JPS59102248A - Photosensitive body and its manufacture - Google Patents

Abstract

PURPOSE:To form an electrophotographic sensitive body good in resolution, gradation, and image density and moreover, long in life by forming a protective film of a polymer contg. a specified substance on an amorphous silicon type photosensitive layer. CONSTITUTION:A P type charge blocking layer 42 made of amorphous silicon hydride (a-Si:H) heavily doped with B or the like and an i-type photoconductive layer 43 made of a-Si:H light doped with B or the like 43 are laminated on a conductive substrate. Then, a protective film 40 made of a polymer contg., such as polyester resin, at least one of (i) Friedel-Crafts catalyts, such as AlCl3, (ii) an organometallic compd., such as Fe(C5H5)2, and (iii) an electron acceptor, such as succinic anhydride is formed on said laminate to obtain a photosensitive body 39.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoreceptor (for example, an electrophotographic photoreceptor) and a method for manufacturing the same.

Conventionally, as an electrophotographic photoreceptor, Se or As is added to 8e.
, Te, Sb, etc. doped photoreceptor, ZnO and C
Photoreceptors, etc. in which dS is dispersed in a resin binder are known. However, these photoreceptors have problems in terms of environmental pollution, thermal stability, and mechanical strength.

- In recent years, electrophotographic photoreceptors using amorphous silico Y(A-8i) as a base material have been proposed.

a-8i has a so-called dangling bond in which the bond of 5i-8i is broken, and many localized levels exist within the energy gap due to this defect. For this reason, hopping conduction of thermally excited carriers occurs, resulting in a small dark resistance, and photoexcited carriers are trapped in localized levels, resulting in poor photoconductivity. Therefore, we replaced the above defects with hydrogen atoms (
By compensating with c) and bonding H to Si, 1,
Filling of dangling bonds is performed.

Such amorphous hydrogenated silicon (hereinafter referred to as a-8
It is called i:H. ) has extremely excellent properties as a photosensitive layer of a photoreceptor because its resistivity decreases greatly when it is irradiated with light in the visible and infrared regions.

Figure 1 shows a-8i:H- as the base material.
An electrophotographic copying machine incorporating a -8i photoreceptor is shown. According to this copying machine, in the upper part of the cabinet 1,
A glass document mounting table 3 on which the document 2 is placed and a platen cover 4 that covers the document 2 are arranged. Below the document table 3, an optical scanning table consisting of a first mirror unit 7 equipped with a light source 5 and a first reflection mirror 6 is provided so as to be movable linearly in the horizontal direction of the drawing. The second mirror unit 20 is used to maintain a constant optical path length with respect to the first mirror unit 20.
The mirror unit moves according to the speed of the mirror unit, and the reflected light from the document table 3 side is incident on the photosensitive drum 9 as an image carrier through the lens 21 and the reflection mirror 8 in the form of a slit. . A corona charger 1 is installed around the drum 9.
0, a developing device 11, a transfer section 12, a separation section 13, and a cleaning section 14 are arranged, and the copy paper 18 fed from the paper feed box 15 through the paper feed rollers 16 and 17 is transferred with the toner image on the drum 9. Afterwards, the image is further fixed in the fixing section 19 (TγIr). In the fixing section 19, a fixing operation is performed by passing the developed copy paper between a heating roller having a built-in heater n and a pressure roller.

However, as a result of the inventor's study of the a-8i photoreceptor, the following facts were discovered. That is, a-8
A photoreceptor having a 1-type material on its surface is exposed to the atmosphere and moisture for a long period of time, so it is easily affected by the atmosphere and moisture, and corona discharge during the electrophotographic process (especially as shown in The chemical stability of the surface is poor due to the influence of chemical species generated in
The following defects occur.

(1) The a-Si layer has a skeleton of bonds between 8i-Si, and the bonding state is relatively good inside the layer, but on the surface side there are defects caused by polyvalent elements (Si). (i.e., many bond discontinuities or dangling bonds) and defect levels exist. Moreover, since a-8i is structurally hard, the defects once generated during film formation are retained. For this reason, when used in a device as shown in Figure 1, ions, molecules, and atoms in the discharge atmosphere due to corona discharge or other atmospheres are
It is easily adsorbed to the surface of the photoreceptor, and its electrical resistance in the surface direction decreases, making it easier for charges to leak in the surface (climbing) direction.

(2) As a result, in addition to unstable electrical and photoconductive properties, phenomena such as image blurring and white spots (white spots) occur. That is, although FIG. 2 (5) shows the surface potential after exposure at the initial stage of copying, after multiple copies, the initial potential shown by the broken line in FIG. The potential of the portion becomes gentle at the boundary with the exposed portion, and the potential itself attenuates. This is considered to be due to the charge leak mentioned in (1) above.

(3) Further, hydrogen is desorbed from the a-8i unphotosensitive material by heat and light after manufacture, which also causes the above-mentioned defects.

(4) Furthermore, the a-8i photoreceptor has poor long-term storage stability due to the above reasons, and this must also be overcome in practical terms.

As a result of extensive studies, the inventors of the present invention have discovered an a-Si non-photosensitive material that effectively solves the above-mentioned problems, and have arrived at the present invention.

That is, in the a-8i photoreceptor according to the present invention, a polymer compound film containing at least one of a Friedel-Crauch catalyst, an organometallic compound, and an electron-accepting substance is provided on the surface as a protective film ( This is characterized in that the defects on the surface are eliminated or reduced.

According to this photoreceptor, a polymer protective film containing a Friedel-Crach catalyst is provided on the surface of the a-8i semiconductor, and surface defects specific to the a-8i are eliminated or reduced. It is possible to prevent the effects of ions, molecules, and atoms that try to adsorb onto the surface of the material, and improve electrical and photoconductive properties.

Therefore, it is possible to eliminate image blurring and white spots in the copying process as described above, improve resolution, gradation, and image density, prevent changes in image quality even during repeated copying, and preserve photoreceptors for long periods of time. The properties are also improved.

The reason for this remarkable effect is that the metal atoms of the Friedel-Craft catalyst contained in the above-mentioned protective film are adsorbed, or that Friedel-Craf as a skeletal bone container is absorbed by the Friedel-Craft catalyst through its Lewis acid action. The fluorocatalyst accepts electrons from dangling bonds caused by defects on the surface of the a-Si based semiconductor layer, and forms bonds between the two (covalent or ionic bonds between the metal atoms of the Friedel-Craft catalyst). It is thought that this is because In addition, when the organometallic compound is included in the protective film, the properties of the organometallic compound as an electron acceptor (for example, electron affinity close to 2 eV) may be due to defects on the surface of the a-Si semiconductor layer. This is thought to be because the electrons from the dangling bonds are accepted and bonds are formed between them. It is also believed that when the electron-accepting substance is present in the protective film, it accepts electrons from dangling bonds and forms chemical bonds. The Friedel-Craft catalyst, organometallic compound, and electron-accepting substance described above may each be contained in the protective film alone, or a plurality of types may be contained in combination.

The content of these is 0.01 to 70% by weight (preferably 1% by weight)
-% by weight), but if the amount falls outside of this range, the effect of containing it will be lost, and if it is too large, the mechanical strength of the protective film will deteriorate and the retention of the contained substances will deteriorate.

In addition, an important feature of the photoreceptor of the present invention is that a protective film made of a polymer compound containing each of the above-mentioned substances is provided on the surface. In other words, this protective film confines processing substances such as Friedel-Crach's catalyst that have acted on the surface to the same surface, so they do not come off during use or handling of the photoreceptor, and the remarkable effects described above are achieved. It is possible to retain more than enough.

The protective film is preferably formed of a material as described below, but is preferably formed of a thermosetting resin having a three-dimensional structure. Further, the thickness of this protective film has a certain desirable range in order to achieve the above effects, and is preferably 0.1 to 50 μm.

If it is less than 0.1 .mu.m, it is too thin and the effect is weak, and if it exceeds 1.0 .mu.m, it is too thick and tends to impair the characteristics of the photoreceptor.

The present invention also proposes to manufacture the above-mentioned photoreceptor by the following method. That is, this method includes the steps of forming an amorphous silicon-based semiconductor layer on a support; The method is characterized by comprising a step of coating the surface of the amorphous silicon-based semiconductor layer.

In this method, a Friedel-Craft catalyst, an organometallic compound, an electron-accepting substance, and an activated or ionized hydrogen and/or halogen or hydrogen and/or a halogen are added before forming the protective film. The surface can be previously treated with at least one active species. In this case, the Friedel-Craft catalyst, organometallic compound, or electron-accepting substance has the effect of removing at least some of the defects on the surface of the photoreceptor based on the above-mentioned action, so the above-mentioned protective film is provided. In this case, the above-mentioned protective effect of the protective film is added, and even more effective effects can be achieved. In addition, the surface of the photoreceptor is
When treated with ionized or activated hydrogen and/or halogen or active species containing hydrogen and/or halogen, the hydrogen and/or halogen binds to the surface of the photoreceptor and eliminates defects. It is thought that the protective film fills up the defects and reduces the defects and defect levels, and the effect of the protective film becomes even more sufficient as described above.

The free chill crude catalyst that can be used in the present invention is AJI
C13, SbC&, PeC12, FeCl3.5nC1
l, TiC74, TeC4, B1C1a, ZnC4, B
It may be H3, P2O5, H2SO4, H3PO4, etc., or a mixture thereof, and the above catalysts can be used in the form of a solution.

In addition, as organometallic compounds that can be used, compounds having a carbon-metal bond, and this bond mode is C5H.
Those with ionic bonds such as s-N, i+, [(CH
3) aAJJ: Examples include those having an electron-deficient bond as in [2], those having a σ bond as in (CH3) < Ti, and those having a π bond as in Fe (C3H3)2. Among these, the most effective one is No. A of the periodic table.
It is a π complex compound having a so-called d-pro-nk transition metal, such as Group VA, Group VA, Group VIA, Group VIIA, Group I, and Group IB. For example, above (
In addition to D Fe (C5Hs)2, Fe (C5H
s ) (CH3COC3H4), Fe2 (CO)
4 (C5Hs)2, Fe (Co)3 (C4H4
), Fe (CgH7)2, Fe (C5Hs) (C
5H4σD), Fe (C3H5) (CHaCsHa
), Ti (c5a5)2, Ti (Os (CH3)
s )2, Ni (C5Hs )z, Ni (C6H1
□)2, Ni(C4H7)2, Ni(CaHs) (
C5Hs ), Co (C5Hs ) (1,5-C3
l-112), Co (C5HsCHCA!2) (C
5Hs), CoI2 (C5H5) (NC5H5)
In addition to these, there are also bismuth, chromium, manganese,
Organometallic complexes such as molybdenum, tungsten, copper, palladium, gold, platinum, and silver are also effective. In addition, Zn
(C2H5)2, Zn(CsHs)2, M(C2H5
) a, AA! (C6H5) 3, Cr (CH3)
4, Cr(C5H6)2, Cr(CO)s, CO2(
CO) a, Co (C3H5)2, Co(C3H5)
3, Fe(CO)5, Ni(CO)4, etc. can be used. Further, each of the above-mentioned organometallic compounds may be used alone or as a mixture, or in the form of a solution.

Examples of electron-accepting substances that can be used include succinic anhydride, maleic anhydride, dibromaleic anhydride,
Phthalic anhydride, tetrachlorophthalic anhydride, tetrabromo phthalic anhydride, 3-nitro phthalic anhydride, 4-nitro phthalic anhydride, pyromellitic anhydride, mellitic anhydride,
Tetracyanoethylene, tetracyanoquinodimethane, ρ
-Dinitrobenzene, m-dinitrobenzene, chloro-
2,4-dinitrobenzene, 1.3.5-) dinitrobenzene, varanitrobenzonitrile, vicryl chloride, quinone chlorimide, chloranil, promanil,
2.5-cyclop-benzoquinone, dichlorodicyanobarabenzoquinone, haloquinone, anthraquinone, dinitroanthraquinone, 2.7-sinitrofluorenone, 2,4.7-) 'J=)rofluorenone, 2,4
, 5.7-titranitrofluoreno7.9-fluorenylidene-[dicyanomethylenemalonodinitrile], polynitro-9-fluorenyritene-[dicyanomethylenemalonodinitrile], picric acid, 0-nitrobenzoic acid,
p-Nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3.5-
Examples include dinitrosalicylic acid, phthalic acid, mellitic acid, acrylonitrile, methyl methacrylate, ethyl cyanoacrylate, cyclopentadiene, trichloroethylene, or carbon tetrachloride, 7-rogenated alkyl iodine, chlorine, fluorine, and other compounds with high electron affinity. be able to. Among these, halogens and rhodanated alkyls act as σ-electron acceptors, and aromatic or unsaturated compounds such as trinitrobenzene, chloranil, tetracyanoethylene, quinones, etc. act as π-electron acceptors. act. Each of the electron acceptors mentioned above may be used alone or in the form of a mixture, and can be used in a solution state.

In addition, examples of the polymer compounds forming the protective film in the present invention include polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, and alkyd resin. , addition polymerization type resins such as polycarbonate resins, silicone resins, melamine resins, polyaddition type resins, polycondensation type resins, and copolymer resins containing two or more of the repeating units of these resins, such as vinyl chloride-acetic acid. Examples include vinyl copolymer resins, hinyl chloride/L=-pinylacetate-maleic anhydride copolymer resins, and the like. In order to coat the surface of the photoreceptor with this polymer compound, the polymer compound is made into a solution, the above-mentioned Friedel-Craft catalyst, etc. is mixed and dispersed in this solution, and using this, a known dipping method, spraying method, etc. are used. A polymer compound film can be formed to a desired thickness on the surface of a photoreceptor by a coating method or the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the drawings.

3 to 6 illustrate an a-8i electrophotographic photoreceptor based on the present invention.

The photoreceptor 39 in FIG. 3 has a P-type charge blocking layer 42 made of a-Si:H heavily doped with an HIA group element of the periodic table, such as boron, on a conductive support substrate 41 such as An, and a P-type charge blocking layer 42 made of an a-Si:H element of the mA group of the periodic table. , and an i-type photoconductive layer 43 made of, for example, a-Si:H lightly doped with boron. The photoconductive layer 43 has a ratio of resistivity ρD in the dark and resistivity ρL during light irradiation that is sufficiently large as an electrophotographic photoreceptor, and has good photosensitivity (particularly to light in the visible and infrared regions). . In addition, elements of group mA of the periodic table,
For example, for boron, the flow rate ratio (B2H6/SiH4) =
By doping at 1 to 500 ppm, it becomes intrinsic, i.e., i-type (specific resistance is 1011 to 1012Ω).
-a), it is possible to increase the resistance. By increasing the resistance, the charge retention ability can be improved. As a result, a photoconductive layer having good photosensitivity and potential holding ability can be obtained. In addition, in order to sufficiently prevent the injection of electrons from the substrate 41, the charge blocking layer 42 contains an element of Group ⅠA of the periodic table (for example, boron) at a flow rate ratio of B2H6/SiH4=5.
00 ~ 100.000 1) I) Doped with m, P
It is better to make it into a type (or even type 1). There is also an appropriate range for the thickness of each layer of the photoreceptor, and the photoconductive layer 43 has a thickness of 2.
~80 μm (preferably 5-30 μm), and the blocking layer 42 has a thickness of 100X ~1 ttm (preferably 40
0 to 5000X). The photoconductive layer 43 has a thickness of 2μ
If it is less than m, the charging potential will not be sufficient, and if it exceeds 80 μm, it is not practical and it takes time to form a film.

If the blocking layer 42 has a thickness of less than 100 A, there will be no blocking effect, and if it exceeds 1 μm, the charge transport ability will be poor. Note that each of the above layers needs to contain hydrogen. In particular, the hydrogen content in the photoconductive layer 43 is essential to compensate for dangling bonds and improve photoconductivity and charge retention, and is usually 1 to 40%.
atomic height, 10 to 30 atomic t
4 is more desirable. In addition, the blocking layer 42
In addition to boron, M and Ga are used as impurities to control the conductivity type of P-type.

Group 11rA elements of the periodic table, such as In and TA, can be used.

This blocking layer can also be N-type, and this (7)
The fC menu can be doped with Group VA elements of the periodic table, such as P1AsS8b and Bi.

The photoreceptor in FIG. 4 is mounted on a conductive support substrate 41 such as M.
It has a structure in which photoconductive layers 43 made of a-8iC:H are sequentially laminated. In particular, the photoconductive layer 43 has a nitrogen atom content of 1 to 30 atomic % (preferably 1
5 to 25 atomic%). In addition, if it is made into an i-type by doping with boron as described above, it is possible to increase the resistance and improve the photosensitivity (particularly in the visible and infrared regions). By setting the carbon atom content to 5 to 90 atomic % (preferably 10 to 50 atomic %), the charge blocking layer 42 is made thin and has a high resistance (ρ==1012 to 1013 Ω), which lowers the charging potential of the photoreceptor. Retention ability can be improved.

This charge blocking layer may also be doped with impurities as described above.

The photoreceptor shown in FIGS. 5 and 6 has a first a-8iC:H layer 42, an a-84:1-1 (photoconductive layer 43, a second a-8iC: The first a-8iC:H layer 42, in the example shown in FIG. and 2μ
It is preferable to form the film with a thickness of m to 80 μm (more preferably 5 μm to 80 μm). 1st a-8iC: 14 layers 4
2 mainly indicates a charge blocking function in the example of FIG. 5, similar to FIG. 4. The photoconductive layer 43 in FIG. 6 generates charge carriers in response to light irradiation, and its thickness is 3000λ to 5μm (particularly 5000X to 5μm).
3μ, m) is desirable. Furthermore, the second a-8i
The C:H layer 44 improves the surface potential characteristics of this photoreceptor, maintains the potential characteristics over a long period of time, maintains environmental resistance (prevents the influence of humidity, atmosphere, and chemical species generated by corona discharge), and improves surface hardness. It has functions such as improving printing durability due to its high temperature, improving heat resistance when using a photoreceptor, and improving thermal transferability (particularly adhesive transferability), and functions as a surface modification layer. The thickness t of this second a-8iC:H layer 44 is 100
X≦t≦5oooi<preferably 400X≦t≦200
OA) is important.

As described above, the surface of each photoreceptor illustrated in FIGS. 3 to 6 has many defects and defect levels, and is likely to cause charge leakage due to adsorption of ions and the like. For this,
According to the present invention, on the surface (a-8i surface) of each photoreceptor,
A polymer compound film 40 (see FIGS. 3 to 6) containing the above-mentioned Friedel-Craft catalyst and the like is formed, thereby eliminating or reducing surface defects.

Next, a method and apparatus (glow discharge apparatus) for manufacturing the above-mentioned photoreceptor (for example, drum-shaped) will be explained with reference to FIG.

Inside the vacuum chamber 52 of this device 51, a drum-shaped substrate 41
is set so as to be vertically rotatable, and the substrate 4 is heated by a heater 55.
1 can be heated to a predetermined temperature from the inside.

A cylindrical high-frequency electrode 57 with a gas outlet 53 is disposed around and facing the substrate 41, and a high-frequency power source 56 generates a jiglow discharge between the electrode 57 and the substrate 41. In addition,
In the figure, 62 is a source of 8iH4 or a gaseous silicon compound, 63 is a source of nitrogen such as NH3 or N2, and 64 is a C
65 is a carrier gas supply source of Ar$, 66 is an impurity gas (for example, B2H6 or PH3) supply source 67 is each flow meter. In this glow discharge device, first, the support After cleaning the surface of a body, for example, the M substrate 41, the substrate is placed in a vacuum chamber 52.
The gas pressure inside 2 is adjusted to 10" Torr, and the substrate 41 is heated to a predetermined temperature, particularly 100 to 350 Torr.
The temperature is maintained at a temperature of 150 to 300°C.

Next, using a high purity inert gas as a carrier gas, 8
iH4 or gaseous silicon compounds, and NH3 or N2
A mixed gas prepared by diluting an appropriate amount of CH, i, B2H6, etc. is introduced into the vacuum chamber 52, for example, 0.01 to 10T.
The high frequency voltage (
For example, 13.56 MHz) is applied. As a result, each of the reaction gases described above is decomposed by glow discharge between the electrode 57 and the substrate 41, and a-8iN:H containing a-8i:H, a-8iC:H1 hydrogen is dissolved in the above-mentioned layers 42, 43, 44. (i.e., corresponding to the examples of FIGS. 3 to 6)
deposit

Furthermore, the photoreceptor produced using the above-mentioned glow discharge device is coated with a known dipping method or spray coating method.
Contacting a polymer compound (e.g. polyester resin liquid) containing a Friedel Krach catalyst (e.g. FeC13),
The same resin film is formed on the surface of the photoreceptor.

In the above manufacturing method, the support temperature is set at 100 to 350°C in the step of forming an a-Si layer on the support, so it is possible to improve the film quality (especially electrical properties) of the photoreceptor. can.

Note that when the surface of the photoreceptor is pretreated with a Friedel-Craft catalyst, an organometallic compound, or an electron-accepting substance before forming the above-mentioned protective film, the photoreceptor may be immersed in a solution of these. For pretreatment with activated or ionized hydrogen and/or halogens or active species containing hydrogen and/or halogens, the apparatus of FIG. The active hydrogen or hydrogen ions can be generated by glow discharge and applied to the surface of the photoreceptor. Introduced gases include H2, H2S, NH3, CH4, C2H6, C3H8.
Saturated hydrocarbon gases such as C2H4, C2H2, C3
Unsaturated hydrocarbon gases such as H6 can also be used. In the case of halogen, F2, BF3, S i F 4, PF5
, SF6, CF4, C2F6, C3F8 @'s purple compound gas, C12, BCl33.5iCA! 4. PCl
3. It can be introduced as a chlorine compound gas such as FeC73 or CCZ4. In addition, when processing with both hydrogen and halogen, the above-mentioned gases may be used together and supplied at the same time, or HF, SiHF3.5iH2Fz, CH3F, CHF3, HCζ5iHC13,5iH2
It is preferable to introduce C12, CH3cz, CHCl3, etc. for glow discharge decomposition.

In addition, in order to compensate for dangling bonds in the above a-Si-based layer, fluorine is introduced in place of the above-mentioned H or in combination with H, and the a-Si2 F
, a-si:)(:F', a-8iN:F,
a-5jN:I(:F', a-8iC:F,
It can also be a-8iC:H:F. In this case, the cumulative amount of fluorine is preferably 0.01 to 20 atomic %, and preferably 0.5 to 10 atomic %.

The above manufacturing method is based on the glow discharge decomposition method, but there are also methods such as sputtering method, ion blating method, and method of evaporating 81 while introducing activated or ionized hydrogen with a hydrogen discharge tube. (In particular, Japanese Patent Application Laid-Open No. 56-78413 (Patent Application No. 54-152) filed by the present applicant)
The above photoreceptor can also be manufactured by the method of No. 455).

FIG. 8 shows the photoreceptor according to the present invention in the above-mentioned Japanese Patent Application Laid-Open Publication No.
This figure shows a vapor deposition apparatus used for producing the film by the vapor deposition method No. 13.

A vacuum pump (not shown) is connected to the Pel jar 71 via an exhaust pipe 73 having a butterfly valve 72, and the inside of the Pel jar 71 is thereby pumped, for example, from 10-3 to 10".
``A high vacuum state of 7 Torr is created, and the substrate 41 is placed inside the Pel jar 71 and heated to a temperature of 100 to 350°C, preferably 150 to 300°C by a heater 75, and also heated by a DC power source 76. 0 to -10 on board 1
A DC negative voltage of KV, preferably -1 to -6 KV is applied, and active hydrogen and hydrogen ions are discharged into the Pelger 71 from a hydrogen gas discharge tube 77 whose outlet is connected to the Pelger 71 so that its outlet faces the substrate 41. While heating the internal source 79, each upper shutter S is opened to simultaneously evaporate silicon and aluminum at an evaporation rate such that the evaporation rate ratio is, for example, 1:10, and into the Pelger 41.
Activated NH3 gas or CH4 gas is appropriately introduced into the discharge tube 7o, thereby forming the above-mentioned layers 42, 43, and 44 containing a predetermined amount of aluminum, if necessary.

For example, the structure of the discharge tube 77 is shown in FIG. 9, as shown in FIG. , a discharge space member made of, for example, cylindrical glass that surrounds the discharge space 83, and a ring-shaped other electrode member 86 having an outlet 85 provided at the other end of the discharge space member 84. member 82 and the other electrode member 8
When a direct current or alternating current voltage is applied between 6 and 6, for example hydrogen gas supplied via gas port 81 generates a glow discharge in discharge space 83, thereby emitting electronic energy tL. The discharge space members 8 and 1 in this illustrated example have a double-tube design and are configured to allow cooling water to flow therethrough, with reference numerals 87 and 88 indicating the cooling water inlet and outlet.

89 is a cooling fin of one electric plate member 82). The distance between the electrodes in the hydrogen gas discharge tube 77 is 10 to 1
5 crn, the applied voltage is 600 V, and the pressure in the discharge space 83 is about 1 O-2 Torr.

In the apparatus shown in Fig. 8, after forming each layer of the a-8i system, a polymeric protective film containing Friedel-Craft catalytic heat, etc. is formed on the surface of the -2 photoreceptor to eliminate defects. The process can be carried out.

Next, specific examples of the present invention will be described.

Example 1 An M drum that had been triturated, washed with 1 ethylene ethylene, and etched with a 0.1% NaOH aqueous solution and a 0.1% HNO3 aqueous solution was placed in the glow discharge apparatus shown in Fig. 7, and the inside of the reaction tank was heated to a temperature of lo-6 Torr. After evacuation to a high degree of vacuum and heating the support temperature to 200°C, high purity Ar gas was introduced.
Torr back pressure source frequency 13.56 M) Iz
, 100 W of high frequency power was applied, and preliminary discharge was performed for 15 minutes. Next, by glow discharge decomposition of the (Ar + 5iI-14) mixed gas and, if necessary, the B2H6 gas, P-type a-8i:H to prevent carrier injection and i-type a-8i:H as a photoconductive layer are formed. A photoreceptor (see FIG. 3) consisting of a photosensitive layer was formed.

Next, the photoreceptor was immersed in a solution in which FeCl2.6H20 was mixed and dispersed in a polyester resin solution to form a protective film.

To form the protective film, the photoreceptor is immersed in a polyester resin solution with its axial direction perpendicular, and then the photoreceptor is pulled up in the opposite direction to form a polyester resin film on the treated surface of the photoreceptor. It was formed to have a thickness of 10 μm. In addition, for comparison, a photoreceptor without resin coating was prepared.

Regarding the photoreceptor coated with resin as described above,
Copy machine (U-Bix 1600: manufactured by Konishiroku Photo Industry)
Images were created using the following methods. As a result, the photoconductor coated with the resin described above provided a clear image with good resolution, no white spots, and no capri, whereas the photoconductor without the resin coating process produced a clear image with good resolution and no white spots. , the resolution was poor, and only a lot of white spots and foggy images were obtained.

Even after repeated copying, stable and high-quality images were continuously obtained when the above-mentioned coating treatment was performed.

Example 2 When a resin containing 7-erocene was used in place of FeCAa.5H20 in Example 1 and resin coating was performed in the same manner, good results similar to those in Example 1 were obtained.

Example 3 In Example 1, when the surface of the photoreceptor was coated with a resin containing trinitrobenzene, the same good results as in Example 1 were obtained.

In addition, in the above-mentioned examples, even if phenol resin, polyurethane resin, etc. are used in addition to the above-mentioned polyester,
Results similar to those above were obtained.

Example 4 An aluminum doped a-8i:H layer and a-8iS as a photoconductive layer were deposited on a support in the deposition apparatus shown in FIG.
The H layer and the H layer were sequentially laminated. The H2 flow rate at this time was 150c
c/min, evaporation source is polycrystalline 81 and M, evaporation rate ratio Si
/) J is 1, /1.0-' in the former, 1 / in the latter
10-', evaporation source is electron beam heating method, discharge tube is D
The power of the C discharge tube was 350 W, the substrate temperature was 250° C., and the substrate voltage was 15 KV.

Then, when a resin film containing a Friedel-Krach catalyst was formed on the surface of the obtained photoreceptor in the same manner as in Example 1, the image forming operation and evaluation results were the same as described in Example 1. there were.

[Brief explanation of drawings]

FIG. 1 is a schematic sectional view of a conventional electrophotographic copying machine. 2nd position, σ3) is a graph showing the change in surface potential of the a-Si photoreceptor after exposure. 3 to 9 show examples of the present invention, and FIGS. 3, 4, 5, and 6 are cross-sectional views of each a-8i photoreceptor, and FIG. The figure is a schematic sectional view of a glow discharge device, FIG. 8 is a schematic sectional view of a vacuum evaporation device, and FIG. 9 is a sectional view of a gas discharge tube. In addition, in the symbols shown in the drawings, 39......a-Si non-photosensitive member 41...
......Support (substrate) 42...
Blocking layer or charge transport layer 43...
Photoconductive layer 44...Narrow surface modified layer I...Heater 56...High frequency power source 57... - Electrodes 62 to 66... Gas supply source 70.77... Gas discharge pipe 78.79... Evaporation source. Agent: Patent attorney Hiroshi Aisaka (and 1 other person) Figure 1 Figure 2 Figure 3

Claims (1)

[Claims] 1. An amorphous silicon-based photoreceptor protected by a polymeric compound film containing at least one of a Friedel-Craft catalyst, an organometallic compound, and an electron-accepting substance. A photoreceptor characterized in that the protective film is provided as a film on the surface. 2. The protective film contains at least one of a Friedel-Craft catalyst, an organometallic compound, and an electron-accepting substance in a total amount of 0.01 to 0.01. 70% by weight of the photoconductor according to claim 1. 3. The photoreceptor according to claim 1 or 2, wherein the protective film has a thickness of 0.1 to 50 μm. The photoreceptor described above. 4. Friedelkraff catalyst, organometallic compound,
The surface is pre-treated with at least one of an electron-accepting substance and an activated or ionized hydrogen and/or halogen, or an active species containing hydrogen and/or a halogen, and a protective film is provided on the treated surface. A photoreceptor according to any one of claims 1 to 3. 5. The photosensitive material according to any one of claims 1 to 4, wherein the surface side on which the protective film is provided extends from the amorphous aqueous hydrogenated and/or fluorinated nitrided 7-licon layer. body. 6. The layer forming the surface on which the protective film is provided has the number m of the periodic table.
Item 1 of the claims, which contains a Group A element.
The photoreceptor described in any one of item 5. 7. Step of forming an amorphous silicon-based semiconductor layer on a support; 1. A method for manufacturing a photoreceptor, comprising the step of coating a surface of a semiconductor layer. 8. Before applying the protective film, apply a Friedel Krach catalyst,
At least one of an organometallic compound, an electron-accepting substance, and an activated or ionized hydrogen and/or hydrogen or an active species containing hydrogen and/or a nitrogen.
Method 09 described in claim 7, in which the surface is pretreated with seeds, when forming an amorphous silicon layer on the support, the temperature of the support is 100 to 100℃.
Claim 7 or 8, maintained at 350°C
The method described in section. 10. The method according to any one of claims 7 to 9, characterized in that the surface layer on which the protective film is provided is an amorphous hydrogenated and/or fluorinated nitride cricon layer. 11. The seventh aspect of claim 1, wherein the layer forming the surface on which the protective film is provided contains an element of group 111A of the periodic table.
The method described in any one of Items 1 to 10.