphere. This can be done by passing it through.

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

Father, when introducing hydrogen atoms, water vg11! Raw material gas for child introduction, for example, H! A plasma atmosphere of the gas may be formed by introducing a gas such as the above-described gas into a deposition chamber for sputtering.

Oxygen JQ atoms contained in the formed amorphous layer with a desired distribution state in the layer thickness direction are formed by a glow discharge method, an ion blasting method, or a reactive sputtering method. In this case, the raw material gas for introducing oxygen atoms may be introduced into the deposition chamber for layer formation according to a desired flow rate in conjunction with the growth of layers.

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

In the present invention, oxygen (02) is effectively used as a raw material gas for introducing oxygen atoms.

The constituent atoms are ozone (03), Si, 0, and H.

Examples include lower siloxanes such as disiloxane EIsSi081H, and ToIJ siloxane H38i08iH, 0818.4. In the present invention, materials that can be effectively used to form a target for introducing oxygen atoms include sto, sio, and the like.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen used when forming the amorphous layer. In addition, HF, Hcj
, HBr, hydrogen halides such as HI, 5iH1F
1, 8iH■C1g, 5iHCI2 jliHl
Brl.

Halides having a hydrogen atom as one of their constituents, such as halogen-substituted silicon hydrides such as 5iHBr3, which are in a gaseous state or can be cassified, can also be cited as effective starting materials for forming an amorphous layer.

When these halides containing hydrogen atoms are formed into an amorphous state, hydrogen atoms, which are 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. It is used as a suitable raw material for introducing halogen.

In order to structurally introduce hydrogen ions into the amorphous layer, in addition to the above, hydrogen, SiH4, 5tlH@, 5i3
H Hatake.

This can also be achieved by causing a discharge to occur by causing a silicon hydride gas such as 8i4 to coexist with a silicon compound for producing a -3i in the deposition chamber.

For example, in the case of the reactive sputtering method, an 8i target is used, and a gas for introducing halogen atoms, H gas, and inert gases such as Lie and Ar are introduced into the deposition chamber as necessary to create a plasma atmosphere. By forming and sputtering the St metal, an amorphous 1- having predetermined characteristics and mainly consisting of a-8i (H,X) is formed.

Furthermore, BII (-+PH
It is also possible to introduce s*PFm4 gas.

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

To control 1 of ■ or/and X contained in the layer,
For example, the temperature of the deposition support, the amount of the starting material used to contain H into the deposition system, the discharge force, etc. may be controlled.

In order to make the amorphous layer N-type, P-type, or i-type, an n-type impurity is added when forming the layer J by a glow discharge method, a reactive sputtering method, or the like.

This is achieved by doping a type impurity or both impurities into the layer to be formed while controlling the amount thereof.

As impurities doped into the amorphous layer, in order to make the amorphous layer 1 type or p type, elements of group Ⅰ A of the periodic table, such as B, mul, G4゜In, rt4 is preferred.

In the case of an n-type tendency, suitable elements include elements of Group ⅠA of the periodic table, such as N, P, AI, 8b, and Bl.

In the present invention, the amount of impurity introduced into the amorphous material in order to have the desired conductivity type is 3×1o'''1 (below OmjC) in the case of impurities in group A of the periodic table. In the case of impurities belonging to group V of the periodic table, doping may be carried out in an amount of 5 x 10-3 atogmic% or less.

The layer thickness of the amorphous VL size is determined as desired so that the photocarriers generated in the amorphous layer are efficiently transported in a predetermined direction, and is usually 3 to 100 μm, preferably 5 to 100 μm.
It is assumed to be 50μ.

Example 1 Using the apparatus shown in FIG. 6 installed in a completely shielded clean room, an electrophotographic image forming member was produced by the following operations.

A molybdenum plate (substrate) 609 with a square surface of Q, 5 tx * thickness 10 cIL, whose surface has been cleaned, is placed in a glow discharge deposition chamber 601.
They were fixed substantially in the same manner to a fixing member 603 located at a predetermined position inside.

The substrate 609 is connected to the heater 608 inside the fixing member 603.
is heated with an accuracy of ±0.5°C. Mll was made to measure substrate back blood directly by thermocouple (alumel-chromel). Next, after confirming that all valves in the system are closed, the main valve 610 is fully opened and the inside of the chamber 601 is evacuated.
The vacuum level was set to rr. Thereafter, the input voltage of the heater 608 was increased, and the input terminal was changed while detecting the temperature of the molybdenum substrate, and the temperature was stabilized at a constant value of 250°O.

After seven, the auxiliary pulp 641, then the outflow pulp 626,
627,629 and inflow pulp 621°622.624
The total Ml, mass flow controllers 616, 617,
The interior of 619 was also sufficiently degassed and vacuumed. Auxiliary pulp 64
11 Pulp 626°627.629,621,622.
After closing 6'24, SiH4 gas (purity 99.999, hereinafter 31H4QO) diluted to 10vo/% with H-rich
)/H Yuki) pulp 631 from cylinder 611. II
01 gas diluted to 0.1 vol with @ (purity 99.
999%, hereafter O snow (0, 1) / picture e (!: Abbreviation.

) Open the pulp 632 of the cylinder 612 and check the outlet pressure gauge 6.
The pressure of 36,637 was adjusted to 1#/-2, and the inflow pulp 6
21, 622 were gradually opened to allow s+ui(10)/Hs gas and Oeg (old)/&I gas to flow into mass flow controllers 616, 617. By pulling, the outflow pulps 626 and 627 are gradually opened, and then the auxiliary pulp 641
I gradually opened it. At this time, the ratio of 5iH4(1o)/Fh gas flow rate and O snow, l)'le gas flow rate is 10:0.3
The mass flow controllers 616 and 617 were adjusted so that

Next, adjust the opening of the auxiliary pulp 641 while paying close attention to the reading on the Villany gauge 642, and adjust the opening of the auxiliary pulp 641 so that the inside of the chamber 601 is I
The auxiliary pulp 641 was opened until the pressure was -2 Torr. After the internal pressure of the chamber 601 stabilizes, the main pulp 610 is gradually closed and the indications on the Villany gauge 642 are Q and l Tor.
I narrowed down the aperture until it reached r.

After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 643 and close the shutter (
Also serves as an electrode. ) 605 was closed, and a high frequency power of 13.56 Mklg was applied between the electrode 603 and the shutter 605 to generate a glow discharge in the chamber 601, resulting in an input power of 1OW. The above conditions were maintained for 3 hours to form a lower layer region that would become part of the amorphous layer exhibiting photoconductivity.

Thereafter, the high frequency power supply 643 is turned off, the outflow pulp 627 is closed, and the glow discharge is stopped, and then the O! Gas (purity t99.999) is passed from the cylinder 614 through the pulp 634 at a rate of 1 kg/cx*'' (reading of the outlet pressure gauge 639), and the inflow pulp 624,
Gradually open the outflow pulp 629 and set the mass flow controller 619 to 0 snow gas fr KL.
)/It It was stabilized at 1/1O of the gas flow rate.

Subsequently, turn on the 11th frequency power supply 643 again,
Glow discharge was restarted. The input power at that time was set to 3W. After continuing the glow discharge for 10 minutes in this manner to form the E section 1-region that constitutes a part of the amorphous layer to a thickness of 600 mm, the heating heater 608 is turned off.
The high frequency power supply 648 is also turned off, and the board type is 100.
℃, close the outflow pulps 626, 629 and inflow pulps 621, 622, 624, fully open the main pulp 610, and bring the inside of the chamber 601 to 10'Torr or more. The chamber 601 was closed and the inside of the chamber 601 was brought to atmospheric pressure by the leak pulp 606, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member thus obtained was placed in a charging exposure experimental device, subjected to corona charging at 05.5 KV for 0.2111 C, and immediately irradiated with a light image. A light image was generated using a tungsten lamp light source, and a light field of 1.0 /ax sac was irradiated through a transmission type test chart.

Immediately thereafter, a chargeable developer (containing toner and carrier) was cascaded onto the surface of the member to obtain a good toner layer on the surface of the member. Toner 1 on the member
When I was transferred onto a transfer paper using ES and OXV corona charging, a clear, high-density image with excellent image resolution and good secondary appearance was obtained.

Example 2 A molybdenum substrate was installed in the same manner as in Example 1, and then the inside of the glow discharge deposition chamber 601 was
X 10' Torr vacuum, substrate a degree 25
After being maintained at 0°C, the same operation as in Example 1 was performed to prepare the auxiliary pulp 641 and then the effluent pulps 626, 627, 629.
and the inflow pulps 621, 622, 624 are fully opened, and the mass flow controller 616. 617. The interior of 619 was also sufficiently degassed and vacuumed. After closing the auxiliary pulp 641° pulp 626, 627, 629, 621, 622° 624, 5oH4 (10)/Fix gas (pure [99,9
Pulp 631 in cylinder 611 of 99tfb), O, (
0,1)'■Open the pulp 632 of the C gas cylinder 612, adjust the pressure of the outlet pressure gauges 636, 637 to 1 kg/♂, gradually open the inflow pulps 621, 622, and inject 5tu4( 1))
/) Tm gas, o and (0,1)/e were respectively introduced.

Subsequently, the outflow pulps 626 and 627 were gradually opened, and then the auxiliary pulp 641 was gradually opened.

At this time, 8iHa (10)/Hm gas it and o, (
Mass flow controllers 616 and 617 were adjusted so that the ratio of 0,1)/■C gas flow rate was 10:0.3. Next, while paying close attention to the reading on the Billany gauge 642, adjust the opening of the auxiliary pulp 641 to make sure that the inside of the chamber 601 is
The auxiliary pulp 641 was opened until the pressure reached 10' Tort.

After the internal pressure of the chamber 601 stabilizes, the main pulp 610 is gradually closed until the indication on the Villany gauge 641 is 0.1 tons or more.
I narrowed down the aperture until it reached e. After confirming that the gas inflow is stable and the internal pressure is stable, close the shutter (which also serves as an electrode).
6o5 is closed, the switch of the high frequency power source 643 is turned on, and a high frequency power of 13.56 MHz is applied between the electrodes 603 and 605 to generate a glow discharge in the chamber 601.
The input power was 10W. At the same time as starting to deposit an amorphous layer on the substrate under the above conditions, 5tuF14(10)/I
The ratio of s gas flow rate and O, ω, 1)/Ia gas xR amount is 1:
1 to form an amorphous layer exhibiting photoconductivity.

After that, the high frequency power supply 643 is turned off, the outflow pulp 627 is closed with the glow discharge stopped, and then the
1 from gas cylinder 614 through Palflo 34 #
/ (m” gas pressure (outlet pressure gauge 639 reading),
Inflow pulp 624. rIt, gradually open the output half flow 29 and mass flow control o-:>6194Co, gas t-KL By adjusting the mass flow controller 619, O, gas! 911 (4α (1/Fil gas flow rate 1/
It was stabilized to 10.

Subsequently, the high frequency power supply 643 was turned on again to restart the glow discharge. The input power at that time was 3W. After continuing the glow discharge for another 15 minutes to form the upper barrier layer, the heating heater 608 is turned off, the high frequency electric current 5643 is also turned off, and after the substrate temperature reaches 100°C, the outflow pulp 626 ,62
9 and inflow pulps 621, 622, 624 are closed, the main pulp 610 is fully opened, and the inside of the chamber 601 is heated to 10' Ta.
After reducing the temperature to below rr, the main pulp 610 is closed and the chamber 601
The inside was brought to atmospheric pressure using leak pulp 606, and the substrate was extracted. In this case, the total thickness of the layer formed was approximately 15μ. Using this image forming member, a 5bJ-image was formed on a transfer paper under the same conditions and procedures as in Example 1, and an extremely clear image quality was obtained.

Example 3 A molybdenum substrate was installed in the same manner as in Example 1, and then the inside of the glow discharge deposition chamber 601 was made into a vacuum of 5810'r by the same operation as in Example 1, and the substrate temperature was 250°C.
Then, by the same operation as in Example 1, the auxiliary pulp 641, then the outflow pulps 626, 627, and the inflow pulps 621 and 622 were fully opened, and the mass flow controllers 616 and 617 were also sufficiently degassed and vacuumed. . Auxiliary pulp 6411 pulp 626, 627.62-1゜62
After dividing 2, 81H4(1(1/Ha ka, x, (
Pure T-99,999%) Posipero 11 pulp 631
, 0x(0,11e Pulp 63 of gas cylinder 612
2, adjust the pressure of the outlet pressure gauges 636, 637 to 14/door, gradually open the inflow pulp 621, 622, and move the mass 7 a -=t 7 into the toler 616, 617.
1H4Ql174 [1 gas, O! ω and IV were respectively injected. Subsequently, the outflow pulps 626 and 627 were gradually opened, and then the auxiliary pulp 641 was gradually opened. At this time, the inflow pulp 621 is adjusted so that the gtH4ao/Is gas flow rate and o,
, 622 was adjusted.

Next, adjust the opening of the auxiliary pulp 641 while paying close attention to the reading on the Villany gauge 642, and adjust the opening of the auxiliary pulp 641 so that the inside of the chamber 601 is I
'I opened the auxiliary pulp 641 until I got to Torr. room 6
01 After the internal pressure stabilizes, the main pulp 610 is gradually closed and the Villany gauge 641 reads 0.1 Terr.
I narrowed my aperture until it was. Confirm that the gas inflow is stable and the internal pressure is stable, then close the shutter (also serves as an electrode) 6
05 and turn on the switch of the high frequency power source 643, 13.56 MHI of high frequency power is applied between the electrodes 603 and 605 to generate a glow discharge in the chamber 601.
The input power was 1OW. At the same time as the photoconductive layer was started to be deposited on the substrate under the above conditions, the flow rate setting of the mass flow controller (op-617) was continuously increased, and after 5 hours, the SiH4 (J/ 'H@Gas flow rate and (h(0,1)/Is KasIt, t ratio, 1
:IJ to make it 10! 411.

After forming an amorphous layer exhibiting photoconductivity in this way, the heating heater 60B is turned on, and the high frequency power source 643 is also turned on.
ff state, and after waiting for the substrate temperature to reach 100°C, the outflow pulps 626, 627 and the inflow pulps 621, 6
22, fully open the main pulp 61G, and open the chamber 60.
After reducing the inside of 1 to 104T@rr or less, main pulp 61
0 was closed, the inside of the chamber 601 was brought to atmospheric pressure by the leak pulp 606, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 15μ. Regarding this wound forming member,
An image was formed on a transfer paper under the same conditions and procedures as in Example 1, and extremely clear 1ii(*) was obtained.

Example 4 8iH4QQ/Hm gas cylinder 611 was replaced with 8iF4 gas (
H degree 99.999) In the cylinder, 'h(0,1)/l@
The gas cylinder 612 was filled with argon containing 0°2 m/tqb of oxygen (instead of gas, S-F4 gas, tA-Omon, and o, (o, 2)/
Set the gas direct weight ratio to l:0.6, start layer formation, and adjust the SiF4 gas flow rate and Om(
Photoconductivity was exhibited on the molybdenum substrate under the same operating conditions as in Example 3, except that the gas flow was continuously applied and the input power of the glow discharge was set to IOOW. An amorphous layer was formed. The thickness of the skin formed in this case is
It was about 18μ. An image was formed on a transfer paper using this Tsugai powder under the same conditions and procedures as in Example 1, and an extremely clear Ithi image was obtained.

Example 5 A molybdenum substrate was installed in the same manner as in Example 1, and then the inside of the glow discharge deposition chamber 601 was filled with 50% by the same operation as in Example 1.
X 10' Tarr vacuum and no substrate i! degree is 25
After being kept at 0°C, the auxiliary pulp 641 and then the effluent pulp 626. 627. 628°629, inflow pulps 621, 622, 623°624tlaL, and mass plow controllers 616°617, 618, 619 were also sufficiently degassed and vacuumed.

Auxiliary pulp 641. Pulp 626, 627°628, -
629, 621, 622, 623, 624 closed (&
8iH40 (1/-pulp 63 of gas cylinder 611
Pulp 632 from cylinder 612 of 1,0 tonne CO, Wk gas
．． BIH@gas diluted to 50 to7 ppm with H, (pure - [99,999%, hereinafter hH@(50)/H,
It is abbreviated as ) Open the pulp 633 of the cylinder 613, adjust the pressure of the outlet pressure gauges 636, 637, 638 to 1 kg/ad, gradually open the inflow pulp 621, 622, 623, and set the mass flow controller 61'6°617.6. 1
81HaQ (1/Ha scum, 0s(0,1)/
IS gas, B, H, (50)/H1 gases were introduced.

Subsequently, the outflow pulps 626, 627, and 628 were gradually opened, and then the auxiliary pulp 641 was gradually opened. At this time, 8iH4 (Ill/Hl gas flow violet and 0 mushroom Φ, 1)/
The ratio of lie gas Ilt amount is 10:0.3,! 1
lH40 (1/H snow gas flow rate and B鵞Ha(50)/H
The mass flow controllers 616, 617. The auxiliary pulp 64 is adjusted while paying close attention to the reading of the zero-order Billany gauge 642 after adjusting the stg.
Adjust the opening of 1 to iA [2, the inside of chamber 601 is I x 10'T
The auxiliary pulp 641 was opened until it reached arr. Room 601
After the internal pressure became stable, the main pulp 610 was gradually closed and the opening was narrowed until the Villany gauge 642 indicated Q, l Torr. Confirm that the gas inflow is stable and the internal pressure is stable, then turn on the high frequency power supply 643.
Shutter (also serves as tJt pole) 605
with electrode 603. closed. 13 between the shutters 605.
A high frequency power of 56 MFIg was applied to generate a glow discharge in the chamber 601, resulting in an input power of 1OW. The above conditions were maintained for 3 hours to form a lower 1-region constituting a part of the amorphous layer exhibiting photoconductivity. After that, high frequency power supply 6.1
3 is turned off and glow discharge is stopped,
Effluent pulp627. 628 is closed, and a gas pressure of 1 kg/cd (
The outlet pressure gauge 639 is used to gradually open the inflow pulp 624 outflow valve 629 and the mass flow controller 6
19, Hegas t-ML mass flow controller 616.
6tsola! Seiyo, Tsute Hegas, giH4 (i
The IAO was stabilized to a flow rate of 1/'H+ gas.

Subsequently, the high frequency power supply 643 was turned on again to restart the glow discharge. The human power at that time was set to 3W. In this way, after continuing the glow discharge for 10 minutes to form an upper layer region that will become a part of the amorphous layer to a thickness of 600 mm, the heating heater 608 is turned off, and the high frequency power source 643 is also turned off. After waiting for the substrate temperature to reach 100°C, close the outflow pulps 626, 629 and inflow pulps 621, 622, 623, 624, fully open the main pulp 610, and reduce the inside of the chamber 601 to 104〒ore or less, The main pulp 610 was closed, and the inside of the chamber 601 was brought to atmospheric pressure by the leak pulp 606, and the substrate was cut out. In this case, the total thickness of the layer formed was approximately 9μ.

The image forming member thus obtained was placed in a charging exposure experiment apparatus, and the image forming member was set at θ5. Corona charging was performed for 0.28 hours using SKY, and a light image was immediately irradiated. The optical image was obtained by irradiating light of 1.0 /ax -5 ac through a transmission type test chart using a tungsten lamp light source.

Immediately thereafter, (1) a charged developer (including toner and gear) was cascaded onto the surface of the member to obtain a good toner image on the surface of the member. When the toner image on the member was transferred onto transfer paper using ES and OXV corona charging, it was eroded by the resolving power and a clear, high-density TH image with good gradation reproducibility was obtained.

Next, on the above-mentioned forming member, es was applied to the electrostatic exposure experimental device.
o K v-t'0.2seei41o) o - is charged, and image exposure is immediately performed with a light intensity of 0.81ux@wwz. Immediately thereafter, a θ-chargeable developer is cascaded onto the surface of the member, and then When transferred and fixed onto transfer paper, an extremely clear image was obtained.

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

Example 6 Using the apparatus shown in FIG. 6, an electrophotographic image forming member was produced by the following operations.

It was firmly fixed to the fixed member 603 in position.

忤) was installed. The substrate 609 is the fixing member 6
It is heated with an accuracy of ±0.5° C. by a heater 608 in 03. Temperature is measured using a thermocouple (alumel-chromel)
The backside of the board was measured directly using the method. Next, after confirming that all the pulp in the system is closed, the main valve 610 is fully opened and the 5 x 104t
The vacuum is evacuated to about
After the mass flow controllers 616, 617, 619, 620 are sufficiently deaerated by opening the mass flow controllers 616, 627, 629, 630, the outflow valves 626, 627, 629, 63 are opened.
0 and the auxiliary valve 641 was closed. Argon (purity 99.99 ([6) Gas cylinder 615 valve 6
35 and the outlet pressure needle 640 is 1 kg/
cm", the inflow valve 625 was opened, and then the outflow pulp 630 was gradually opened to allow argon gas to flow into the chamber 601. The reading on the Pirani gauge 611 was 5 x 10". The outflow pulp 630 is gradually opened until it reaches tart, and after the flow becomes stable in this state, the main valve 610 is gradually closed and the opening is narrowed until the indoor pressure reaches I x 10-2 totr. Ta. After opening the shutter 605 and confirming that the mass flow controller 620 is stable, turn on the high frequency power supply 6.
43 was turned on, and AC power of 13.56 MHz, OOW was input between the target 604 and the fixing member 603.

Under these conditions, matching was performed to continue stable discharge, and a layer was formed. Continue discharging in this way for 1 minute and
A lower barrier layer of 0λ1 was formed. Then high frequency power supply 6
43 was turned off, and the discharge was stopped for one cycle. Subsequently, the outflow pulp 630 was closed, and the main valve 610 was fully opened to remove gas from the chamber 601, creating a vacuum of 5×10′ otr. After that, the input voltage of the heater 608 is increased, and the input voltage is changed while detecting the substrate temperature.
It was stabilized until it reached a constant value of 0°C. Thereafter, an amorphous layer exhibiting photoconductivity was formed under the same operations and conditions as in Example 1. Example 1 The image forming member thus obtained
When an image was formed on transfer paper under the same conditions and procedures as described above, an extremely clear image quality was obtained.

Example 7 A molybdenum substrate was formed on a molybdenum substrate under the same operations and conditions as in Example 4, except that the argon gas cylinder 612 containing 0.2 vo/% oxygen in Example 4 was replaced with a helium gas cylinder containing 0.2 vol/% oxygen. An amorphous layer exhibiting photoconductivity was formed.

The thickness of the layer formed in this case was approximately 15μ. When this image forming member was used to form an image on a transfer paper under the same conditions and procedures as in Example 1, a very clear image was obtained.

[Brief explanation of the drawing]

FIG. 1 is a schematic block diagram for explaining the layer structure of a preferred embodiment of the photoconductive member of the present invention, and FIGS. 2 to 5 each show an amorphous structure of the photoconductive member of the present invention. 1j contained in
II; Schematic explanatory diagram for explaining the distribution state of J atoms,
FIG. 6 is a schematic explanatory diagram showing an example of an apparatus for producing the photoconductive member of the present invention. 100--photoconductive member, 101... support, 10
2... Barrier layer, 103... Amorphous layer. Applicant Canon Co., Ltd.

Claims (1)

[Claims] The amorphous layer includes a support for a photoconductive member, an amorphous layer made of an amorphous material having silicon atoms as a matrix and which reduces photoconductivity, and a barrier layer. It has a layer region containing oxygen atoms in part, and the distribution of oxygen atoms in the layer region is uneven in the thickness direction of the layer, and the oxygen atoms contained in the layer region are A photoconductive material that is characterized by its large distribution on the surface opposite to the body.