JPS5833259A - Manufacture of 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 atmosphere, 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 times. CONSTITUTION:Desired internal pressure is obtained by leading desired gas into an accumulation chamber whose pressure can be reduced, an amorphous photoconductive layer 102 whose base body is a silicon atom is formed on a supporting body 101 by providing electric discharge energy to a starting substance for feeding the silicon atom, being in the accumulation chamber concerned, and subsequently, a surface barrier layer 103 is formed on said photoconductive layer 102 by providing electric discharge energy to a starting substance for forming an amorphous material consisting of a silicon atom as its base body and containing a carbon atom and a halogen atom. 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 method for manufacturing a photoconductive member that is sensitive to electromagnetic waves such as light (light here in a broad sense, including ultraviolet light, visible light, infrared light, X-rim, rlil, etc.). As a photoconductive material for forming a photoconductive layer in a solid-state imaging AT1 or an image forming member for electrophotography in the image forming field, a document Ta take-up device, etc., it has a high sensitivity and a low signal-to-noise ratio [original current (I)].
p)/dark electric fi(Id)') is high, has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has a desired dark resistance m', and during use. No pollution to the human body,
Furthermore, solid-state imaging devices are required to have characteristics such as being able to easily process IA images within a predetermined time. In particular, in the case of an electrophotographic image forming member incorporated in an electrophotographic apparatus used in an office as a business machine, the upper m
The non-polluting nature of the use of l is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-8i and Re-t)-1 is a photoconductive material that has recently attracted attention.
)”h9.94LF!, M Etil Public 11iI I
Publications I 2746967 and I 2855718 include I# Kaisho 55-39 as an image forming member for electrophotography.
Publication No. 404 describes the application to photoelectric conversion/reading devices.
has been done. According to Heigo et al., a photoconductive member having a photoconductive layer composed of conventional A-8I has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. There are points that can be further improved in terms of 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. For forming parts, etc.
The reality is that it cannot be used effectively considering productivity and mass production. For example, when applied to electrophotographic image forming members, it has often been observed that residual potential remains during use, and when such photoconductive members are used repeatedly for a long time,
There have been many inconveniences, such as the accumulation of fatigue due to repeated use and the so-called ghost phenomenon in which an afterimage occurs. 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
-8i is conventional Be, , Od8゜ZnO or P
It has many advantages compared to 0PO (organic photoconductive materials) such as vOz+TNF, but it has properties for use in conventional solar cells and has a single-layer photoconductive layer consisting of 9A-8I. Dark decay (
(dark decay) is extremely fast, making it difficult to apply normal electrophotography; and in a humid atmosphere, the above tendency is remarkable, and in some cases, it may not be possible to retain any electrical charge at all until the current time. It has been found that there are possible points that can be solved, such as the following. Therefore, while efforts are being made to improve the properties of the A-8S material itself, it is also necessary to take measures to obtain the desired electrical, optical, and photoconductive properties as described above when designing photoconductive members. be. The present invention has been made in view of the above-mentioned points, and is particularly concerned with applicability and applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research from this perspective, we have found that an amorphous material that uses silicon atoms as its base and contains at least either a water bulk atom (H) or a halogen atom (X), hydrogenated amorphous silicon, and halogen oxidized thiamorphous silicon, or halogenated amorphous silicon IIL, the generic notation for these is a.
-8i (H, In addition, we have found that it is superior in most respects to conventional photoconductive materials, and in particular, has significantly superior properties as a photoconductive material for electrophotography. Based on. The electrical, optical, and photoconductive properties of the present invention are stable at all times, and it is suitable for all environments with almost no restrictions on usage environments.It is extremely resistant to light fatigue and does not cause deterioration even after repeated use. The main purpose of the present invention is to propose a method for producing a light guide Ls material in which no or almost no residual potential is observed. Another object of the present invention is to propose a method for manufacturing a photoconductive member that has high photosensitivity, has a spectral sensitivity range that covers almost the entire visible light range, and has a fast photoresponsiveness. Another object of the present invention is to have charge retention ability during charging treatment for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an osteogenic member for electrophotography. It is an object of the present invention to propose a method for producing a photoconductive member having excellent electrophotographic properties, which has sufficient electrophotographic properties and shows almost no deterioration in its properties even in a humid atmosphere. Still another object of the present invention is to propose a method for manufacturing a photoconductive member for electrophotography, which can produce high-quality images with high density f, clear halftones, and high resolution. It is. The method for producing a photoconductive member of the present invention is to introduce a desired gas into a deposition chamber that can be reduced in pressure to achieve a desired internal pressure, apply discharge energy to a starting material for supplying silicon atoms in the deposition chamber, and deposit the material onto a support. forming a photoconductive layer made of an amorphous material having silicon atoms as a host, then applying discharge energy to a starting material for forming the amorphous material having silicon atoms as a host, and containing carbon atoms and nitrogen atoms; A surface barrier layer is formed on the photoconductive layer using t-% mold. The photoconductive member produced by the production method of the present invention is I#
It can solve all of the various problems associated with the arrangement, and exhibits extremely excellent electrical, optical, and photoconductive properties as well as usage environment characteristics. In particular, when applied as an image forming member for electrophotography or an imaging device, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has excellent electrical properties even in a humid atmosphere. It is stable, has high sensitivity, has a high 8N ratio, and has excellent resistance to light fatigue and repeated use. Furthermore, in the case of electrophotographic image forming members, it has a high density,
It is possible to obtain a high-quality visible image with clear halftones and a high degree of resolution. Furthermore, when applied to an electrophotographic image forming member, a5t (H, x) with high dark resistance has low photosensitivity, and conversely, a -8i (H,
In either case, the photoconductive layer with the conventional layer structure is not applicable to the defect forming member for electrophotography, and in the case of the present invention, the specificity is low. The layered structure has a relatively low resistance (more than 5 x 10 Ω bacteria).
Since a-84 (H, a-8
Restrictions from the characteristics of i(H,X) can be alleviated. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. Figure 1 is a schematic configuration diagram schematically shown to explain a basic configuration example of the photoconductive member of the present invention. A photoconductive member 100 shown in FIG. 1 has a photoconductive layer 102, a dazzling conductive layer 1,
02 and a surface barrier layer 103 provided in direct contact with the surface barrier layer 103. The support 101 may be either electrically conductive or electrically insulating. As the conductive support, for example, N t Or
+Stainless steel, Al+Or, Mo, Au. Examples include metals such as Nb, Ta, V, Ti, Pt, and Pd, and alloys such as these. 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, and polyamide, and glass. Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NtCr is applied to its surface. Az, Or, Mo, Au, Ir, Nb, Ta, V, Ti
, Pt, Pd. In, 0. ．． 8nO,, ITO(In, 03+SnO,
) Conductivity is imparted by providing a thin film consisting of fat, or in the case of a synthetic resin film such as a polyester film, N+Or+A/, Ag, Pb, Zn, Ni
, Au. A thin film of metal such as Or, Mo+Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal to make the surface conductive. gender is given. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If used as a component, in the case of continuous high-speed copying,
It is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that the desired photoconductive member is formed, but if the photoconductive member is required to have flexibility, the thickness of the support may be determined to ensure that it does not fully perform its function as a support. It is made as thin as possible within the range. In such cases, the thickness is usually set to 10 μ or more in view of manufacturing and handling of the support, mechanical strength, etc. The surface barrier layer 103 has a function of preventing surface charges from being injected into the photoconductive layer 102 when its surface is subjected to charging treatment. The selection of the material constituting the surface barrier layer 103 and the determination of its layer thickness are determined by the irradiation when the photoconductive member 100 is used in such a way that the electromagnetic waves that the photoconductive layer 102 senses are irradiated from the surface barrier layer 103 side. This is done carefully so that a sufficient amount of the electromagnetic waves generated can reach the photoconductive layer 102 to efficiently generate photocarriers. The surface barrier layer 103 is made of a non-photoconductive amorphous material Ca-(SixOt-x), which is made of silicon atoms and carbon atoms and contains halogen atoms (denoted as X). However, the surface barrier layer 103 prevents surface charges from being injected into the photoconductive layer 102 when the surface thereof is subjected to charging treatment. It is loaded with functions. The surface barrier layer 103 formed by a-(Sizel-x)y; These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, equipment capital investment, load level, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured, so that the desired characteristics can be obtained. The glow discharge method has advantages such as it is relatively easy to control the manufacturing conditions for manufacturing photoconductive members, and it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the surface barrier layer to be manufactured. Alternatively, a sputtering method is preferably employed. Furthermore, in one embodiment of the present invention, the surface barrier layer 103 may be formed by using a glow discharge method and a sputtering method in the same apparatus system. K to form the surface barrier layer 103 by glow discharge method is a-(8iz01-2)y:Xt-yM composition (D
The raw material gas is mixed with a dilution gas at a predetermined mixing ratio as needed, and introduced into a deposition chamber for vacuum deposition where the support 101 is installed, and the introduced gas is caused to cause glow discharge. As a result, the gas becomes plasma and 2-
(81XOIX)Y'X1-9 may be deposited. In the present invention, a-(8jz01-x)y:Xt-
As the raw material gas for forming y, most gaseous substances containing at least one of 8t, O, and X as a constituent atom or gasified substances that can be gasified can be used. When using a raw material gas having 8i'f as a constituent atom as one of S + +0 +

[The raw material gases having constituent atoms are mixed at a desired mixing ratio, or the raw material gases having S+ constituent atoms and the raw material gases having O and Alternatively, a raw material gas having 5it- constituent atoms and a raw material gas having three constituent atoms, Si, O, and X, can be mixed and used. Father, separately, C is added to the raw material gas whose constituent atoms are Si and X.
A mixture of raw material gases having constituent atoms may be used. In the present invention, the preferred halogen atom X is i'
, 0/, Br, and I, with F and Ot being particularly desirable. In the present invention, the surface barrier layer 103 Fi,a-(Sj
zOs-x)y: It is composed of Xt-y,
The surface barrier layer 103 can further contain hydrogen atoms. The inclusion of hydrogen atoms in the surface barrier 11111103 is advantageous in terms of production costs since it is possible to share some of the raw material gas types when forming a continuous layer with the photoconductive layer 102. In the present invention, raw material gases that can be effectively used to form the surface barrier layer 103 include gaseous substances or substances that can be easily gasified at normal temperature and normal pressure. I can do it. Such substances for forming the surface barrier layer include, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, simple halogens, and halogens. Hydrogenide, interhalogen compounds, silicon halides. Examples include halogen-substituted silicon hydride and silicon hydride. Specifically, the saturated hydrocarbon is methane (OH4). Ethane (Ox Ha), Propane (OsHa),”
- Geta 7 (n-0, H, 0), pentane (CsHl), ethylene hydrocarbons such as ethylene (0, H,)
, propylene (Os Hs), butene-1 (04H
s), butene-2 (C6). Isobutylene (04H1), pentene (OsH+o
), acetylene hydrocarbons include acetylene (O
tHz). Methylacetylene (03H4), butyne (0,H,),
Single halogens include fluorine, chlorine, bromine, and iodine, and hydrogen halides include FH and Hl.
, HO/, HBr, as an interhalogen compound, B
rP, OzF, OtF, OtF, BrF, BrF3°IF7. IF, IOz, IBr, halogenated silicon is 8tP, , 8itFa, 8tOta, S
*0z3)3r, 8i0/, Br, 18+0IBr
B , StO/sI , 5tBr41 As the halogen-substituted silicon hydride, 8 *H,F, , 8 IH,O
z, , S 1HOz, +81H10/ , 8 i
H, Br, SiH, Br, Is 1HBr,
, as silicon hydride, 5i)I, +8itHs,
8i,)(,,si,)(1゜special silane (8i 1a
ne), etc. In addition to these, %oar, ,OHF, ,OH,F,
,OH,F. OH, Oj, OH, Br, OH, I, 0. H, Or
Halogen-substituted paraffinic hydrocarbons such as 33, 8F4.
Fluorinated sulfur compounds such as 8Fs, 5i(on,)4
．． 8i(OtHs)4. Alkyl silicides such as 8 i
C1(OHs)s = 8i01tC0Hs%
. Derivatives of silanes such as halogen-containing alkyl silicides such as 8 ill, OH, etc. can also be mentioned as effective. The surface barrier layer forming substance ◆ contains silicon atoms in a predetermined composition ratio in the surface barrier layer to be formed. They are selected and used as desired when forming the surface barrier layer so that they contain carbon atoms, halogen atoms, and optionally hydrogen atoms. For example, 8 i (OHs )4, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms and form a surface barrier layer with desired characteristics, and 8 iHO, which can contain halogen atoms. /, , S io/4゜8
ASI
-1: A surface barrier layer consisting of Ol:H can be formed. To form the surface barrier layer 103 by the sputtering method, a single crystal or polycrystalline 8i wafer or 0 wafer or a mixture of St and C is used. Be sure to use these as halogens to target wafers that contain them! Depending on the requirements, sputtering may be performed in various gas atmospheres containing hydrogen as a component. For example, if a T or ST wafer is used as a target, all the raw material gases for introducing C and The Sl wafer may be sputtered by forming a gas plasma. Alternatively, sputtering can be performed in a gas atmosphere containing at least nitrogen atoms by using Si and C as separate targets or by using a single mixed target of St and C. Ru. C
The material for forming a surface barrier layer shown in the glow discharge example described above can also be used as a material gas for the introduction of X and, if necessary, H, as an effective material for the sputtering method. In the present invention, so-called rare gases such as He, Ne, Ar, etc. are preferably used as the diluent gas used when forming the surface barrier layer 103 by a glow discharge method or a sputtering method. I can do it. The surface barrier layer 103 in the present invention is carefully formed so as to provide the required properties as desired. In other words, a substance whose constituent atoms are Si, 0, X, and optionally H has a structure ranging from crystalline to amorphous depending on its preparation conditions, and an electric property ranging from conductivity to amorphous. In the present invention, non-photoconductive a-( 8
i) The production conditions are strictly selected so that (Ot-x)y'X1-9 is formed. a-(8i) constituting the surface barrier layer 103 of the present invention
cat-x)y:XI Y has a function of preventing surface charges from being injected into the photoconductive layer 102 when the surface of the surface barrier layer 103 is subjected to charging treatment. Therefore, it is formed to exhibit electrically insulating behavior. Furthermore, when the photocarriers generated in the photoconductive layer 102 pass through the surface barrier layer 103, the passage is made smoothly @fK, and the mobility (mo
a ( bi l ity ).
SIXOI-X) A: X, An important factor in the production conditions is the temperature of the support during production. That is, a (stxct x) on the surface of the photoconductor 102
When forming the surface barrier layer 103 consisting of y: In the present invention, a-(8ixOx-1
)y: The temperature of the support during layer formation is strictly controlled so that X knee y can be formed as desired. In order to effectively achieve the desired purpose in the present invention, the temperature of the support during formation of the surface barrier layer 103 is selected in an appropriate range in accordance with the method of forming the surface barrier layer 103. , the formation of the surface barrier layer 103 is carried out, typically from 100 to 300"O, preferably 150-2
It is desirable to set the value to 50'0. In forming the surface barrier layer 103, the photoconductive layer 1o2 and the surface barrier layer 103 can be formed continuously in the same system, and the composition ratio of atoms constituting each layer can be carefully controlled. It is advantageous to employ a glow discharge method or a sputtering method because the control is relatively simple compared to other methods, but when forming the surface barrier layer 103 using these layer formation methods, Similar to the support temperature described above, these are 11 important factors that influence the characteristics of a-(8 amount x OX-,) y:Xl-y, which is generated by the discharge power during layer formation. a- having the characteristics for achieving the object of the present invention;
The discharge power conditions for (at, (Ol-x)y:
200W, preferably 20-100W. The gas pressure inside the deposition chamber is normally 0. The amount of carbon atoms and halogen atoms in the surface barrier layer 103 in the photoconductive member of the present invention is as follows: Surface barrier layer 10
Similar to the 3Q development conditions, this is an important factor in forming the surface barrier layer 103 that provides the desired characteristics to achieve the object of the present invention. 1 lti of carbon 1 g atoms contained in the surface barrier layer 103 in the present invention, usually 40 to 90 atomic % r
Preferably 50-90 atomic %, optimally 60
It is desirable that it be ~8° atomic*. The content of halogen atoms is usually 1 to 20
atomic * + preferably 1 to 18 atomic
% + most preferably 2 to 15 atomic %, and these ranges are sufficient for practical application of photoconductive members made with halogen contents. The content of hydrogen atoms included according to the membership fee is usually 19 atomic or less. Preferably, it is 13 atomic% or less. That is, the previous 1-(8izOt-x)y:Xt
-y C) If done in display, X is usually 0.1 to 0.47
．． Preferably 0.1 to 0.35. 0,15~0 for fi suit
．． 30. y is usually 0.99 to 0.80. Preferably 0.9
9-0.82. Optimally, it is between 0.98 and 0.85. If both a halogen atom and a hydrogen atom are included, the numerical range of x and y in this case is also a-( 8
ix01-X)y: Almost the same as the case of Ly. The numerical range of the layer thickness of the surface barrier layer 103 in the present invention is as follows:
This is one of the important factors for effectively achieving the purpose of the present invention. If the layer thickness of the surface barrier layer 103 is too thin, it will not be able to sufficiently prevent surface charges from flowing into the photoconductive layer 102 from its surface, and if it is too thick, The probability that photocarriers generated in the photoconductive layer 103 pass through the surface barrier layer 103 and recombine with surface charges is extremely small, so in any case,
Therefore, the object of the present invention cannot be effectively achieved. Surface barrier layer 10 for effectively achieving the object of the present invention
The layer thickness of No. 3 is usually 30X to 5 μm, preferably 50 A to 2 μm. In the present invention, in order to effectively achieve the object, the photovoltaic layer 102 formed on the support 101 is composed of a-8i (H,X) having the semiconductor characteristics shown below. . ■ p-type a-8i (H,X) ・Contains only acceptor. Alternatively, one that contains both a donor and an acceptor and has a high concentration of acceptor (Na). 0p-type a 8 t (H+
Lightly doped with type impurities. ■ n-type a-8i (H,X): Contains only a donor. Or one that contains both a donor and an acceptor and has a high donor concentration (Nd). (2) n-type a-8i (H*X)... In type (2), the donor concentration (Nd) is low, so-called non-doped, or lightly doped with n-type impurities. ■ Type i a-8i (H,X)-Na x d-o or Na and Nd. In the present invention, specific examples of the halogen atoms (X) contained in the photoconductive layer 102 include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it. In the present invention, the photoconductive layer 102 composed of a 8 t (H+ Ru. For example, in order to form a photoconductive layer composed of a-8i (H, A glow discharge is generated in the deposition chamber by introducing raw material gas into a deposition chamber whose interior can be reduced in pressure, and a-8i (H, What is necessary is to form a layer consisting of. In addition, when forming by sputtering method, for example, Ar
When sputtering a target made of Si in an atmosphere of an inert gas such as +He or a mixed gas of these gases, a gas for introducing hydrogen atoms and/or halogen atoms is added to the deposition chamber for sputtering. It would be good to introduce it. The St-generating raw material gas used in the present invention includes:
Silicon hydride (silanes) in a gaseous state or capable of being gasified, such as 8iH4,st,u, ,Si,H,,8i,H,, etc.
Among these, 8iH4, Si, and H. are particularly preferred from the viewpoint of ease of handling during layer formation work and good production efficiency. Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention.
For example, halogen gases, halides, interhalogen compounds, and halogen compounds in a gaseous state or which can be gasified, such as halogen-substituted nine-silane cast conductors, are preferably mentioned. Furthermore, a structure 1 consisting of a silicon atom and a halogen atom!
In the present invention, halogen-containing silicon compounds in a gaseous state or capable of being gasified as a fuel can also be mentioned as effective. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine, and iodine halogen compounds x, BrP, 0/F, 0/F, lBr1', +
Bri+”, *IF, +IF, *IOz
+ IBr and other interhalogen compounds can be mentioned.゛Silicon compounds containing halogens, so-called halogen-substituted silane cast conductors, are specifically, for example, S r F4 + S t I F @ r 8 t
014 e S t B r4 and the like are preferred. When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing halogen, it is not necessary to use silicon hydride gas as a raw material gas that can generate Bit-. , a-8i on a given support:
A photoconductive layer consisting of X can be formed. Photoconductive layer 1 containing halogen atoms according to the glow discharge method
Basically, when manufacturing 02, silicon halide gas, which is a raw material gas for SL generation, and gases such as A1, L(, He, etc.) are mixed at a predetermined mixing ratio and gas flow rate, and photoconductive The photoconductive layer 102 can be formed on a predetermined carrier by introducing these gases into a deposition chamber in which the layer is to be formed and generating a glow discharge to form a plasma atmosphere of these gases. In order to introduce hydrogen atoms, a layer may be formed by mixing a predetermined amount of a silicon compound gas containing hydrogen atoms with these gases. Also, each gas may be used not only singly but also at a predetermined mixing ratio. A-
In order to form a photoconductive and electrically conductive layer made of 8t (H, KFi in case of law
Polycrystalline silicon or monocrystalline silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is heated using a resistance heating method.
Alternatively, it can be carried out by heating and evaporating by electron beam method (EB method) 4 and passing the flying evaporated material through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion grating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H! , if a gas such as the above-mentioned 7-Ran type is introduced into a deposition chamber for sputtering and a plasma atmosphere of the gas is formed. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen, and in addition, HF + HOt and HBr. HI Hiron no 10 Hydrogenide, Sin, p,, 5i) (
,a/,. 5iHO13, 8iH, Br, , 5iHBri41/"10-substituted silicon hydride, etc. in a gaseous state or capable of being gasified, water-X atom 1 to 4101)
- Logenides can also be mentioned as effective starting materials for forming the photoconductive layer. When using these halides containing hydrogen atoms, water atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the layer during the formation of the photoconductive layer. It is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the photoconductive layer, in addition to the above, Hl or 8 iH4+ 8 i, H, + si
,H,. This can also be carried out by causing a discharge by causing a silicon hydride gas such as 8i4H1° to coexist with a silicon compound for producing Si 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, and gas are required! Depending on the situation, a plasma atmosphere is formed by introducing inert gases such as He and Ar into the deposition chamber.
By sputtering the i-target, a photoconductive layer of a-81(H,X) is formed on the substrate. Furthermore, B, H, which also serves as a doping book for impurities. It is also possible to introduce gases such as PN, PP3, etc. In the present invention, the amount of H or X or (H+X) contained in the photoconductive layer of the photoconductive member to be formed is usually 1 to 40 atomic %, preferably 5 to 30 atomic %.
It is desirable that it be atomic-. To control the amount of H 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 photoconductive layer have a nil tendency or a pal tendency line i type, it is necessary to add an n-type impurity, a p-type impurity, or both impurities to the formed layer during layer formation by a glow discharge method, a reactive sputtering method, etc. This is achieved by doping while controlling the amount. The impurities doped into the photoconductive layer include rJl or p! ! 1 trend, use Periodic Table V
Elements of group A, e.g. s B r A l * G a
Preferred examples include rIn, T/ and the like. When the nM tendency is desired, elements of Group V A of the periodic table, such as N, P, As, Sb, and Bi4, are suitable. The amount of impurities doped into the photoconductive layer is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities from group V of the periodic table, it is 3×10.
``It is sufficient to dope within the range of atomic 9g, and in the case of impurities in group V of the periodic table, it is 5 x 10-
It is desirable that the doping be carried out in an amount less than ``atomic''.The layer thickness of the photoconductive layer is determined as desired so that photocarriers are efficiently generated in the photoconductive layer and efficiently transported in a predetermined direction. In the present invention, the surface barrier layer 103 is provided so that the photoconductive layer 102 can be used even if it has a relatively low resistance. However, in order to obtain better results, the dark resistance of the formed photoconductive layer 102 is preferably 5xi
It is desirable that the photoconductive layer 102 be formed so that the resistance is at least o'-01, most preferably at least 101@Ω. In particular, this numerical condition for the dark resistance value is such that the produced photoconductive member is used as an image forming member for electrophotography, a highly sensitive reading device or imaging device used in a low illuminance region, or a photoelectric conversion device. This is an important element in some cases. The thickness of the photoconductive layer 1020 of the photoconductive member according to the present invention is appropriately determined according to the purpose of the application, such as a reading device, a photographing device, or an electrophotographic image forming member. In the present invention, the layer thickness of the photoconductive layer 102 is set such that the surface barrier layer is set such that the function of the photoconductive layer 102 and the function of the barrier layer are each effectively utilized and the object of the present invention is effectively achieved. The layer thickness can be appropriately determined depending on the layer thickness relationship with the layer 103, and in normal cases, the layer thickness is preferably 6 to several thousand times or more than the surface barrier layer 1030 layer thickness. It is. Example 1 Using the apparatus shown in FIG. 2 installed in a completely shielded clean room, a photoconductive member having the layered structure shown in FIG. 1 was produced by the following operations. A molybdenum plate (substrate) 205 with a square surface of 0.5 m and a thickness of 1 ocIL, whose surface was cleaned, was firmly fixed to a fixing member 203 at a predetermined position in the deposition chamber 201 . The substrate 205 is connected to the heater 204 inside the fixing member 203.
is heated with an accuracy of ±0.5°C. Temperature was measured directly on the backside of the substrate by a thermocouple (alumel-chromel). Next, after confirming that all the pulps in the system are closed, the main pulp 228 is fully opened and heated to 5 x 10 torr.
The vacuum is evacuated to about
, 223, 224゜225.226 are opened, and after the flow meters 235゜236.237, 238, 239 are sufficiently degassed, the outflow pulp 222.223.22
4.225. 226 and auxiliary pulp 227 were closed. Here, the heater 204 was turned on and the substrate temperature was set to 250"0. Thereafter, 5tr4 gas (purity 99.999%, hereinafter referred to as 84Fn (70)/Hm
pulp 212. at2+) in cylinder 207. Hs
Dilute 500vpp mK with tL fr-BsHa
Open the pulp 213 of the cylinder 208 (hereinafter referred to as BmH@(500)/H) and set the pressure on the outlet pressure gauges 230, 231 to l kg/cam.
7 o- by gradually opening the inflow pulps 217 and 218
81F4 (70)/lit into No. 1-235, 236
i, fhHs (500″VH!?) The inflow of gas was started.Subsequently, the outflow pulps 222 and 223 were gradually opened, and then the auxiliary pulp 227 was gradually opened.At this time, s+v4 (70)/Hm gas flow rate. a, ti. The openings of the inflow pulps 217 and 218 are adjusted so that the ratio with the (500)/Hz gas flow rate is 70 = 1, and the opening of the auxiliary pulp 227 is adjusted so that the inside of the chamber 201 is 10
'torr was maintained. After the internal pressure of the chamber 201 becomes stable, the main pulp 228 is gradually closed, and the Villany gauge 240 is closed.
The aperture was adjusted at 1 so that the instruction was Q, 2 torr. After confirming that the gas inflow is stable and the internal pressure is stable, the high frequency power source 241 is turned on and the induction coil 20 is turned on.
A glow discharge was generated in the chamber 201 with an input power of 60 W. In this way, the glow discharge was continued for about 10 hours to form the light 4'& layer. After that, all the pulps in the system except the main pulp 228 were closed. Next, s l F4 (70)/H gas cylinder 20
The pulp 212 of No. 7 was diluted to t o vat % with H, and the pulp 215 of the cylinder 210 of H4 gas (denoted as CxH4(10)/H!) was opened, and the outlet pressure gauge 23
0,233 pressure in 1#! /cIIL richness, gradually open the inflow pulps 217 and 220 and connect the flow meter 23.
5,238 Into 81F4 (70)/Hz gas, C
mH4 (10 ν) gas was injected into each. Subsequently, the outflow pulps 222 and 225 were gradually opened, and then the auxiliary pulp 227 was gradually opened. At this time, 81F4 (70)
The inflow pulp 217, 220 was adjusted so that the ratio of the /H gas flow rate and the CmH4(10)/H snow gas flow rate was 1:60.
adjusted. Next, adjust the opening of the auxiliary pulp 227 while paying close attention to the reading on the Vc Villany gauge 240, and
The pressure inside was set to I x 10' torr. Room 201
After the internal pressure stabilizes, the main pulp 228 is gradually closed and the opening is narrowed until the Villany gauge 240 reads 0.5 Torr. It was confirmed that the gas inflow was stable and that E was stable. Next, turn on the switch of the high frequency power supply 241, and apply 13.56 to the induction coil 206.
High frequency power of MHz was applied to generate glow discharge in the chamber 201, resulting in an input power of 6 OW. The above conditions were maintained for 1 minute to form a surface barrier layer on the photoconductive layer. After that, the heating heater 204 is turned off, and the high frequency power supply 2
41 is also in the of4 state, and after waiting for the substrate temperature to reach 100"O, the outflow pulps 222, 225 and the inflow valves 217 and 220 are closed, the main pulps 2' and 28 are fully opened, and the inside of the chamber 201 is 'After lowering the torr,
The main pulp 228 is closed, the inside of the chamber 201 is made atmospheric pressure by the leak valve 229, and the substrate is taken out. In this case, the total thickness of the layer formed was approximately 9μ. The scratch-forming member obtained in this way was installed in a charging exposure experiment equipment, and the Φ
6. Perform corona charging between Ox v + 0.2 w-,
The light image was immediately illuminated. A light image was created by using a tungsten lamp light source and irradiating a set of 081× light intensity through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) onto the surface of the member. The toner image of member-H is transferred to e5. When the image was transferred to transfer paper-H using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Next, the above-mentioned scratch forming member was exposed to 05.
Perform corona charging for 0.2W at 5 KV and immediately reduce to 0.
．． Image exposure was carried out at a light intensity of 8/ax/chess, after which an e-charged developer was cascaded onto the surface of the member, and then transferred and fixed onto transfer paper, resulting in an extremely clear image. From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had the physical properties of a bipolar image forming member whose dependence on the charging electrode was less than force. Example 2 In forming the surface barrier layer, 8iF4 (70')/H*
A photoconductive member was prepared under the same conditions and procedures as in Example 1, except that the surface barrier @fri was variously changed by changing the gas, Ctea(10)/It, and gas flow rate ratios. Each sample was placed in a charging exposure device exactly the same as in Practical Example 1 to form an image, and the image quality was judged, and the results shown in Table 1 below were obtained. 81xC3. Example 3 After forming a photoconductive layer on a molybdenum substrate according to the same conditions and procedures as in Example 1, a photoconductive layer was formed on a molybdenum substrate using Hl.
% diluted to 981C/(OH3), gas (purity 99
．． Open the valve 216 of the cylinder 211 (denoted as s+cz(cus)s(10)/H atmosphere after 000%l), adjust the pressure on the outlet pressure gauge to l kg/cdVC, and gradually close the inflow valve 221 to increase the flow. St to meter 239
c/(CHs)i (10)/lh gas was introduced. Subsequently, the effluent pulp 226 was gradually opened. Next, the opening of the auxiliary valve was adjusted while paying close attention to the reading on the Biller 21 gauge 240, and the auxiliary pulp 227 was opened at a trench where the inside of the valve 201 became I.times.10-2 torr. After the internal pressure of the chamber 201 stabilized, the main pulp 228 was kept closed, and the opening was narrowed until the Villany gauge 240 indicated 0.5 torr. Confident that the gas inflow is stable and the internal pressure is stable [2.Next, turn on the switch of the high frequency power supply 241 and apply a high frequency power of 13.56 MHz to the induction coil 206 to generate glow inside the chamber 201. generate a discharge,
20W of human power was used. After forming a surface barrier layer by maintaining the same conditions for 1 minute, the high frequency power source 342 is turned off, the heating heater 204 is also turned off, and after waiting for the temperature of the substrate to reach lOO''c Vci, the outflow valve 226 is turned off.
After closing the inflow pulp 221 and fully opening the main pulp 228, the entire inside of the chamber 201 is below 10'' tarr.
The main pulp 228 was closed and the inside of the chamber 201 was brought to atmospheric pressure by the leak pulp 229, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member obtained in this way is installed in a charging exposure experiment apparatus, and
．． Corona charging was performed for 0.211 IC using QKV, and a light image was immediately irradiated. The optical image was obtained by irradiating a transmission type test chart with a light amount of 1.0/uxΦ using a tungsten lamp light source. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component. 5. The toner image on the member. When transferred onto transfer paper using OKV's Corona Teitun, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Similarly, a clear and good image was obtained in the same manner as in Example 1 even when the corona polarity was changed to O and the developer edge was changed to ■. Example 4 Heater 20 was used when forming a photoconductive layer on a molybdenum substrate.
The input terminal of No. 4 was raised, the input terminal was changed while detecting the substrate temperature, and the temperature was stabilized until it reached a constant value of 250'0. Thereafter, the auxiliary pulp 227, then the outflow pulp 222, and the inflow pulp 217 were fully opened, and the inside of the flow meter 235 was also sufficiently degassed and vacuumed. After closing the auxiliary valve 227 and pulp 217, 222, S+F4 (70)/Hz
Open the pulp 212 of the cylinder 207 of KaX (pure [99,999%)
cs, and gradually opened the inflow pulp 217 to allow the s r F4 (70)/Ht gas to flow into the flow meter 235. Subsequently, the outflow pulp 222 was gradually opened 1, and then the auxiliary valve 227 was gradually opened. Next, pay close attention to the reading on the Villany gauge 240, and check the first aid valve 2.
The opening of 27 is adjusted to AI#, and the inside of chamber 201 is 1 x 10't.
The auxiliary valve 227 was opened until o r r. After the internal pressure of the chamber 201 stabilizes, the main pulp 22B is gradually closed and the Villany gauge 240 indicates Q, 5 tor.
I narrowed down the aperture until it reached r. After confirming that the gas inflow is stable and the internal pressure is stable, the switch of the high frequency power supply 241 is turned on, and high frequency power is applied to the induction coils 206, 13, and 56 to generate a glow discharge in the chamber 201. The power was set to 60W. After sustaining the glow discharge for 3 hours to form 1 dt of light, the heating heater 204 is turned off, and the high frequency power source 241 is also turned off.
After waiting for the temperature of the substrate to reach 100°C, m (SlxCt-x) was formed on the photoconductive layer by the same operation as in Example 1.
A surface barrier layer consisting of y'(H+X)x-y was provided. In this case, the total thickness of the layer formed was approximately 9μ. When an image was formed on a transfer paper using the thus obtained image forming member according to the same procedure as in Example 1, it was found that forming an image by performing θ corona discharge was better than forming an image by performing corona discharge. The image quality was excellent and extremely clear. From this result, it was confirmed that the image forming member obtained in this example had charge polarity dependence. Example 5 The inside of the deposition chamber was heated under the same conditions and procedures as in Example 1.
Exhaust to X 10-'torr, 81F4 (70)
/H@ gas was introduced into the room using the same procedure as in Example 1. PHs was then diluted to 25 vol PPm with H1
Gas cylinder (denoted as P Hs (25)/H2) 2
09 through the inflow pulp 219 at a gas pressure of 1#/j (
By adjusting the inflow pulp 219 and outflow pulp 224 according to the reading of the outlet pressure gauge 232, the opening of the outflow pulp 224 is determined and stabilized so that the reading of the flow meter 237 is at the same level as the flow rate of s iF4 (70)/fh gas. I let it happen. Subsequently, the high frequency power supply 241 was turned on to generate glow discharge. At that time, the input voltage and pressure were set to 60 W. After sustaining the glow discharge for 4 hours to form a photoconductive layer, the heating heater 204 was turned off, the high frequency power supply 241 was also turned off, and the substrate temperature was raised to 100°C.
After waiting for the formation of m (SIXCI-x)y' (
A surface barrier layer consisting of H + The image forming member thus obtained was formed on a transfer paper under the same conditions and procedures as in Example]. Mosono II! The II members were excellent and very clear. As a result, dependence on charging polarity was observed in the image forming member obtained in this example. Example 6 In fact, under the same conditions and procedures as in the flow side 1, the inside of the deposition chamber was
Exhaust to X 10'torr, 5ty4 (70)
71 m gas was introduced into the chamber 201. Then a, u@(
500)/H, from the gas cylinder 208, the inflow pulp 2
B! in the flow meter 236 at a gas pressure of 1 kg/cd (reading on the outlet pressure gauge 231) for 18 sessions. H
4 (J) 0 gods 1 gas was introduced. Then the inflow pulp 21
8. By adjusting the fi outlet valve 223, the opening of the outflow pulp 223 was determined and stabilized so that the reading of the flow meter 236 was 1/10 of the flow rate of 81F4 gas. The high-frequency power source 241 was turned on to generate a glow discharge. The human power at that time was set to 60W. In this way, the glow discharge was continued in the east for 4 hours, the bale on which the photoconductive layer was formed, and the heating Peter 204 was turned off.
High frequency 1i [source 241 is also turned off, substrate @ degree is 1
After waiting for the temperature to reach 00°C, a-(S transport C5-x)y' (H+
A surface barrier extending from x) and y was provided. The total thickness of I- formed in this case was about 10 microns. 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. The image quality was superior and extremely clear. From this result, it was confirmed that the image forming member (C) obtained in this example had a dependence on the charge polarity.However, the dependence on the charge polarity was different from that of the 1-quadratic acid members obtained in Examples 4 and 5. It was the opposite.

[Brief explanation of drawings]

FIG. 1 shows a preferred embodiment of the photoconductive member of the present invention. Schematic explanatory diagram for explaining the ll formation, 2nd
The figure is a schematic explanatory diagram for explaining an apparatus for producing a photoconductive member of the present invention. 100... Photoconductive member 101... Support body 102.
...Photoconductive layer 103...Surface barrier layer 104...
・Freely appointed consultant Canon Co., Ltd. agent Maru 11-

Claims (1)

[Claims] A desired gas is introduced into a deposition chamber that can be reduced in pressure to achieve a desired internal pressure, and discharge energy is applied to a starting material for supplying silicon atoms in the deposition chamber to form an amorphous material containing silicon atoms on a support. Next, a photoconductive layer consisting of silicon atoms as a host, counting atoms and 7
- A method for producing a photoconductive member, characterized by applying discharge energy to a starting material for forming an amorphous material containing a rogen atom to form a surface barrier layer on a basic conductive layer.