JPS62276558A - Light receiving member - Google Patents

Abstract

PURPOSE:To prevent degradation of the surface of a light receiving member by using a diamond-like carbon thin film containing at least on of H or halogen as a surface protective layer. CONSTITUTION:A photoconductive layer 102 and the surface protective layer 103 of the diamond-like carbon thin film containing at least one of H or halogen are formed in this order on a support 101, and this layer 103 has a free surface 107. The addition of at least one of H or halogen permits the noncombined valence of the diamond-like carbon to be compensated and the surface protective layer 103 very few in defect to be obtained.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Technical Field to Which the Invention Pertains] The present invention relates to a light-receiving member having a leading conductive layer made of amorphous silicon having silicon atoms as a matrix, and a light-receiving member having particularly excellent characteristics. The present invention relates to a light-receiving member suitable for an electrophotographic photoreceptor, in which a surface protective layer having the following is provided on the photoconductive layer.

(Description of the Prior Art) Conventionally, light-receiving members used for electrophotographic photoreceptors, etc., have superior consistency in their photosensitivity regions compared to other types of light-receiving members. Because of its high Vickers hardness and low pollution problems, for example, JP-A-54-
Amorphous materials containing at least one of hydrogen atoms and halogen atoms (hereinafter referred to as 'a-5i()l, The light-receiving member (denoted as “X)” is attracting attention.

By the way, such a light-receiving member has a-Si on a support.
()I, It prevents charge from being injected into the photoconductive layer from the free surface side when buried, and also improves the moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, and In order to improve durability and obtain stable image quality over a long period of time, it is known to provide a surface protective layer on the photoconductive layer.

As for the surface protective layer, a diamond-like carbon thin film is used as one of various materials having high resistance and sufficient light transmittance, since it is required to efficiently exhibit the various functions described above. It is known. (Refer to Japanese Unexamined Patent Publication No. 60-61761.) However, when the diamond-like carbon thin film is used as a surface protective layer, it prevents various mechanical damages such as contact with cleaning blades, etc., and also prevents corona during charging. Although it is particularly effective in preventing deterioration of the surface of the light-receiving member due to ozone and ions generated by discharge, the light-receiving member using the surface protective layer has insufficient electrophotographic properties such as charging ability and dark decay. However, when an image is formed using such a light-receiving member, there is a problem in that image quality may deteriorate, such as ghosts appearing on the image.

[Purpose of the invention]

The present invention solves the above-mentioned problems related to the surface protective layer of a light-receiving member used in electrophotographic photoreceptors, etc., and provides a light-emitting device having an improved surface protective layer that exhibits desired functions over a long period of time. The main purpose is to provide a receiving member.

Another object of the present invention is to provide a light-receiving member for use in electrophotographic photoreceptors and the like, which has a stable charging ability at all times and provides images of excellent quality over a long period of time.

(Structure of the Invention) The present inventors have conducted extensive research in order to solve the above-mentioned problems related to the surface protective layer of a light-receiving member used in an electrophotographic photoreceptor, etc., and to achieve the above-mentioned object of the present invention. As a result, it was found that the above-mentioned problems can be solved by using a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms as a surface protective layer.

That is, when a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms is used as a surface protective layer of a light-receiving member for an electrophotographic photoreceptor, hydrogen atoms (H) or The dangling bonds of the diamond-like carbon are compensated by at least one of the halogen atoms (X), and a surface protective layer with very few defects is obtained.6 Furthermore, at least one of a hydrogen atom or a halogen atom is contained in the diamond thin film. As a result, the effective coordination number of each atom constituting the diamond thin film is reduced, defects in the thin film are reduced, and the adhesion with other layers provided below the layer is also improved. It will be a place where you can

For these reasons, a light-receiving member for an electrophotographic photoreceptor that has a surface protective layer composed of a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms has high f-power, low dark decay, and high It is possible to obtain a photoreceptor that is excellent in various characteristics that an electrophotographic photoreceptor should have, such as being photosensitive and free from image smearing, and further has a strong m contract strength and good environmental resistance.

The present invention has been completed based on this knowledge, and its main points are a support, and on the support,
A photoreceptive member comprising a photoconductive layer made of an amorphous material based on silicon atoms and containing at least one of hydrogen atoms or halogen atoms, and a photoreceptor layer having at least a surface protective layer. In the light-receiving member, the surface protective layer is made of a diamond-like carbon thin film containing at least one of hydrogen atoms and halogen atoms.

The light-receiving member provided by the present invention is characterized by its surface protective layer, and in addition to the support,
Other constituent layers including the photoconductive layer can be arbitrarily selected depending on the purpose of use. Therefore, below, typical examples of the layer structure of the photoreceptive member of the present invention will be those for electrophotography. Although the case will be explained, the light receiving member of the present invention is not limited thereto.

FIGS. 1(^) to (1) are diagrams schematically showing typical examples of the layer structure of the light-receiving member of the present invention for use in electrophotography.

In the example shown in FIG. 1(A), a photoconductive layer 102 and a surface image jfF11o3 are provided in this order on a support 101, and a surface protective layer 103 has a free surface +07.

In the example shown in FIG. 1(B), a charge injection blocking layer 104, a photoconductive layer 102, and a surface protection layer LQI are provided in this order on a support 101.

First (the example shown in FIG.
are arranged in this order.

In the example shown in FIG. 1(D), the contact 1i is
110B, the photoconductive layer 102, and the surface protection F1103 are provided in this order.

The example shown in FIG. 1(E) is the one in which the charge injection blocking W1104, the adhesive layer 106, the photoconductive layer 102, and the surface protective layer 103 are provided in this order, and the example shown in FIG. Wavelength light absorption @ 105. Close contact 1i1108. Photo 4 electric layer 1
02 and the surface protective layer 103 are provided in this order.

In the example shown in FIG. 1(6), a long wavelength light absorption layer ios, a charge injection blocking layer 104, a photoconductive layer 102 are provided on a support 101.
and a surface protection layer 103 are provided in this order, and in this example, the order of the long wavelength light absorption layer 105 and the charge injection blocking layer 104 can be changed.

The example shown in FIG. 1(H) includes a support 101, a long wavelength light absorption layer 105, a charge injection blocking layer 191104. Photoconductive layer L
Q2 and the surface protection layer 103 are provided in this order.

1st (the example shown in FIG. 11 is a photoconductive layer 102, a charge injection blocking FJto4.
8 and the surface protective layer 103 are provided in this order.

The support +01 used in the light-receiving member of the present invention may be electrically conductive or electrically insulating. Examples of the electrically conductive support include NiCr, stainless steel, AQ, I :r, Mo, ^u, Nb, Ta, V
, Ti, Pt, Pb, or alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramic, paper, and the like. It is preferable that at least one surface of these electrically insulating supports is electrically conductive treated, and that a pre-ordered customer layer is provided on the electrically conductive treated surface side.

For example, if it is glass, NiCr, HaQ,
Cr, Mo, Au, Ir, Nb, Ta, V, Ti
, Pt, Pd, +nO3, ITO (Inxo, +Sn)
By providing a thin film consisting of etc., conductivity is imparted,
Or, if it is a synthetic resin film such as polyester film, NiCr, 8Q, Ag, Pb, Zn, Ni, ^
u, Cr, Mo, Ir, Nb, Ta, V, TIQ, Pt
Conductivity is imparted to the surface by providing a thin film of metal such as by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support can be a plate, an endless belt, a cylinder, etc. with a smooth surface or an uneven surface, and its thickness is determined as appropriate to form a desired light-receiving member. When flexibility as a member is required, it can be made as thin as possible within a range that allows the function as a support to be fully exhibited. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

In the photoreceptive member of the present invention shown in FIG. 1 (8), the charge injection blocking layer +04 provided between the support 101 and the photoconductive layer 102 supports This layer is provided to prevent electrons from being injected into the photoconductive layer 102 from the body side, and the charge injection blocking layer 104 is made of hydrogen or polycrystalline silicon (hereinafter referred to as '').
p01y-5i (H,
It is called n-5t (11,X) J. )〔In addition,
What is commonly called microcrystalline silicon is classified as a-S+. ], atoms belonging to Group 1II of the periodic table (hereinafter,
Cars are called "Group 1 II atoms". ) or periodic table V
Atoms belonging to Group V (hereinafter referred to as "Group V atoms")
It is made up of something containing.

Specifically, the Group 1 II atoms contained in the charge injection blocking layer 104 include B (boron), M (aluminum), Ga (gallium), In (indium 1.Tl1
Although thallium (l) and the like can be used, particularly preferred are B and Ga. In addition, as group V atoms,
Specifically, P (phosphorus), As (arsenic), sb (antisulfur), Bi (bismuth), etc. can be used, but P and As are particularly preferred. The amount of Group 1 II atoms or Group V atoms contained in the charge injection blocking layer 104 is 3 to 5 X lO'atomic pp.
m, preferably 50 to 1 x lo'atomic
ppm, 1 x 10” ~ 5
x 103atoIIlicpp111 is preferable.

Further, the amount of halogen atoms or hydrogen atoms contained in the charge injection blocking layer 104 is lXl0' to 7x10' at
omic ppm, especially poly-5i (H,
Preferably I x 103~2
X 105105ato ppm, a-5i(H,
X) if it is composed of I X 10' ~ 6 x
It is desirable to set lo'atomjc ppm,
Furthermore, the layer thickness of the charge injection blocking layer +04 of the photoreceptive member of the present invention is 0.03 to 15μ, preferably 004 to 1Oμ,
The optimum value is 005 to 8μ.

Summary 1 (C> In the light-receiving member of the present invention shown in the figure, the long-wavelength light absorption layer +05 provided between the support 101 and the photoconductive layer 102 is composed of germanium atoms (Ge) or tin atoms (Sn). Non containing at least one of
-5i (H,
02, the long wavelength light absorption layer 105 efficiently absorbs the long wavelength light that could not be completely absorbed in the support 1.
It has the function of significantly preventing the appearance of interference phenomena due to reflection of long wavelength light on the 01 surface. The amount of Ge atoms, the amount of Sn atoms, or the sum thereof contained in the long wavelength light @ collection jig 105 is 1 to lO'at
omic ppm, preferably 1x 102-9X
10' Mtomic ppm, more preferably 5x
It is desirable to set it as 10'-8 x 10' atomic ppm. Further, the amount of hydrogen atoms or halogen atoms contained in the long wavelength light absorption layer 105 is preferably 1 x 10' to 3 x 10' atomic ppm, particularly poly-3i (Ge, S
n) (H,X) preferably 1 x 103~2
X 105atollic ppm, a-5
1 (Ge.

Sn) (In the case of l(,X), preferably l XIO'
It is desirable to set it as 6 XIO'atomic ppm.

Furthermore, the long wavelength light absorption layer 105 in the light receiving member of the present invention
The layer thickness is 0.05-25μ, preferably 0.07-20μ
μ, optimally, it is desirable to set it to 0.1 to 15 μ.

"51 (D) In the light receiving member of the present invention shown in FIG.
The adhesive layer 106 provided between the support 101 and the photoconductive layer 102 is a layer that functions to improve the adhesion between the support 101 and the photoconductive layer 102, and contains oxygen atoms, carbon atoms, and nitrogen atoms. Non-5i containing at least one selected from the following [)1. X) After I, it is composed of 'Non-5i (denoted as 0, (:, N) (H, X) J). The amount of oxygen atoms, carbon atoms, and nitrogen atoms contained in the adhesive layer 106, or the sum of at least two of them, is 100 to 9.
X 10'atomic ppm preferably 1O(1
-4X 10' atomic ppm is desirable. Further, the amount of hydrogen atoms or halogen atoms contained in the adhesion layer 106 or the sum thereof is preferably lO~7 x I05atomicppI11,
Especially in the case of poly-5+(0,C,N)(H,X), 10 to 2 x lO'atomic ppm, a-
5i(0,C,N) (H,X) then I x 1
It is desirable to set it as 03-7 x lo5 atomic ppm.

By the way, the charge injection blocking layer +04, the long wavelength light absorbing layer +05, and the adhesion layer 105 in the light receiving member of the present invention can be used in combination, and the first example shows a typical example thereof. (E) to (1()).

Furthermore, in the light-receiving member of the present invention, by containing at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms in the charge injection blocking layer 04 or the long wavelength light absorption layer 105, these layers It is also possible to make the long-wavelength light absorption layer 105 contain Group I+ atoms or Group II atoms, or the charge injection blocking layer 104 may contain germanium atoms. Alternatively, by containing tin atoms, a layer having both of the functions of these layers can be obtained.

By the way, the charge injection blocking layer 104, the long wavelength light absorption layer 105, and the adhesion layer 1i 110B in the light receiving member of the present invention are made of a material based on Non-5i (H,X), but poly-Si ( There are various methods for forming a layer composed of H, X), including the following methods.

One method is to raise the substrate temperature to a high temperature, specifically 400℃.
In this method, the temperature is set at ~450° C., and a film is deposited on the substrate by plasma CVD.

Another method is to first form an amorphous film on the surface of the substrate, that is, to form the film by plasma CVD on the substrate whose temperature is about 250°C, and then annealing the amorphous film. This is a method of The annealing process involves heating the substrate to 400-450°C for about 20 minutes, or applying laser light for about 20 minutes.
This is done by irradiating for a minute.

The photoconductive layer 102 of the light receiving member of the present invention is a-5t(H
.

X) or a-5t(Ge, Sn) ()1. X) and has a leading-edge property, the layer further contains a group 1II atom or a group Ⅰ atom or/and an oxygen atom,
At least one type selected from carbon atoms and nitrogen atoms can be contained.

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. The amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the photovoltaic layer 102, or the sum of the amounts of hydrogen atoms and halogen atoms (H×X) is preferably from 1 to 40 atoa+ic. Preferably 5-30
It is desirable to use atomic 'l+. Further, the purpose of containing Group 1 II atoms or Group V atoms in the photoconductive layer 102 is to control the conductivity of the photoconductive layer +02. As such Group 11+ atoms and Group V atoms, the same atoms as those contained in the charge injection blocking layer 104 described above can be used, but when they are contained in the photoconductive layer 102, charge Injection blocking layer 10
4 contains a substance of opposite polarity to that contained in the charge injection blocking layer 104, or contains a substance of the same polarity as that contained in the charge injection blocking layer 104 in an amount much smaller than that contained in the layer 104. You can force it.

The amount of Group 1 II atoms or Group V atoms contained in the photoconductive layer 102 is preferably I x 10-3 to 1 x t
o' atomic ppm, more preferably 5xlO
-2 to 5x10' atomic ppIll, optimally I x 10-' to 2 x 102102ato p
It is desirable to set it to pm.

Further, the purpose of containing at least one type of oxygen atom, carbon atom, and nitrogen atom in the photoconductive layer 102 is to increase the dark resistance of the photoconductive layer 102 and to
The objective is to improve the film quality of the photoconductive layer 102. The amount of these atoms contained in the photoconductive layer 102 is preferably 1 x 10-' to 50 atomic%, more preferably 2 x 10-' to 40 atomic%.
, it is optimally desirable to set it to 3 x to-3 to 3 Gatomic%.

Furthermore, germanium atoms (Ge) are added to the photoconductive F1102.
) or tin atoms (Sn), but the purpose of containing such atoms is to improve the sensitivity to long wavelength light such as laser light, and in this case, the photoconductive layer The amount of these atoms contained in 102 is preferably 1 to 9.5
It is desirable to set the amount to x lO'ajomic ppm.

In addition, in the light-receiving member of the present invention, the layer thickness of the photoconductive layer is one of the important factors for efficiently achieving the object of the present invention.
In order to give the light-receiving member the desired characteristics, it is necessary to pay sufficient attention when designing the light-receiving member, and the thickness is usually 1 to 100μ, but preferably 3 to 8
0μ, optimally 5 to 50μ.

The surface protection layer 103, which is a feature of the light-receiving member of the present invention, is provided on the photoconductive layer 102 described above and has a free surface 107. The surface protective layer 103 improves various properties required of a light-receiving member, such as moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, use environment characteristics, and durability, and particularly, the surface of the light-receiving member. It has the function of preventing mechanical damage and deterioration due to ions and ozone generated by corona discharge, and has excellent electrophotographic properties such as charging ability and dark decay, and prevents image deletion and residual potential during image formation. It has an effective prevention function.

The surface protection FiL of the light receiving member of the present invention (13 is composed of a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms, and the hydrogen atoms contained in the surface protection layer 103) Or the amount of halogen atoms or the sum of those amounts is 1 x 10
'~4 x 10' atomic ppm.

In the light-receiving member of the present invention, the layer thickness of the surface protective layer 103 is also one of the important factors for efficiently achieving the purpose of the present invention, and may be determined as appropriate depending on the desired purpose. However, it is necessary to decide based on mutual and organic relationships depending on the amount of constituent atoms contained in the surface protective layer or the properties required of the surface protective layer. Furthermore, it is also necessary to consider economic efficiency, including productivity and mass production.

For these reasons, the surface protective layer 1 of the light-receiving member of the present invention
The layer thickness of 03 is preferably 0.003-30μ, more preferably 0.004-20μ, optimally 0.005-1
It is 0μ.

Furthermore, in the light-receiving member of the present invention, an intermediate layer 108 may be formed between the surface protective layer 103 and the light-guiding layer 102, and the intermediate layer 108 is composed of a-5i ( H,X) or poly-5i (H,X
), and the amount of carbon atoms contained in the intermediate layer 108 is preferably 20 to 90 atomic%.
The amount of hydrogen atoms (H) contained in the intermediate layer 108 is more preferably 30 to 85 atomic %, and most preferably 40 to 80 atomic %.
The amount of halogen atoms (x) and the amount of hydrogen atoms + halogen atoms (H + X) are preferably 1 to 70 atomic%
, more preferably 2 to 65 atom fc%, optimally 5
It is desirable to set it to 60 ajomic%. Further, the layer thickness of the intermediate layer 108 is preferably 0.003 to 30 μm, more preferably 0.0G4 to 20 μm, and most preferably 0.0G4 to 20 μm.
It is desirable to set it as 05-10 micrometers.

Next, a method for forming the constituent layers of the light-receiving member of the present invention will be explained.

The amorphous material constituting the light-receiving member of the present invention can be prepared using a glow discharge method (low frequency (fLCVD, high frequency CVO or micro-CVD, AC frequency T1.CvD, or direct current discharge CVD, etc.), sputtering method, etc. It can be formed by various thin film deposition methods such as vacuum evaporation, ion blating, photo CVD, and thermal CVD.
The method is selected and adopted as appropriate depending on factors such as the production scale and the desired characteristics of the light-receiving member to be produced, but it is relatively easy to control the conditions for producing a light-receiving member with the desired characteristics. However, since halogen atoms and hydrogen atoms can be easily introduced together with silicon atoms,
Glow discharge method or sputtering method is suitable. Further, the glow discharge method and the sputtering method may be used together in the same apparatus system.

For example, in order to form a surface protective layer composed of a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms by a glow discharge method, basically a C supply that can supply carbon atoms (C) is required. A raw material gas for N supply that can supply nitrogen atoms (N), and a raw material gas for N supply that can supply hydrogen atoms (H) or/and halogen atoms (
X) A source gas for 4 people is placed in a deposition chamber that can have a reduced pressure inside, and 8 people are placed in the deposition chamber to generate a glow discharge in the deposition chamber,
Form a deposited film.

The raw material gas for C supply includes saturated hydrocarbon compounds (CnH2n-2, n≦10), ethylene hydrocarbon compounds (CnH2n, n≦10), and acetylene hydrocarbon compounds (':nH2n-2.n). ≦lO), cyclic hydrocarbon compounds, or halogenated compounds thereof, which are in a gaseous state or can be gasified. in particular,
Clh, C2H6, C5Hs, CF4, CH3 as saturated hydrocarbon compounds or halogenated saturated hydrocarbon compounds
Examples of the cyclic hydrocarbon compounds include benzene, toluene, xylene, adamantanone, and the like.

In addition, the raw material gas for supplying H and the raw material gas for supplying X include hydrogen gas, halogen gases such as fluorine, chlorine, bromine, and urin, HF, 1-ICI, HBr, HI,
Hydrogen halides such as BrF, CIF,
(Ih, BrF, , [1rF3, [Ft , Ill:l
Examples include gaseous or gasifiable compounds such as interhalogen compounds such as , EBr, and the like.

In addition, in order to form a surface protective layer by a sputtering method, a C (graphite) target is used as a target, and the raw material gas for H supply and/or the raw material gas for X supply is introduced into the deposition chamber together with an inert gas such as a gas. The C target is formed by sputtering the C target in a plasma atmosphere.

Furthermore, in order to form a layer composed of a-5i(H,X) by the glow discharge method, basically silicon atoms (
Introducing a source gas for introducing hydrogen atoms (+1) and/or a source gas for introducing halogen atoms (x) into a deposition chamber whose interior can be made under reduced pressure, along with a source gas for supplying Si that can supply Si), A glow discharge is generated in the deposition chamber, and a-5t (H,
form a layer consisting of

The gas for supplying Si is SiH4,5i2)1
．． ．． Examples include silicon hydride (silanes) in a gaseous state or that can be gasified, such as 5iJ6 and SiJ+o. In particular, 51+1
4, Si2H6 is preferred.

Further, as the raw material gas for introducing halogen atoms, there are many halogen compounds, such as halogen gas,
Gaseous or gasified halogen compounds such as halides, interhalogen compounds, and halogen-substituted silane derivatives are preferred. Specifically, fluorine, chlorine, bromine,
Iodine halogen gas, BrF, (:IF, (:IF
s, BrF5. Interhalogen compounds such as BrF5, IFy, [1, IBr, etc., and SiF4, Si, F6.5i
Examples include silicon halides such as 114.5i8r4.

When using a gaseous silicon halide or one that can be gasified as described above, a-
This is particularly effective since a layer composed of 5i can be formed.

Further, as the raw material gas for supplying hydrogen atoms, hydrogen gas, HF, HCI, halides such as )IBr, HI, S+H4,5lz)Is, 5t=Ha,
Silicon hydride such as 5I4H1゜, or 5i) 12F2
．． 5i) 1,1□, 5iH2C1□, Sil+Ch, 5
Gaseous or gasified materials such as halogen-purchased silicon hydrides such as iH2Br2 and 5iHBr3 can be used, and when these raw material gases are used, there are problems in terms of controlling electrical or charging characteristics. This is effective because the content of hydrogen atoms (H), which is extremely effective, can be easily controlled.

When the hydrogen halide or the halogen-substituted silicon hydride is used, hydrogen atoms (H) are also introduced at the same time as the halogen atoms, which is particularly effective.

In order to form a layer consisting of a-5i(l(, The silicon compound gas containing the halogen atoms described above may be introduced into the deposition chamber to form a plasma 7 surrounding the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as +2 or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma of the gas; an surrounding atmosphere. Bye.

For example, in the case of the reactive sputtering method, a Si target is used, and gas for introducing halogen atoms and H2 gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to generate plasma; A layer made of a-Si(H,X) is formed on the support by sputtering the Si target.

To form a layer composed of a-5iGe (H,
e) and a raw material gas for Ge supply that can supply hydrogen atoms (
Introducing a raw material gas for supplying hydrogen atoms (H) and/or halogen atoms (X) into a deposition chamber at a desired gas pressure while reducing the internal pressure; A glow discharge is generated in the deposition chamber, and a-5
A layer composed of iGe (H,X) is formed.

The materials that can be used as the raw material gas for supplying S1, the raw material gas for supplying halogen atoms, and the raw material gas for supplying hydrogen atoms are used when forming the layer composed of the above-mentioned a-5i (H, X). What you have is used as is.

In addition, as the material gas for supplying Ge, GeHa, Ge2116, Ge31(6, Ge
4) 1+o, Ge511+z, Ge, old 4, Ge711
Germanium hydride in a gaseous state or in a gasified state such as +s, GeaH16, Ge*Hzo, etc. can be used. In particular, from the viewpoint of ease of handling during layer creation work and good Ge supply efficiency, GeH4, Ge2Hs, and Ge3H
a is preferred.

To form a layer composed of a-5iGa(H, etc., by sputtering in an atmosphere of a desired gas.

a-5iGe (H,
When forming a layer consisting of X), for example, polycrystalline silicon or crystalline silicon and polycrystalline germanium or! #Crystalline germanium is placed in a deposition boat as an evaporation source, and the evaporation source is heated and evaporated by a resistance heating method or an electron beam method (E, B, method), etc., and the evaporated material is evaporated into a desired gas plasma atmosphere. This can be done by letting it pass.

In both the sputtering method and the ion blasting method, in order to contain halogen atoms in the layer to be formed, a gas of the above-mentioned halide or a silicon compound containing halogen atoms is introduced into the deposition chamber, and the gas is It is sufficient to form a plasma atmosphere of In addition, when introducing hydrogen atoms, a raw material gas for supplying hydrogen atoms, such as H2 or the above-mentioned gases such as hydrogenated silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. What is necessary is to form a plasma atmosphere of the following gases. Further, as the raw material gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen are effective, but in addition, HF, HCI,
Hydrogen halides such as HBr, )II, 5iH2h
, 5iH2h, 5jH2C12, 5iHC13, 5iH
2Br2.5iHBr3, etc. 1^ silicon hydride, and GeHF1, GeHBr3, Ge
H3F, GeHCl, Ge) I, C12,
GeH3f:l, GeHBr3, Ga)12Br2.
Ge1(3ir, GeHI*, Ge2116GeH3
1st class hydrogenated germanium halide etc., GeF4, G
eCl4. GeBra, GeI4, GaF,,G
Gaseous or gasified materials such as germanium halides such as aC11, GeBr2, Ge12, etc. can also be used as effective starting materials.

A photoreceptive layer made of amorphous silicon containing tin atoms (hereinafter referred to as 'a-5iSn(II,X)') is formed using a glow discharge method, a sputtering method or an ion blating method The above-mentioned a-5iGe 01. During the formation of a layer consisting of
This is done by using it in place of the starting material for supplying nl and controlling its amount in the layer to be formed.

Substances that can be used as raw material gas for supplying the tin atoms (Sn) include tin hydride (SnH4), SnF, 5nF, etc.
4.5nC12, 5nCI4. SnBr2, Sn
Gaseous or gasified tin halides such as Br4.5nlz, 5n14, etc. can be used. When using tin halides, a-5L containing halogen atoms can be used on a predetermined support. This is particularly effective because it allows the formation of layers consisting of Among them, Sr+I:14 is preferable from the viewpoint of ease of handling during layer forming work and good Sn supply efficiency.

When 5nC14 is used as a starting material for supplying tin atoms (Sn), in order to gasify it, solid 5nCLa is heated and an inert gas such as A', He is blown into the inert gas. It is preferable to use a gas for bubbling, and the gas thus generated is introduced at a desired gas pressure into a deposition chamber whose interior is kept under reduced pressure.

Using the glow discharge method, sputtering method, or ion blating method, a-5i(H,
In order to form a layer composed of an amorphous material containing a group I atom or a group I atom, a nitrogen atom, an oxygen atom, or a carbon atom, when forming a layer of a-5i (H, X), The starting material for introducing a Group 1 II atom or a Group V atom, a starting material for introducing an oxygen atom, a starting material for introducing a nitrogen atom, or a starting material for introducing a carbon atom is added to the a-5t described above.
This is done by using them together with the starting materials for the formation of (H,

For example, in order to form a layer composed of a-5t(H,X) containing atoms (0, C, N) using the glow discharge method, When forming the layer composed of atoms, a starting material for introducing atoms (0, (:, N) is used together with a starting material for forming a-5i (l(, This is done by controlling the amount.

As a starting material for such introduction of atoms (0, C, N), most of the gaseous substances or substances that can be gasified have at least atoms (0, C, N) as constituent atoms. Things can be used.

Specifically, as starting materials for introducing oxygen atoms (0), for example, oxygen (0□), ozone (0,), -nitrogen oxide (N
O), -nitrogen dioxide (N20), nitrogen sesquioxide (N20
3), trinitrogen tetraoxide (N204), nitrogen sesquioxide (N2
05), nitrogen trioxide (NO3), silicon atom (Sl)
For example, disiloxane (11,5iO5+)H3) whose constituent atoms are an oxygen atom (0) and a hydrogen atom (H),
Examples include lower siloxanes such as trisiloxane (JSiOSiH20Sit(,), etc., and starting materials for introducing carbon atoms (C) include, for example, methane (CH4),
Saturated hydrocarbons with 1 to 5 carbon atoms such as ethane ((:2H6), propane (csoa), n-butane (n-c4H,a), pentane (C8H12), ethylene (C2H4)
, propylene (Ctllsl, butene-t (C414
6), butene-2 (C41(a), isobutylene (ca
Ethylene hydrocarbons with 2 to 5 carbon atoms such as nal and pentene (CsH+o), acetylene hydrocarbons with 2 to 4 carbon atoms such as acetylene (II:2H2), methylacetylene (C3H4), butyne (C4116), etc. Examples of starting materials for introducing nitrogen atoms (fN) include nitrogen (N2), ammonia (NHi), hydrazine (H,
NNL), hydrogen azide (HN*), ammonium azide (NLNs), nitrogen trifluoride (F3N), and nitrogen tetrafluoride (F4N).

For example, when a glow discharge method is used to form a layer or layer region containing oxygen atoms, a material for introducing oxygen atoms is added to a starting material selected as desired from among the starting materials for forming the photoreceptor layer described above. Starting materials are added. As such a starting material for introducing oxygen atoms, almost any gaseous substance or substance that can be gasified can be used as long as it has at least an oxygen atom as a constituent atom.

For example, a raw material gas containing silicon atoms (S+), a raw material gas containing oxygen atoms (0), and hydrogen atoms (H) or/and halogen atoms (X
) with a raw material gas having constituent atoms at a desired mixing ratio, or a raw material gas having silicon atoms (Si) with oxygen atoms (0) and hydrogen atoms (H).
A raw material gas having constituent atoms is mixed at a desired mixing ratio, or a raw material gas having silicon atoms (Si), oxygen atoms (0), and It can be used in combination with a raw material gas having three hydrogen atoms (H) as its constituent atoms.

Also, separately, silicon atoms (S[) and hydrogen atoms (14)
A raw material gas containing oxygen atoms (01 as constituent atoms) may be mixed with a raw material gas containing oxygen atoms (01 as constituent atoms).

Specifically, for example, oxygen (C2), ozone (0,), -
Nitrogen oxide (NO), nitrogen dioxide (N(b), -nitrogen dioxide (N20), nitrogen sesquioxide (N203), nitrogen tetroxide (N204), nitrogen sesquioxide (N2os), nitrogen trioxide (NO3), silicon atoms (Si) and oxygen atom (0)
For example, disiloxane (l(ssLGsi)Is), trisiloxane (
Examples include lower silochitins such as HsSiO5iHzO5ith).

In order to form a layer or a layer region containing oxygen atoms by sputtering, a single crystal, a St wafer, a SiO2 wafer, or a wafer containing a mixture of St and SiO□ is used as a target, and various types of these are used. This can be done by sputtering in a gas atmosphere of

For example, if you use it as a target for Si Milani,
A raw material gas for introducing oxygen atoms and hydrogen atoms and/or halogen atoms as necessary is diluted with a diluent gas as necessary, and introduced into a deposition chamber for sputtering to generate a gas plasma of these gases. What is necessary is just to form and sputter the said 51 way 8.

Alternatively, by using St and 5I02 as separate targets or using a single mixed target of Si and 5i02, at least hydrogen atoms (l () or /
It can be formed by sputtering in a gas atmosphere containing halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the example of glow discharge described above can be used as an effective gas also in the case of sputtering.

For example, in order to form a layer made of amorphous silicon containing carbon atoms by a glow discharge method, a raw material gas containing silicon atoms (St) and a raw material gas containing carbon atoms (C) are used. The gas and, if necessary, a raw material gas containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms are mixed at a desired mixing ratio, or silicon atoms (Si) are used as constituent atoms. A raw material gas consisting of carbon atoms (C) and hydrogen atoms (+1) is mixed at a desired mixing ratio, or a raw material gas consisting of silicon atoms (Si) is used. Raw material gas to be atoms, silicon atoms (S i), carbon atoms (
A raw material gas containing C) and hydrogen atoms ()l) as constituent atoms is mixed together, or a raw material gas containing silicon atoms and hydrogen atoms as constituent atoms is mixed and used.

Si is effectively used as such raw material gas.
5in4, Si, II6.5i with and H as constituent atoms
3H.

Silanes such as Si a II lo (silicon hydride gases such as Silanels, saturated hydrocarbons containing C and H as constituent atoms, for example, having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, Examples include acetylene hydrocarbons having 2 to 3 carbon atoms.

Specifically, examples of saturated hydrocarbons include methane (C
H4), ethane (c2oe), propane (c3oa),
n-Butane (n-CaHta), Henta'J (C5
H+t), ethylene hydrocarbons include ethylene (
C2H6), propylene (C3HJ, butene-1 (C
411a), butene-2 (c4oa), isobutylene (
C4116), pentene (CsH+). Examples of acetylene hydrocarbons include acetylene (c2Hz), methylacetylene (c3H41), butyne (C4H6), and the like.

As a raw material gas containing SL, C, and H as constituent atoms, S
Examples include alkyl silicides such as t ([:H3) 4.5r(C2Hs)4. In addition to these raw material gases, H7 can of course also be used as the raw material gas for H introduction.

To form a layer composed of a-5iC(l(,X) by sputtering method, !# crystal or polycrystalline Sj
This is carried out by sputtering a sea urchin wafer, a C (graphite) wafer, or a wafer containing a mixture of Si and C in a desired gas atmosphere.

For example, when using St wafer 8 as a target, raw material gas for introducing carbon atoms, hydrogen atoms, and/or halogen atoms may be used as necessary.
The diluent gas may be diluted with a diluent gas such as E and introduced into a deposition chamber for sputtering to form a gas plasma of these gases and sputtered onto the Si Milani.

In addition, if SI and C are used as separate targets, or if SI and C are used as a mixed target, the raw material for introducing hydrogen atoms and/or halogen atoms may be used as sputtering gas. The gas is diluted with a diluent gas as needed to prepare the deposit for sputtering!
What is necessary is to introduce it into a room, form a gas plasma, and perform sputtering.

As the raw material gas for introducing each atom used in the sputtering method, the raw material gas used in the glow discharge method described above can be used as is.

For example, when a glow discharge method is used to form a layer or layer region containing nitrogen atoms, a starting material for introducing nitrogen atoms is added to a starting material selected as desired from among the starting materials for forming the photoreceptive layer described above. Add substance. As the starting material for introducing nitrogen atoms, almost any gaseous substance or gasifiable substance having at least nitrogen atoms as a constituent atom can be used.

For example, a source gas containing silicon atoms (Si), a source gas containing nitrogen atoms (N), and hydrogen atoms (H) or/and halogen atoms (X) as necessary.
A raw material gas containing constituent atoms is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (St) and nitrogen atoms (N) and hydrogen atoms (H) are used. The atoms and source gas can also be used in a desired mixing ratio.

Also, separately, silicon atoms (Si) and hydrogen atoms (11)
You may mix and use the raw material gas which has an oxygen atom (0) as a constituent atom with the raw material gas which has a constituent atom.

A starting material that is effectively used as a raw material gas for introducing nitrogen element (N) used when forming a layer or layer region containing nitrogen atoms is one that has N as a constituent atom or a mixture of N and H.
For example, nitrogen (N2), ammonia (
Mention may be made of gaseous or gasifiable nitrogen such as hydrazine (NH3), hydrazine ()12NNHtl, hydrogen azide ()1N3), ammonium azide (NH4N3), and nitrogen compounds such as boron nitrides and azides. In addition to the above, halogenated nitrogen compounds such as nitrogen trifluoride (F3N+) and nitrogen tetrafluoride (F4N1) can be mentioned since they can also introduce halogen atoms in addition to nitrogen atoms.

To form a layer or layer region containing nitrogen atoms by a sputtering method, a monocrystalline or Si wafer or a polycrystalline Si Uni-8, or a Si3N, wafer, or a mixture of Si and 5i384 is used. This can be carried out by sputtering these wafers in various gas atmospheres using a wafer as a target.

For example, if a Si wafer is used as a target,
A raw material gas for introducing nitrogen atoms and hydrogen atoms or/and halogen atoms as necessary is diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering. The Si wafer may be sputtered by forming plasma.

Alternatively, by using Si and 5iJ4 as separate targets, or by using a single target containing Si, Si, and N4, it is possible to use at least hydrogen atoms ( It can be formed by sputtering in a gas atmosphere containing H) or/and halogen atoms (x) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In addition, when forming a layer composed of a-5i (H, Starting materials for the introduction of Group 1 II atoms or Group V atoms are used together with the starting materials for forming a-5i()I,X) to control their amount in the layer being formed. Do it by doing it.

Specifically, starting materials for introducing group (III) atoms include +12)18, B4HIO, R5He
, BsHz, BsHz. , BsH+z, B6H
Boron hydride such as I4, BF, , BCI, , BBr,
Examples include boron halides such as. In addition, Al13
, Ga(:Ls, Ga (CH312, InCl3, T
ΩC1, etc. can also be mentioned.

As a starting material for introducing a group V atom, specifically, for introducing a phosphorus atom, hydrogenated phosphorus such as PH, PJ, etc. is used.
F3. PFS, P(:13, Pct, PBrs, P
Examples include phosphorus halides such as Brs and PI3. In addition, 8sH, 8sF=, 85C13, 85Brs,
8sFs, 5bHs, SbF3, SbF,.

5bC13, 5bC1, BiHz, B111. ,B1
Br3 and the like can also be mentioned as effective starting materials for introducing Group V atoms.

As described above, the light-receiving layer of the light-receiving member of the present invention is formed using a glow discharge method, a sputtering method, etc.
The content of each of EL and tin atoms, Group 111 atoms or Group V atoms, oxygen atoms, carbon atoms, nitrogen atoms, or hydrogen atoms and/or halogen atoms can be controlled by each of the elements flowing into the deposition chamber. This is carried out by controlling the gas flow rate of the starting material for supplying atoms or the gas flow rate ratio of each starting material for supplying atoms.

In addition, conditions such as support temperature, gas in the deposition chamber, discharge power, etc. when forming each constituent layer such as the photoconductive layer and the surface protective layer are as follows.
In order to obtain a light-receiving member having desired characteristics, it is an important factor and should be selected as appropriate, taking into consideration the function of the layer to be formed.

Furthermore, these layer formation conditions may differ depending on the type and amount of each of the atoms mentioned above to be contained in each constituent layer such as the photoconductive layer and the surface protective layer. It is also necessary to take this decision into consideration.

Specifically, when forming a surface protective layer made of a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms by high frequency (13,56 MH2) plasma CVD method, the gas pressure in the deposition chamber is usually 10- 3~
100 Torr, more preferably LQ-2~
5flTorr, optimally 10-' to 50Tarr.

Further, the support temperature is usually 50 to 900°C, more preferably 100 to 600°C, and most preferably 150 to 50°C.
The temperature shall be 0°C. Furthermore, the discharge power is usually 0.05 to 100W.
/cm2, more preferably 0.1-70W/cm
', optimally set to 05 to 50 W/Cm2.

In addition, when forming a surface protective layer consisting of a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms by microwave (2,45Gl(z) plasma CVD method), the gas pressure in the deposition chamber is usually 10-4. ~10
0 Torr, more preferably 10-3 to 50 Torr.

The optimum value is 2 x 10-' to 45 Torr, and the discharge power and support temperature are the same as in the case of the high-frequency plasma CVD method described above.

Furthermore, when forming a surface protective layer consisting of a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms by sputtering, the gas pressure in the deposition chamber is usually 10-4 to 1 O Torr, more preferably 5 X
10-' to 5 Torr, optimally 10-3 to 1 Torr
rr, and the discharge power and support temperature are the same as in the case of the high frequency plasma CVD method described above.

In addition, when a layer containing nitrogen atoms, oxygen atoms, carbon atoms, etc., such as a-5i ()I, Particularly preferably, the temperature is 50 to 250°C.

The gas pressure inside the deposition chamber is normally 0. O1 to I Torr, particularly preferably 0.1 to 0.5 Torr.

The discharge power is usually 0.005 to SOW/am', more preferably 0.01 to 3QW/am'.
Let it be am'. Particularly preferably 0. O1~20W/c
Let it be m2.

When forming the a-5iGe (H, The support temperature is usually 50 to 350°C, more preferably 50 to 300°C, particularly preferably 100 to 300°C. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.001 to 3 Torr, and particularly preferably o, oi to 1 Torr. Also, the discharge power is 0
．． It is normal to set it as 0.05-50W/cm2, but it is preferably set as 0.01-30W/cm2. Particularly preferably o, at to ZOW/C1n2.

However, the specific conditions for layer formation, such as support temperature, discharge power, and gas pressure in the deposition chamber, are usually difficult to determine individually.

Therefore, in order to form an amorphous material with desired characteristics,
It is desirable to determine optimal conditions for layer formation based on mutual and organic relationships.

Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method will be described.

FIG. 2 shows an apparatus for producing electrophotographic light-receiving members using the glow discharge decomposition method.

In the gas cylinders 202, 203, 204, 205, and 206 in the figure, raw material gases for forming the respective layers of the present invention are sealed, for example,
202 is a 5iHa gas (99.999% purity) cylinder,
203 is 8, H6 gas diluted with H2 (purity 99.9
99%, hereinafter abbreviated as B, O, /H) cylinder, 204 is NO gas (purity 99.5%) cylinder, 205 is CH4 gas (purity 99.999 zero) cylinder, ZQa is H1 gas (
(purity 9g, g99%) Bonhe.

To allow these gases to flow into the reaction chamber 201, make sure that the valves of the gas cylinders 202 to 206 and the leak valve 235 are closed, and also make sure that the inflow valves 212 to 21 are closed.
6, outflow valves 217-221, auxiliary valve 232
．． 233 is open, first check the main valve 234 to evacuate the reaction chamber 201 and gas piping. Next, the vacuum gauge 236 reads approximately 5 x 10"6 Torr.
When the temperature reaches r, the auxiliary valves 232 and 233 and the outflow valves 217 to 221 are closed.

1 when forming the first layer on the base cylinder 237
For example, S i II 4 from gas cylinder 202
Gas, gas cylinder, 8 from 203. )1. /H2H2 gas cylinder, NO gas from 204, valve 222, 2
23, 04 open and outlet pressure gauges 227, 228
, adjust the pressure of 229 to 1 kg 7 cm", and open the inlet valve 2.
12, 213, 214 are gradually opened to allow flow into mass flow controllers 207, 208, 209. Subsequently, the outflow valves 217, 218, 219, and the auxiliary valve 2
32 is gradually opened to allow the respective gases to flow into the reaction chamber.

At this time, adjust the outflow valves 217, 218, and 219 so that the ratio of the 5in4 gas flow rate, B2H8/82 gas flow, and NO gas flow becomes the desired value, and also adjust the pressure inside the reaction chamber to the desired value. Adjust the opening of the main valve 234 while checking the reading on the vacuum gauge 236 so that the opening of the main valve 234 is correct. Then, the temperature of the base cylinder 237 is raised to 50~50 by the heating heater 238.
After confirming that the temperature is set at 350℃,
The power source 240 is set to a desired power level to generate a glow discharge within the reaction chamber 201 to form a first layer on the substrate cylinder.

When the first layer contains halogen atoms, for example, SiF4 gas is further added to the above gas to form the reaction chamber 201.
send to.

Depending on the selection of gas species when forming each layer, the layer formation speed can be further increased. For example, if layer formation is performed using Si, H, or gas instead of 5rHa gas, the productivity can be increased several times, thereby improving productivity.

To form a second layer on the first layer created as described above, the outflow valves 217 to 221 are closed, the auxiliary valves 232 and 233 are opened, and the main valve 234 is fully opened to drain the system. Once evacuated to a high vacuum, CH4 gas and H2 gas are flowed into the reaction chamber 201 at a desired flow rate ratio by the same valve operation as in the case of forming the first layer, and glow discharge is generated according to desired conditions. It is accomplished by

When changing the amount of hydrogen atoms contained in the second layer, it can be controlled as desired, for example, by arbitrarily changing the flow rate of H2 gas introduced into the reaction chamber 201 as desired. can.

When the second layer contains halogen atoms, for example, CF4 gas is further added to the above gas and the mixture is sent into the reaction chamber 201.

Needless to say, when forming each layer, all outflows other than the gases necessary are closed. Also, when forming each layer, the gas used to form the previous layer is inside the reaction chamber 201, and the outflow valves 217 to 217 are closed. 221 to the inside of the reaction chamber 201, the outflow valves 217 to 22
1, open the auxiliary valves 232 and 233, fully open the main valve 234, and temporarily evacuate the system to a high vacuum, as necessary.

During layer formation, the base cylinder 237 is constantly rotated by a motor 239 at a desired speed to ensure uniform layer formation.

Next, a method for manufacturing a photoconductive member formed by a microwave discharge decomposition method will be described.

FIG. 3 shows an apparatus for manufacturing a light receiving member for electrophotography using a microwave discharge decomposition method.

Raw material gases for forming the respective layers of the present invention are sealed in the gas cylinders 302, 303, 304, 305, and 306 in the figure.
02 is SiH, gas (purity 99.999%) cylinder, 3
o3 is 82H6 gas diluted with H2 (purity 99.99
9%, hereinafter abbreviated as a, 5/F2) cylinder, 304 is NO
Gas (purity 99.5%) cylinder, 305 is CH4 gas (
306 is an H2 gas (purity 99.999%) cylinder.

To allow these gases to flow into the reaction chamber 301, make sure that the valves of the gas cylinders 302 to 306 and the leak valve 335 are closed, and also make sure that the inflow valves 312 to 31 are closed.
6, outflow valves 317-3211 auxiliary valve 332.
333 is open, first open the main valve 334 to exhaust the reaction chamber 301 and gas piping.
Next, the reading on the vacuum gauge 336 is approximately 5 X 1O-6 Torr.
At that point, close the auxiliary valves 332, 333 and outflow valves 317-321.

1 when forming the first layer on the base cylinder 337
For example, SiH4 gas from gas cylinder 302, gas cylinder from 303, a, H, /F gas from 303, NO gas from 304, valves 322, 323, 32
4 and adjust the pressure of the outlet pressure gauges 327, 328, 329 to 1 kg/cm', and then open the inlet valves 3H, , :l1.
3. Gradually open 314 and install mass flow controller 30.
7.308, :109. Subsequently, the outflow valves 317.3+8.319 and the auxiliary valve 332 are gradually opened to allow the respective gases to flow into the reaction chamber. SiH4 gas flow at this time! , B>Ha/Hz The outflow valve 317.
318 and 319, and also adjust the opening of the main valve 334 while checking the reading on the vacuum gauge 336 so that the pressure inside the reaction chamber reaches the desired value. and base cylinder 3
37 temperature is 50-350℃ by heating heater 338
After confirming that the temperature has been set to the desired temperature, the microwave power source 340 is set to the desired power, and a micro discharge is generated in the reaction N301 through the waveguide 341 and the dielectric window 342, and the temperature is set on the base cylinder. 1 layer is formed.

When the first layer contains halogen atoms, for example, 5tFi gas is further added to the above gas to form the reaction chamber 301.
send to.

Depending on the selection of gas species when forming each layer, the layer formation speed can be further increased. For example, if layer formation is performed using Si, H, gas instead of 5xH4 gas, the number of layers can be increased several times and productivity will be improved.

To form a second layer on the first layer created as described above, close the outflow valves 317 to 321, open the auxiliary valves 32 and 333, and fully open the main valve 334 to remove the inside of the system. After once evacuating to a high vacuum, CH4 gas and H2 gas are flowed into the reaction chamber 301 at a desired flow rate ratio by the same valve operation as in the case of forming the first layer, and microwave treatment is performed according to desired conditions. This is accomplished by causing an electrical discharge.

When changing the number of hydrogen atoms contained in the second layer, it can be controlled as desired by arbitrarily changing the flow rate of H2 gas introduced into the reaction chamber 301 as desired.

When the second layer contains halogen atoms, for example, CF4 gas is further added to the above gas and the mixture is sent into the reaction chamber 301.

Needless to say, when forming each layer, all outflows other than the gas required are closed, and when forming each layer, the gas used for forming the previous layer is inside the reaction '4301, and the outflow valves 317 to 317 are closed. 321 to the inside of the reaction chamber 301, the outflow valves 317 to 3
21 is closed, the auxiliary valves 332 and 333 are opened, the main valve 334 is fully opened, and the system is temporarily evacuated to a high vacuum, as necessary.

During layer formation, the base cylinder 337 is constantly rotated by a motor 339 at a desired speed to ensure uniform layer formation.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

<Example 1> Using the manufacturing apparatus shown in FIG. 2, an electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the preparation conditions shown in Table 1.

The light-receiving member (hereinafter referred to as a drum) is set in an electrophotographic apparatus, and electrophotographic characteristics such as initial charging ability, residual potential, and ghost are checked under various conditions.
After 00,000 sheets were printed on an actual machine, the decrease in charging ability, surface scraping, increase in image defects, etc. were investigated. Furthermore, image deletion on the drum was also evaluated in a high temperature, high humidity atmosphere of 85% at 35°C.

In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. The scratch resistance was examined by applying a certain load to a needle with a spherical tip and scratching the drum surface. The above evaluation results are shown in Table 2.

As shown in Table 2, remarkable superiority was observed particularly in terms of initial chargeability, ghost, image defects, surface abrasion, dielectric strength voltage, and scratch resistance.

<Example 2> In the same manner as in Example 1, the aluminum cylinder on which the photoconductive layer was formed was set in the manufacturing apparatus shown in Fig. 3, and a surface layer was formed on the photoconductive layer according to the preparation conditions shown in Table 3. , the same evaluation as in Example 1 was performed.

The results are shown in Table 4.

As seen in Table 4, the same characteristics as in Example 1 were obtained.

<Example 3> When creating the surface layer, the bias voltage of the cylinder was set to 115
Drums and samples were produced in the same manner as in Example 1 under the production conditions shown in Table 1 so that the voltage was 0V, and the same evaluation was performed.

The results are shown in Table 5.

As seen in Table 5, the same characteristics as in Example 1 were obtained.

Moreover, as a result of measuring the sample, it was found that it is 4-coordinated.

<Example 4> A drum was prepared in the same manner as in Example 1 under the conditions shown in Table 6 for the charge injection blocking layer, photoconductive layer, and surface layer, and the same evaluation was performed.

The results are shown in Table 7.

As shown in Table 7, the same characteristics as in Example 1 were obtained.

<Example 5> An aluminum cylinder is anodized to create an aluminum oxide layer (#203) on the cylinder surface, this is used as a charge injection blocking layer, and a photoquadratic layer and a surface layer are formed on this layer. A drum was prepared using the same layers as in Example 4, and
The same evaluation as in Example 1 was performed.

The results are shown in Table 9.

As shown in Table 9, the same characteristics as in Example 1 were obtained.

<Example 6> A drum was produced in the same manner as in Example 1, with the IR absorption layer, photoconductive layer, and surface layer each under the production conditions shown in Table 10, and the same evaluation was performed.

Furthermore, the drum was set in an electrophotographic apparatus using a semiconductor laser having a wavelength of 785 nm as a light source for image exposure, and it was checked whether interference fringes appeared on the image.

The results are shown in Table 11.

As seen in Table 11, characteristics similar to those of Example 1 were obtained, and no interference fringes appeared.

<Example 7> A drum was prepared in the same manner as in Example 1 under the conditions shown in Table 12 for the adhesion layer, the photovoltaic layer, and the surface layer, and the same evaluation was performed.

The results are shown in Table 13.

As seen in Table 13, a custom order similar to that of Example 1 was obtained.

<Example 8> A drum was produced in the same manner as in Example 1, with the IR absorption layer, charge injection blocking layer, photoconductive layer, and surface layer each under the production conditions shown in Table 14, and evaluated in the same manner as in Example 6. I did it.

The results are shown in Table 15.

As seen in Table 15, the same characteristics as in Example 1 were obtained.

<Example 9> A drum was prepared in the same manner as in Example 1 with the adhesion layer, charge injection blocking layer, photoconductive layer, and surface layer prepared under the conditions shown in Table 16, and the same evaluations were performed.

The results are shown in Table 17.

As seen in Table 17, the same characteristics as in Example 1 were obtained.

<Example 10> The adhesive layer, IR absorption layer, charge injection blocking layer, photoconductive layer, and surface layer were prepared under the conditions shown in Table 18, respectively, in Example 1.
A drum was prepared in the same manner as in Example 6, and the same evaluation as in Example 6 was performed.

The results are shown in Table 19.

As seen in Table 19, the same characteristics as in Example 1 were obtained.

<Example 11> A plurality of drums were prepared under the same conditions as in Example 1 except that the conditions for forming the photoconductive layer were changed to several conditions shown in Table 20.

As a result of subjecting these drums to the same evaluation as in Example 1,
In all cases, similar to Example 1, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 12> A plurality of drums were prepared under the same conditions as in Example 2 except that the conditions for forming the photoconductive layer were changed to several conditions shown in Table 21.

As a result of subjecting these drums to the same evaluation as in Example 2,
In all cases, similar to Example 2, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 13> A plurality of drums were prepared under the same conditions as in Example 3 except that the conditions for forming the photovoltaic layer were changed to several conditions shown in Table 22.

As a result of subjecting these drums to the same evaluation as in Example 3,
In all cases, similar to Example 3, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 14> A plurality of drums were prepared under the same conditions as in Example 4 except that the conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 23.

As a result of subjecting these drums to the same evaluation as in Example 4,
In all cases, similar to Example 4, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 15> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, the conditions for forming the photovoltaic layer were changed to several conditions shown in Table 25, and the other conditions were the same as in Example 15. Under the same conditions as 4, the second
A plurality of drums shown in Table 6 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 4,
In all cases, similar to Example 4, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 16> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to several conditions shown in Table 27. A plurality of drums shown in Table 29 were prepared under the conditions shown in Table 28.

As a result of subjecting these drums to the same evaluation as in Example 4,
In all cases, similar to Example 4, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 17> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to several conditions shown in Table 27. A plurality of drums shown in Table 31 were prepared under the conditions shown in Table 30.

As a result of subjecting these drums to the same evaluation as in Example 4,
In all cases, similar to Example 4, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 18> A plurality of drums shown in Table 32 were prepared under the same conditions as in Example 5 except for the conditions for forming the photoconductive layer, which were changed to several conditions shown in Table 25.

As a result of subjecting these drums to the same evaluation as in Example 5,
In all cases, similar to Example 5, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 19> The conditions for forming the surface layer were changed to those shown in Table 28, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the other conditions were the same as in Example 5. A plurality of drums shown in Table 33 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 5,
In all cases, similar to Example 5, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 20> The conditions for forming the surface layer were changed to those shown in Table 30, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the other conditions were the same as in Example 5. A plurality of drums shown in Table 14 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 5,
In all cases, similar to Example 5, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 21> The conditions for creating the rR absorption layer were changed to several conditions shown in Tables 35 and 36, and the third
A plurality of drums shown in Table 7 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 6,
In all cases, similar to Example 6, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 24> The conditions for creating the IR absorption layer were changed to i3s, several conditions shown in Table 38, the conditions for creating the photoconductive layer were changed to several conditions shown in Table 25, and the other conditions were as in Example 6. A plurality of drums shown in Table 39 were prepared under the same conditions as above.

As a result of subjecting these drums to the same evaluation as in Example 6,
In all cases, similar to Example 6, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 23> The conditions for forming the IR absorption layer were changed to several conditions shown in Table 35.38, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to several conditions shown in Table 27. A plurality of drums shown in Table 40 were prepared under the conditions shown in Table 28.

As a result of subjecting these drums to the same evaluation as on the example day,
In all cases, similar to Example 6, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 24> The conditions for forming the IR absorption layer were changed to several conditions shown in Table 35.38, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to several conditions shown in Table 27. A plurality of drums shown in Table 41 were prepared under the conditions shown in Table 30.

As a result of evaluating these drums in the same manner as in Example 6,
In all cases, similar to Example 6, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 25> The conditions for creating the adhesive layer were changed to several conditions shown in Table 42,
A plurality of drums shown in Table 43 were prepared under the same conditions as in Example 7 except for the above.

As a result of subjecting these drums to the same evaluation as in Example 7,
In all cases, drums that fully satisfied the electrophotographic characteristics were obtained, similar to Example F.

<Example 26> The conditions for creating the adhesive layer were changed to several conditions shown in Table 44,
A plurality of drums shown in Table 45 were prepared under the same conditions as in Example 7 except that the conditions for forming the photoconductive layer were changed to several conditions shown in Table 25.

As a result of subjecting these drums to the same evaluation as in Example 7,
In all cases, similar to Example 7, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 27> The conditions for creating the adhesive layer were changed to several conditions shown in Table 44,
The conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to the conditions shown in Table 28.
A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 7,
In all cases, similar to Example 7, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 28> The conditions for forming the adhesive layer were changed to several conditions shown in Table 44,
The conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to the conditions shown in Table 30.
A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 7,
In all cases, similar to Example 7, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 29> The conditions for creating the rR absorption layer were changed to several conditions shown in Table 35.36, and the fourth example was performed under the same conditions as in Example 8 except for
A plurality of drums shown in Table 8 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 30> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 49, the conditions for forming the IR absorption layer were changed to several conditions shown in Table 35.38, and the other conditions were not carried out. A plurality of drums shown in Table 50 were prepared under the same conditions as in Example 8.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 31> The conditions for creating the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for creating the IR absorption layer were changed to several conditions shown in Table 35.38, and the surface layer was created. A plurality of drums shown in Table 52 were prepared under the conditions shown in Table 28.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 32> The conditions for creating the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for creating the IRc & collection layer were changed to several conditions shown in Table 35.38, and the surface layer was created. A plurality of drums shown in Table 53 were prepared under the conditions shown in Table 30.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 33> A plurality of drums shown in Table 55 were prepared under the same conditions as in Example 9 except that the conditions for forming the adhesive layer were changed to several conditions shown in Tables 44 and 54.

As a result of subjecting these drums to the same evaluation as in Example 9,
In each case, similar to Example 1, drums that fully satisfied the electrophotographic characteristics were obtained.

<Example 34> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 56, the conditions for forming the adhesive layer were changed to several conditions shown in Tables 44 and 57, and the other conditions were the same as in Example. Under the same conditions as 9,
A plurality of drums shown in Table 58 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 9,
In all cases, similar to Example 9, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 35> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, the conditions for forming the adhesive layer were changed to several conditions shown in Table 44.57, and the conditions for forming the surface layer were changed to several conditions shown in Table 44.57. A plurality of drums shown in Table 59 were prepared under the conditions shown in Table 28.

As a result of subjecting these drums to the same evaluation as in Example 9,
In all cases, similar to Example 9, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 36> The conditions for creating the charge injection blocking layer were changed to several conditions shown in Table 24, the conditions for creating the adhesive layer were changed to several conditions shown in Table 44.57, and the conditions for creating the surface layer were changed to several conditions shown in Table 44.57. A plurality of drums shown in Table 60 were prepared under the conditions shown in Table 30.

As a result of subjecting these drums to the same evaluation as in Example 9,
In all cases, similar to Example 9, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 37> The conditions for forming the charge injection blocking layer were changed to several of the conditions shown in Table 61, and otherwise the conditions were the same as in Example 10.
A plurality of drums shown in Table 2 were prepared.

These drums were subjected to the same evaluation as in Example 1o, and as in Example 10, all drums were obtained that fully satisfied the electrophotographic characteristics.

<Example 38> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 64, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 63, and the other conditions were as in Example 1O. A plurality of drums shown in Table 65 were prepared under the same conditions as above.

As a result of subjecting these drums to the same evaluation as in Example 10, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 1O.

<Example 39> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 64, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 66, and the conditions for forming the surface layer were changed to several conditions shown in Table 66. A plurality of drums shown in Table 67 were prepared under the conditions shown in Table 28.

These drums were subjected to the same evaluation as in Example 1O, and as in Example 10, all drums were obtained that fully satisfied the electrophotographic characteristics.

<Example 40> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 64, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 66, and the conditions for forming the surface layer were changed to several conditions shown in Table 66. A plurality of drums shown in Table 68 were prepared under the conditions shown in Table 30.

These drums were subjected to the same evaluation as in Example 10, and as in Example 10, all drums were obtained that fully satisfied the electrophotographic characteristics.

<Example 41> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Table 35.38, and the conditions for forming the photoconductive layer were changed to several conditions shown in Table 35.38. A plurality of drums shown in Table 71 were prepared under the conditions shown in Table 69 for the preparation conditions and the conditions shown in Table 70 for the preparation conditions of the surface layer.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 42> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the rRi collection layer were changed to several conditions shown in Table 35.38, and the conditions for forming the photoconductive layer were changed to several conditions shown in Table 51. A plurality of drums shown in Table 73 were prepared under the conditions for forming the surface layer as shown in Table 72 and the conditions for forming the surface layer as shown in Table 70.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 43> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Table 35.38, and the conditions for forming the leading; A plurality of drums shown in Table 74 were prepared under the conditions for forming the surface layer as shown in Table 69 and the conditions for forming the surface layer as shown in Table 28.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 44> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Table 35.38, and the conditions for forming the photoconductive layer were changed to several conditions shown in Table 35.38. A plurality of drums shown in Table 75 were prepared under the conditions shown in Table 72 for the production conditions and the conditions for the production of the surface layer shown in Table 28.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 45> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Table 35.38, and the conditions for forming the photoconductive layer were changed to several conditions shown in Table 51. A plurality of drums shown in Table 76 were prepared under the conditions shown in Table 69 for the production conditions and the conditions for the production of the surface layer shown in Table 30.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 46> The conditions for creating the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for creating IR@ and several layers were changed to several conditions shown in Table 35.38, and photoconductive A plurality of drums shown in Table 77 were prepared under the conditions for forming the layer as shown in Table 72 and the conditions for forming the surface layer as shown in Table 30.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 47> A plurality of drums were prepared in which the conditions for forming the charge injection blocking layer and the photoconductive layer were as shown in Table 78, and the conditions for forming the surface layer were shown in Table 79.

As a result of subjecting these drums to the same evaluation as in Example 4,
In all cases, similar to Example 4, drums fully satisfying the electrophotographic characteristics were obtained.

Example 48 A plurality of drums were prepared, with the IR absorbing layer, charge injection blocking layer, and photoconductive layer prepared under the conditions shown in Table 80, and the surface layer formed under the conditions shown in Table 81.

As a result of subjecting these drums to the same evaluation as in Example 8,
In all cases, similar to Example 8, drums fully satisfying the electrophotographic characteristics were obtained.

<Example 49> A plurality of drums were prepared with the conditions for forming the adhesion layer, IR absorption layer, charge injection blocking layer, and photovoltaic layer shown in Table 82, and the conditions for forming the surface layer shown in Table 83. did.

These drums were subjected to the same evaluation as in Example 1O, and as a result, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 1O.

<Example 50> A drum was prepared in the same manner as in Example 1, with the charge injection blocking layer, photovoltaic layer, intermediate layer, and surface layer being prepared under the conditions shown in Table 84, and the same evaluation was performed. Similar to Example 1,
A drum with extremely excellent electrophotographic properties was obtained.

<Example 51> The mirror-finished cylinder was further subjected to turning processing using a sword bit with various angles to obtain cylinders with cross-sectional shapes as shown in Figure 4 and various cross-sectional patterns as shown in Table 85. I have prepared several books. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 2 and subjected to drum manufacturing under the same manufacturing conditions as in Example 1. The produced drums were evaluated in the same manner as in Example 1, and as a result, drums that fully satisfied the electrophotographic characteristics were obtained in all cases as in Example 1.6 <Example 5
2> The surface of the mirror-finished cylinder is then subjected to a so-called surface dimple treatment, in which the surface of the cylinder is exposed to the falling of many bearing balls, resulting in countless dents on the cylinder surface, resulting in a surface as shown in Figure 5. A plurality of cylinders having various cross-sectional patterns as shown in Table 86 were prepared.

The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 2 and subjected to drum manufacturing under the same manufacturing conditions as in Example 1. The produced drums were evaluated in the same manner as in Example 1, and as a result, drums that fully satisfied the electrophotographic characteristics were obtained in all cases, as in Example 1.

Table 23 Table 24 Table 25 Table 32 Table 33 Table 34 Table 35 Table 35 (continued) Table 36 Table 36 (continued) Table 37 Table 38 Table 38 (continued) Table 39 Table 40 Table 41 Table 43 Table 45 Table 46 Table 47 Table 48 Table 49 Table 50 Table 51 Table 52 Table 53 T% 55 Table 56 Table 61 Table 62 Table 64 Table 65 Table 67 Table 68 Table 71 Table 73 Table 74 Table 75 Table 76 Table 77 F%85 Table 86 [Summary of Effects of the Invention] Light-receiving member of the present invention By providing a surface protective layer composed of a diamond-like carbon thin film containing at least one of hydrogen atoms or halogen atoms, the photoreceptor surface can be prevented from mechanical damage and deterioration by ions and ozone caused by corona discharge. In addition to being able to effectively prevent electrification, a product with excellent electrophotographic properties such as charging ability and dark decay can be obtained, and when the light receiving member of the present invention is applied as an electrophotographic image forming member, it is possible to prevent There is no influence of electric potential,
Its electrical characteristics are stable, and images obtained using it are excellent without ghosts or image defects.

[Brief explanation of drawings]

Figures 1 (A) to (+) are diagrams schematically showing some typical examples of the layer structure of the light-receiving member of the present invention;
The figure shows a typical example of an apparatus for manufacturing the light-receiving member of the present invention, FIG. 2 is a schematic illustration of a manufacturing apparatus using a glow discharge method, and FIG. 3 is a schematic illustration of a manufacturing apparatus using a microwave discharge method. It is an explanatory diagram. FIGS. 4 and 5 are diagrams showing examples of the cross-sectional shape of the support of the light-receiving member of the present invention. 100... Light receiving member, 101... Support, 102
... Photoconductive layer, 103 ... Surface protective layer, 104 ...
- Charge injection blocking layer, 105...Long wavelength light absorption layer, 10
6... Adhesive layer, 107... Free surface, 108...
Intermediate layer, 2 (11,301... reaction chamber, 202-20
B, 302-30B... Gas cylinder, 207-211
．． 307-311...mass flow controller, 212
~216.312~316...Inflow valve 217~2
21.317~321...Outflow valve, 222~22
6,322~326...Valve, 227~231.3
27-331...Pressure regulator, 232.233.33
2.333...Auxiliary valve, 234.334...Main valve, 235.335...Leak valve 23B
, 33δ... Vacuum gauge, 237.337... Base cylinder, 238.338... Heater, 239.
339...Motor 240.340...High frequency power supply, 341...Waveguide, 342...Dielectric window

Claims (6)

[Claims] (1) A support, a photoconductive layer made of an amorphous material based on silicon atoms and containing at least one of hydrogen atoms or halogen atoms, and a surface protective layer on the support. 1. A light-receiving member comprising at least a light-receiving layer, wherein the surface protective layer is comprised of a diamond-like carbon thin film containing at least one of hydrogen atoms and halogen atoms. (2) The light-receiving member according to claim (1), wherein the light-receiving layer has a multilayer structure of three or more layers. (3) The light-receiving member according to claim (2), wherein the light-receiving layer has a charge injection blocking layer. (4) The light-receiving member according to claim (2), wherein the light-receiving layer has a long wavelength light absorption layer. (5) The light-receiving member according to claim (2), wherein the light-receiving layer has an adhesive layer having a function of improving adhesiveness. (6) The light-receiving member according to claim 2, which has an intermediate layer between the photoconductive layer and the surface protection layer.