JPS5832009A - Preparation of photosensitive material for electrophotography - Google Patents

Abstract

PURPOSE:To manufacture a photosensitive material for electrophotography, having an amorphous silicon photoconductive layer having high photosensitivity and durability, by forming a silicon layer on the surface of a substrate cleaned with glow discharge treatment. CONSTITUTION:The substrate 11 cleaned to a certain degree by chemical treatment is fixed with a fixing member 12 in the glow discharge evaporation chamber 10, which is evacuated as shown by the arrow A by opening the main valve 29. The surface of the substrate 11 is cleaned sufficiently by the glow discharge between the capacitance-type electrodes 15, 15' with the high frequency electrical source 14. Then proper amounts of Ar, SiH4 as raw material, and if necessary PH3 gas, etc. as impurities are fed to the chamber from the gas bombs 16, 17, 18 through the flow meters 19, 20, 21 to maintain the vacuum degree in the evaporation chamber to about 10<-2>-3Torr expressing in terms of the raw material gas pressure. The substrate 11 is heated at about 50-350 deg.C with the heater 13, and exposed to the glow discharge. By this procedure, the SiH4 is decomposed and Si is evaporated and deposited on the substrate 11 forming an amorphous silicon layer.

Description

[Detailed description of the invention] The present invention relates to a method for manufacturing an electrophotographic photoreceptor.

Conventionally, photoconductive materials constituting the photoconductive layer of an electrophotographic photoreceptor include inorganic photoconductive materials such as 8e, CtlR, and ZnO, and poly-N-vinyl carno ζ sol (PVK).
Organic photoconductive materials such as linitrofluorenone (TNF) (
opc) is commonly used.

In electrophotographic photoreceptors that use materials such as Hyakunen, etc., there are still a number of points that can be solved, and certain conditions must be met. In reality, an appropriate electrophotographic photoreceptor is used depending on each individual situation.

For example, in an electrophotographic photoreceptor using Se as a material for forming a photoconductive layer, Se alone has a narrow spectral sensitivity range, so T
Efforts have been made to widen the spectral sensitivity range by adding e or As.

Hyakunen et al., such an electrophotographic photoreceptor having a photoconductive layer at the tip of a Se thread containing Te and As certainly improves the spectral sensitivity range, but because the optical fatigue increases, the same original cannot be processed continuously. Repeated copying may cause a decrease in the image density of the copied image and background stains (capri), and if you continue copying other originals, the image of the previous original may be copied as an afterimage (ghost development). have.

However, since Ss, especially As and Te, are extremely harmful substances to the human body, it is necessary to devise ways to use manufacturing equipment that does not come into contact with the human body during manufacturing. The investment in capital is significantly large. Furthermore, if the photoconductive layer is exposed even after manufacturing, the surface of the photoconductive layer will be directly rubbed during cleaning and other treatments, and a portion of it will be scraped off, preventing development. If it gets mixed in with the agent, scatters in the copying machine, or gets mixed in with the copied image, it can cause contact with the human body.In addition, the surface of the Se-based photoguide TTM is susceptible to corona discharge. If the photoconductive layer is repeatedly exposed many times, crystallization or oxidation occurs near the surface of the layer, often resulting in deterioration of the electrical properties of the photoconductive layer. Alternatively, if the surface of the photoconductive layer is exposed, when a liquid developer is used to visualize (develop) an electrostatic latent image, it may come into contact with the solvent, resulting in poor solvent resistance (
However, it cannot be said that the Se-based photoconductive layer necessarily satisfies this requirement.

In order to improve these points, the surface of the Se-based photoconductive layer was
It has been proposed to cover the surface with a surface coating layer called a so-called protective layer or an electrically insulating layer.

Even with these improvements made by Hyakuten et al., the current situation is that it is difficult to say that a sufficient solution has been achieved in terms of the ML electrical characteristics and surface properties required for the leading thy* surface coating layer.

Furthermore, FIE-based light-guiding photoconductive layers are usually formed by vacuum evaporation, which requires significant capital investment in equipment and does not reproducibly produce photoconductive layers with desired photoconductive properties. In order to obtain
It is necessary to strictly adjust various control parameters such as degree of vacuum, deposition rate, and cooling rate. Furthermore, the surface coating layer is
A separate device from the device for forming the photoconductive layer is installed because the photoconductive layer is formed by pasting a film-like material on the surface of the photoconductive layer with an adhesive or by applying a surface coating layer forming material 17. Because of the need to conduct
It is formed in an amorphous state in order to have a high dark resistance as ', i, but since Se crystallization occurs at an extremely low temperature of about 65°C, it cannot be trapped during handling after manufacture or during use. It also has a drawback in terms of heat resistance, in that it is highly affected by the ambient temperature and frictional heat caused by rubbing with other members during the image forming process, causing crystallization and development, which tends to lead to a decrease in dark resistance. .

On the other hand, in electrophotographic photoreceptors that use ZnO, CdS, etc. as photoconductive layer constituent materials, the photoconductive layer is made of ZnO or CdS.
It is formed by uniformly dispersing photoconductive material particles such as in a suitable resin binder. An electrophotographic photoreceptor having this so-called binder-based photoconductive layer has advantages in manufacturing compared to an electrophotographic photoreceptor having an Se-based photoconductive layer, and can relatively reduce manufacturing costs. I can do it. That is.

The binder-based photoconductive layer is prepared by applying a coating solution prepared by kneading ZnO or (7d9) particles and a suitable resin binder using a single vortex solvent onto an appropriate substrate, using a doctor blade method, dipping method, etc. Since it can be formed by simply applying it using the coating method described above and then solidifying it, a considerable amount of capital is invested in manufacturing equipment compared to an electrophotographic photoreceptor having a conductive layer made of Se-based materials. The method itself is simple and easy.

Hyakunen et al., a binder-based photoconductive layer is basically a two-component system consisting of a photoconductive material and a resin binder, and is formed by uniformly dispersing photoconductive material particles in the resin binder. Due to the specificity of the photoconductive layer, there are many parameters that determine its electrical and photoconductive properties as well as its physical and chemical properties.
Unless these parameters are precisely adjusted, a photoconductive layer having desired characteristics cannot be formed with good reproducibility, leading to a decrease in yield and a lack of mass productivity.

In addition, because the binder-based photoconductive layer is a dispersion system,
The entire layer is porous and therefore highly dependent on humidity, resulting in deterioration of electrical characteristics when used in a humid atmosphere, often making it impossible to obtain high-quality copied images.

Furthermore, the porous nature of the photoconductive layer causes developer to enter the layer during development, which not only reduces mold releasability and cleaning properties, but also causes unusability. When a liquid developer is used, the developer penetrates into the layer together with its carrier solvent due to the promotion of capillary action, and the above point becomes significant.
, it is necessary to cover the photoconductive layer surface with a $4 in coating layer as in the case of the photoconductive layer.

The improvement by installing a surface coating layer with Hyakunen et al. also resulted in an uneven interface between the photoconductive layer and the surface coating due to the unevenness of the surface of the photoconductive layer caused by the porous nature of the photoconductive layer. The disadvantage is that it is difficult to obtain good adhesion and electrical contact with the layer.

In addition, when using CdS, since CdS itself has an effect on the human body, care must be taken to prevent it from coming into contact with the human body or scattering into the surrounding area during manufacturing and use. It is necessary to

When using ZnO, there is almost no effect on the human body, but ZnO binder-based photoconductive layers have low photosensitivity, a narrow spectral sensitivity range, significant optical fatigue, and PVK and other materials that have recently been attracting attention. In an electrophotographic photoreceptor using an organic photoconductive material such as TNF, a coating film of the organic photoconductive material such as PVK or TNF is coated on a suitable support such as polyethylene terephthalate whose surface is conductively treated. This method has the advantage in production that a photoconductive layer can be formed by simply forming a photoconductive layer, and that an electrophotographic photoreceptor with excellent flexibility can be manufactured. It has drawbacks such as corona ionicity, lack of cleaning properties, low photosensitivity, and a narrow spectral sensitivity range biased towards short wavelengths, so it can only be used in a very limited range. Powerful.

However, some of these organic photoconductive materials are suspected of being carcinogenic, and there is no guarantee that they are completely harmless to the human body.

As described above, electrophotographic photoreceptors using photoconductive materials, which have been pointed out as photoconductive layer forming materials for photoreceptors, have both advantages and disadvantages, and therefore have certain manufacturing and usage conditions. The current situation is to relax the standards and select an appropriate 11 yen secondary photoreceptor suitable for each purpose for practical use.

The present invention has been made in view of the above points, and since the device can be easily made into a closed system during manufacturing, it is possible to avoid harmful effects on the human body. When using it, not only the human body but also its (
It is non-polluting and has no impact on 10 living things or the natural environment, is heat resistant and moisture resistant, and is an electronic 'lJ refreshing special 44.
1 is an electrophotographic photoreceptor that is stable at all times, can be used in all environments with almost no restrictions on usage conditions, has excellent light fatigue resistance and corona ion resistance, and does not cause deterioration even after repeated use. The main purpose is to provide a manufacturing method for.

Another object of the present invention is to provide a method for manufacturing a photoreceptor that can easily produce high-quality images with high density, clear -7 tones, and high resolution. be.

Another object of the present invention is to have high photosensitivity, a wide range of spectral sensitivity that covers almost the entire visible light range, fast photoresponsiveness, and wear resistance.

Another object of the present invention is to provide a method for producing an electrophotographic photoreceptor having excellent cleaning properties and solvent resistance.

The intended purpose of the present invention is to form a photoconductive layer mainly of amorphous silicon (hereinafter abbreviated as a-Si) by exposing the surface of the support on which the photoconductive layer is to be provided to glow radiation 'L' in advance. achieved.

In the early stages of development, the structure of a-Si film was influenced by its manufacturing method and manufacturing conditions, so various types of 17i were used.
It exhibited t-temperature characteristics and optical characteristics, and had a major problem in reproducibility and Q. For example, in the first jυ1, the a-Si I formed by vacuum evaporation or sputtering has a large amount of defects such as voids, which greatly affects its electrical and optical properties. Although it received much attention as a research material for basic physical properties, no research and development was conducted for its application. It was reported in 3-81 that p-n junction was realized for the first time in amorphous material in early 1976 (App71i).
d Physics++ T, etter i Vog
28゜A; 2, 15 January 1.976
) since it was completed.

A great deal of interest was gathered, and since then, in addition to the fact that a p-n junction can be obtained by doping with the impurities mentioned above, very weak luminescence has been observed in crystalline silicon (abbreviated as cSi) with high efficiency in a-8i. From the point of view of tF, research and development capabilities are mainly focused on applications to solar cells.

In this way, the n −3i 11t reported so far
Since A was developed for use in solar cells, the reality is that it cannot be used as a photoconductive layer of an electrophotographic photoreceptor due to its electrical and optical properties.

In other words, the thick lvJ'f1''L pond converts solar energy into the form of current [7], so it has a good 8N ratio, and in order to extract current efficiently, the resistance of a-Si p must be small. .

If the resistance is too small, the photosensitivity will decrease and the S/N ratio will deteriorate, so one of the characteristics is that the resistance should be between 10' and 10'.
A resistance of about 8Ω·m is required.

Hyakunen et al. have found that the a-8+ film, which has this level of resistance (dark resistance: resistance in the dark), has an even lower (too low) resistance (dark resistance) as a photoconductive layer of an electrophotographic photoreceptor. , it cannot be used at all by applying currently known electrophotographic methods.

Also, as a photoconductive layer forming material for electrophotographic photoreceptors ←j:,
The bright resistance (resistance when irradiated with light) is required to be about 2 to 4 orders of magnitude smaller than the dark resistance, but conventionally reported a
Since the -Si film has a photoconductive layer of about two digits at most, the conventional a-8+ film could not provide a photoconductive layer that satisfactorily satisfies this characteristic.

In addition, in other reports on aS+ films by Tore, increasing the dark resistance decreases the photosensitivity; for example, when the dark resistance =
It has been shown that the photoresistance of the @-Si film at 10Ω・m is about the same, but in this respect as well, the conventional aS1 film is inferior to the photoconductive layer of an electrophotographic photoreceptor. could have happened.

Furthermore, other requirements other than the above required for the photoconductive layer of the electrophotographic photoreceptor, such as electrostatic properties.

Conventionally, the properties such as corona ion resistance, solvent resistance, photofatigue resistance on surface J, humidity on surface 1, heat resistance, abrasion resistance on l1li4, and cleaning properties were completely unknown. .

The present invention is based on a specific 3-8, which is also B-8t, as a result of comprehensive and intensive research and study on a-8i from the viewpoint of its application to a photoconductive layer of a photoconductive layer. If so, it can not only be used satisfactorily as a material for forming the photoconductive layer of electrophotographic photoreceptors, but also has an extremely low RM4 in most respects when compared with materials for forming the photoconductive layer of conventional electrophotographic photoreceptors. It is based on what we have discovered.

//'7/'i,'-'''',7'7,■ %-,,7-L,゛/''//,/7,/ Most typical structural example of the electrophotographic photoreceptor of the present invention is shown in FIGS. 1 and 2. The electrophotographic photoreceptor 1 shown in FIG. It has a free surface 4 that serves as a forming surface.

The support 2 may be electrically conductive or electrically insulating. As the conductive support, for example, stainless steel + A
tt Cr+ Mo, Au, Ir, Nb, Ta,
, y.

Examples include metals such as TiIPt and Pd, or alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, bolier, tyrene, polycarbonate, cellulose triacetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. be done. It is desirable that at least one surface of these electrically insulating supports is conductively treated.)
Yes.

For example, if it is glass, Int Os + Snow
If the surface is conductive treated or made of synthetic resin film such as polyester film, At.

1 with metals such as Ag + Pb, Zn HN +, Au, etc.
[The surface is subjected to conductive treatment by air steaming or laminating with the metal. The shape of one support can be cylindrical, belt-shaped, plate-shaped, etc.;
4-shaped and 12-shaped, the shape ←l is determined by the request l'
However, in the case of continuous high-speed copying, it is preferable to use an endless belt or a cylindrical shape.The thickness Vl of the support is determined as appropriate so that the desired electrophotographic photoreceptor is formed. However, when flexible ffp properties are required as an electrophotographic photoreceptor, the support is made as thin as possible within the range where the ilF' is sufficiently exhibited. and others,
In such a case, the mechanical strength of the support is usually 10μ or more for reasons of production costs and considerations.

Three a-8i light guide 'ttt layers are formed on the support 21 by a glow discharge method, a sputtering method, an ion implantation method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing requirements, equipment capital investment load, desired electrophotographic characteristics, etc., but they are suitable for manufacturing electrophotographic photoreceptors having desired electrophotographic characteristics. A-3 to control the characteristics is 1)
In order to introduce impurities into the i-layer, the glow discharge method is preferably employed because of its advantages such as being able to introduce impurities of group (I) or group V by substitution. Furthermore, in the present invention, O 8 81-based light is an extremely effective method of forming an a-8i layer by using a glow discharge method and a sputtering method in the same system. The conductive layer 3 has a dark resistance that satisfies the value required for a photoconductive layer of an electrophotographic photoreceptor, for example,
■ Control by doping.

a The H doping of the S+-based photoconductive layer 3 is such that when forming the photoconductive layer 3, 5iT (< , 5itH
After introducing compounds such as a or T(,), such compounds can be added to 1 [
, and doped into the a-St layer as the layer grows. Alternatively, doping may be performed by ion implantation.

According to the knowledge of the present inventors, % a Fl! (H doping in the spinning wheel conductive layer 3)
It has been found that the 8i layer is one of the major factors that determines whether or not it can be applied as a photoconductive layer of an electrophotographic photoreceptor, and is extremely important.

In the present invention, in order for the aS+ layer to be formed to be sufficiently applicable as a photoconductive layer of an electrophotographic photoreceptor, a8
Normally, Nl of H doped into one layer is 10~
40 atoms, preferably 0.15 to 30 atoms
ic% is 1m-+ □ A-81 Theoretical support for the reason why the H doping bone in the layer is limited to the numerical range of Ichihihi 1 At present, it has not been clarified. It is beyond the realm of speculation. Hyakunen et al. have found from numerous experimental results that if the amount of H doped is outside the numerical range, for example, the dark resistance will be too low for the photoconductive layer of an electrophotographic photoreceptor, the photosensitivity will be extremely low, or in some cases it will be phantom. , almost no photosensitivity was observed, and a small increase in carriers due to light irradiation was observed, supporting that it is a necessary condition that the amount of H doping be within the above numerical range. In order to dope the a-3i layer with nF, for example, by a glow discharge method, when one layer is formed, the starting material for forming the a-8i is a hydride such as 5iTT, , 5itHe, etc. Since hydrides such as 5iTT, , and 5iJTs are decomposed to form B and Si layers, ■
is automatically doped into the layer, but in order to dope H into the layer more efficiently, H gas should be introduced into the glow discharge system when forming the a-8i layer. Good.

When using the sputtering method, Si is deposited in an atmosphere of an inert gas such as Ar or a mixed gas based on these gases.
When performing sputtering using the target as a target, H gas is introduced or Sl 'H4+ S 1 di
It is sufficient to introduce a silicon hydride gas such as n, or a gas □ such as 13tH6, PHs which also serves as impurity doping.

doping into the a-8+ layer】[to control the deposition substrate temperature or/and O:' -1
Amount to be introduced - City 1] If you do it with 11 sheets, it will be 1". After forming 1.J:, a-8ij/h, activate the layer () 4) It is also possible to expose the R-81 layer to a concave atmosphere. Also, one Jl method is to heat the R-81 layer at a temperature below the crystallization temperature.

a S+ layer d-1 (IC also/II1.l!J) 2
1. k by doping with impurities during manufacturing:
(ll ni ii: 1, also controls the conduction type (1+, ll
Since there was nothing to do, I created an electrophotographic photosensitive (J
Advantage 4: The polarity of the stripping band Ttff that forms an electrostatic image on - can be arbitrarily selected.

This advantage v; 1, conventional, for example, 88 yarn'/(,,'
If it is a layer, it may be P type or case depending on the manufacturing conditions such as 61゛, substrate temperature, type of impurity, doping method 1, etc. ,1
Compared to the fact that it is necessary to strictly control the substrate temperature in order to form a treetop ky (outer mold (i-type), and also ■) mold, the FI8 is much more convenient. Dea
The impurity doped into the SZ layer is m FI
In order to make the S1 layer P-type, an element of group A of the periodic table,
For example, B + A-1r Ga + In, Tt, etc. are required as appropriate, and when n is used, an element of group Ⅰ A of the periodic table, such as N.

P HAs l Sb HBl # Preferred-tr-c enumerated λ]. Impurities such as cracks are S FL
Since the Jlro-111 contained in the S1 layer is on the order of T)I)m, it is not necessary to pay as much attention to its pollution potential as the main material constituting the photoconductive layer, but it is necessary to use a material that is as non-pollutant as possible. I like to use it. From this point of view, considering the electrical and optical properties of the a-8i-based photoconductor to be formed, for example, B, As, P, Sb, etc.
It is y drops.

The amount of impurity doped into asjll'j is appropriately determined depending on the desired electrical and optical properties.
f1 always 10' ~] O-30-3ato% + preferably 10-5 to 10-40-4atn 9th periodic table ■
In the case of group A impurities, i+II usually 1 (1-8 to 1
(1-5 atomic% + 610 ~ 1 (
l atomic'% 11]=preferably.

The method of doping these impurities into the aS+ layer is a
When forming the Si layer, li′, river; ff J), ru(
[, i/lj method, and will not be explained in detail in the following description or examples.

1 shown in FIG. Rufu, child'l￥ IG photoconductor fi
ll, the a-8+ photovoltaic layer 3 has a free surface 44 and 17
, the free surface 4 is provided with a band '71f for electrostatic image formation, a treatment
11! In electrophotographic photoreceptors to which s fl
It is more preferable to provide a barrier layer between the S I-based photoconductive layer 3 and the support 2, which functions to prevent the injection of gear from the support 2 side during charging processing during image formation. It is something. The material for forming the barrier layer having such a function is appropriately selected depending on the type of support and the type of a-8+ optical guiding layer and the chemical characteristics. A suitable product will be used. With such barrier layer forming materials, for example, Au, Ir,
Examples of the support include Pt, Rh, Pd, Mo, etc., and when the barrier layer forming material is Au, for example, At is suitable.

The layer thickness of the R, -8i-based photoconductor is as follows:
[The thickness is determined as appropriate depending on the photographic characteristics and conditions of use, such as whether flexibility is required, etc. Although there are limitations, it is usually 5 to 80μ, preferably 110μ.
~70μ, optimally 10-50μ.

In an electrophotographic photoreceptor having a layer structure in which the surface of the S a Sl photoconductive layer is exposed as shown in FIG.
Since the refractive index of the i film is relatively high at approximately 3.35, light reflection occurs more easily on the surface of the photoconductive layer during exposure compared to conventional photoconductive layers, and therefore the amount of light absorbed by the photoconductive layer decreases. The ratio of light loss decreases, and the light loss rate increases. In order to reduce this optical loss rate as much as possible, it is preferable to provide an antireflection layer on the a-8i photoconductive layer.

As the material for forming the antireflection layer, a-8i light guide 'Fl
In addition to the conditions of not having an adverse effect on the f-layer and having excellent antireflection properties, further electrophotographic properties, such as
Having a certain level of resistance, liquid It'), i
11 for J5, has excellent detergent resistance, and has already been formed within the conditions of formation. Q-8I
The Il′ property of the photoconductivity of the system destination should not be reduced.1q+7
) A/item is required.

Furthermore, to make the anti-reflection 1 effect q1 (r, i %
As can be seen from the optical calculation of 17i1Φ, the reflection resistance is 11-8.
The layer It' is selected such that its refractive index is between the layer of a E>1 layer and the 1fi (refractive index of air).Father, The layer thickness is λ/4 v'i' /)n (where n is a, 111 of the Si layer (refractive index, λfqt, tJ'lr is the likely wavelength.) Taking these various optical conditions into account, the antireflection layer It is preferable that the thickness is 50 to 1 nm, assuming that the wavelength of the exposure light is approximately in the visible wavelength range7).

In the present invention, materials that can be effectively used for forming an antireflection layer include, for example, MgF.

Examples include inorganic fluorides and inorganic oxides such as 5101 TatOv l AI-F3 and 3NaF, or organic compounds such as polyvinyl chloride, polyamide resin, polyimide resin, vinylidene fluoride, melamine resin, Evogin resin, phenol resin, and cellulose acetate. It will be done.

The electrophotographic photoreceptor 1 shown in FIG.
A surface coating layer such as a protective layer or an electrically insulating layer may be provided on the surface of the Ss-based photoconductive layer 3, as in the case of a conventional zelkova electrophotographic photoreceptor.

An electrophotographic photoreceptor having such a surface coating layer f52
As shown in the figure.

The electrophotographic photoreceptor 5 shown in FIG.
- is not essentially different from the electrophotographic photoreceptor 1 shown in FIG. For example, if you are applying electrophotographic stains such as those described in Japanese Patent Publications No. 42-23910 and No. 43-24748, the surface should be
The '0 layer 8 is electrically insulated, has a high sluggishness, has a static charge retention ability when subjected to band 'Fl (processing), and has a JIJ7 strength of at least a certain level. However, if a direct copying process such as the Carlson process is applied, it is desirable that the potential r1 of the four parts after electrostatic image formation is very small. 8 is required to be very thin.Surface 41ν
8 layers of cover, the desired city air bacteria! In addition to satisfying the above requirements, a-3ii) the photoconductive layer should not have any adverse physical or physical effects; , μf are of -C type b15 in consideration of IW resistance, abrasion resistance, cleaning properties, etc.

Typical materials that can be effectively used as surface coating layer forming materials are 11 polyethylene terephthalate, polycarbonate = 1, polypropylene, polyvinyl chloride,
Polyvinylidene chloride.

Polyvinyl alcohol, polystyrene, polyamide, polytetrafluoroethylene, polytrifluorochloroethylene, polyvinyl fluoride, polyvinylidene fluoride.

Hexafluoropropylene-tetrafluoroethylene copolymer.

Ethylene difluoride-vinylidene fluoride copolymer.

Synthetic resins such as polybutene, polyvinyl butyral, polyurethane, and cellulose derivatives such as diacetate and tri-7-chie are added. These four synthetic 467 resins or cellulose derivatives can be applied as a film and laminated onto the A-8I photoconductive layer, forming a coating solution and forming an A-8T yarn. Apply light and 14' layer 5'' to 2,
A film may be formed.

The layer thickness of the surface barrier layer is appropriately determined depending on the desired characteristics and the material used, but in the case of normal use, it is approximately 0.5 to 70 μm. In particular, when the surface coating layer is required to function as the above-mentioned protective layer, it is usually less than 10μ, and on the contrary, it is required to function as an electrical insulating layer). is usually 10μ or more.

Layer thickness A1 that differentiates the protective layer and the electrical insulating layer from each other
．． ! The value of 10μ is not absolute, as it varies depending on the month of use, the applied electrophotographic process, and the structure of the TIi photoreceptor.

This surface coating layer 8 also has the role of an anti-reflection layer as mentioned above. 1″4° is further enlarged and reaches effectively.

Next, the case where the photoreceptor of the present invention is manufactured by the glow emission 41i method and the sputtering method VC will be explained in detail.

FIG. 3 is a schematic explanatory diagram of a glow discharge deposition apparatus for manufacturing the electrophotographic photoreceptor of the present invention by a Gapantance type glow discharge method.

10 is a glow discharge deposition tank, inside which a-8t
A substrate 11 for forming a photoconductive system is fixed to a fixing member 12, and a heater 13 for heating the substrate 11 is installed on the lower side of the plate 11. Vapor deposition tank 10
A capacitance type electrode 15, 15' connected to the high frequency power source 14 is wound around a part of -1, and a high frequency is applied to the high frequency to generate a glow discharge in the vapor deposition tank 10. It has become.

A gas introduction pipe is connected to the upper end of the vapor deposition tank 10, and gas cylinders 16, 17, 18.1:,! l) Gas in each cylinder is introduced into the vapor deposition tank 10 when necessary. 19, 20, and 21 are each flow meters and are meters for detecting the flow rate of gas, and 2
2, 23, and 24 are flow control pulps, and 25, 26, and 27 are pulps.

28 is auxiliary pulp.

Further, the lower end of the vapor deposition tank 10 is connected to an exhaust device (not shown) via a main pulp 29. 30 is pulp for breaking the vacuum in the vapor deposition tank 10.

Using the glow discharge device shown in FIG. To form a characteristic a-8i type photoconductor, first, a substrate 10 that has been subjected to a predetermined cleaning treatment is fixed to a fixing member 12 with the cleaned surface facing upward.

To clean the surface of the plate 11, one commonly practiced method is employed, for example, a chemical treatment method using an alkali or acid. Also, after cleaning a certain 47 degrees, Kyoqt
Install it at a predetermined position in the tank 10, and attach A to its J-.
Even if you perform Grono military treatment before forming a layer on the Si-based light guide 'l'! 4. In addition, since the process from cleaning the substrate 11 to forming the St-based photoconductive layer can be performed without breaking the vacuum within the same system, dirt and impurities will not adhere to the cleaned surface of the w-board. can be avoided. After fixing the substrate 11 to the fixing member 12, the main pulp 29 is fully opened and the air inside the deposition tank 10 is evacuated.
The pressure should be about 10-5 torr. After the inside of the vapor deposition tank 10 reaches a predetermined degree of vacuum, the heater 13 is ignited to heat the substrate 1, and once it reaches a predetermined temperature, it is maintained at that temperature.

Next, open the auxiliary pulp 28 fully L %←; and open the gas cylinder 1.
6 pulp 25 and gas cylinder 17 pulp 26 are fully opened. A gas cylinder of 16 UAr is used for raw gas, and a gas cylinder of 17 is for raw material gas to form A-81.
For example, 5H-L I 5t2I(a +S t 4H
,. Or a mixture thereof is stored. [Cylinder] 8 is for raw material gas to generate impurities to be introduced into the a-8i system photoconductor as necessary, and I'T (
s-PtH4, BtHa, etc. are stored.

After that, the flow rate regulating pulp 22 for the gas cylinders 16 and 17.
23 and the flow meters 19 and 20 are gradually opened to fill the vapor deposition tank 10 with Ar gas and, for example, 5iT.
(A raw material gas such as 4 gas for a-8i formation is introduced. At this time, Ar gas is not necessarily required, and only the above raw material gas may be introduced. When introducing the raw material gas mixed with the raw material gas for the purpose, the quantitative ratio is determined as desired, but usually, the raw material gas is 10 VoL with respect to the Ar gas.
It is considered to be 4 or more. Note that He gas may be used instead of Ar gas.

At the time when gas is introduced into the vapor deposition tank 10 from the cylinders 16 and 17, the main pulp 29 is adjusted 17 to
When the degree of vacuum in Ido is 1, the raw material gas pressure for forming a-8t is maintained at 10-2 to 3 torr. Next, the capacitance type ``1'' wound around the 10 ``74/7'' f tanks is connected to the pole 15, 15' at a predetermined frequency by the high-frequency wave ``Ichihara 14'', in the normal case (1,:! ~ 30 MFfz high frequency). Add 1111 and heat the glue to 11°C in the vapor deposition tank 10.
For example, when the SQL gas is decomposed 7), S+ is evaporated onto the plate 11 to form an aS+ layer 114. When introducing a
- If 11 pieces of S I-based light guides are introduced into the vapor deposition tank 10 when +1q layer is formed, it will be recessed. In this case, if the flow rate iW, 'a section pulp 24 is adjusted appropriately, the introduction 1d of gas from the cylinder 18 to the vapor deposition tank 10 can be appropriately controlled, so that the a-3i formed In addition to arbitrarily controlling the amount of impurities (it) introduced into the red photoconductive layer of the 31-based red photoconductive layer,
1' of impurities in the direction shown! ′ can also be easily changed.

In the glow discharge deposition apparatus shown in FIG.
Although the F (radio frequency 3') capacitance type glow discharge method is employed, other glow discharge methods such as RF inductance type and DC bipolar type are also employed in the present invention. Further, the electrode for glow discharge may be provided outside the vapor deposition tank 10 or may be provided inside the vapor deposition tank 10.

In the present invention, in order to obtain an effective glow discharge, it is preferable to use an AC or DC current with a current density of 0.1 to 10 mA/rdl, and to use sufficient power.
It is best to adjust the voltage to 300 to 5000V in order to

Since the characteristics of the a-8i-based photoconductor formed greatly depend on the temperature of the printing plate during growth, it is preferable to strictly control it. In the present invention, the substrate temperature 10 is usually 50 to 35
By adjusting the temperature to 0° C., preferably in the range of 100 to 200° C., an a-8i-based photoconductive layer having effective characteristics as a light-included 1it layer for electrophotography is formed. Furthermore, the growth rate of the a-8i layer is also a 117 factor that greatly influences the physical properties of the a-8i layer, and to achieve the purpose of the present invention, I/:I
', ;i6 usually 0.5 to 100 people/sec, preferably N', 1 to 5 (IA/sec).

FIG. 4 is a schematic explanatory view showing one of the apparatuses iiV for manufacturing the electrophotographic photoreceptor of the present invention using a sputtering method.

Reference numeral 31 denotes a vapor deposition tank, in which a M-shaped mold 32 for forming a Vj, n F) 1-based photoconductive layer is fixed to a fixing member 33 with a rim. is set up.

A heater 34 for heating the substrate 32 is arranged below the substrate 32, and a polycrystalline or single crystal silicon target 35 is arranged above at a position facing the letterpress 32 with a predetermined interval. ing.

Between the substrate 32 and the silicon target 35, a high frequency signal 1111 is generated by a high frequency power source 36. Father, #young monk 31 (l moss, cylinder 37.38 each, valve: 39.40, flow meter 41, 42, flow +
AJ7J pulp 4 knees 1.44 are connected via auxiliary pulp 45, and gas is introduced into the vapor deposition tank 31 from cylinders 37.38 when necessary.

Now, in order to form an aSt-based photoconductive layer on the substrate 32 using the apparatus shown in FIG. Evacuate to the specified degree of vacuum using llf.

Next, the heater 34 is ignited to heat the substrate 32 to a predetermined temperature. When forming the a-8i-based photoconductive layer by sputtering, the heating temperature of the substrate 32 is usually 50 to 350°C, preferably 100 to 200°C.

The substrate temperature influences the growth rate of the a-8i layer, the structure of the layer, the presence or absence of voids, etc., and is one element that determines the physical properties of the a-8i layer that is formed, so it must be sufficiently controlled.

Further, the substrate temperature may be kept constant during the formation of the a-8i layer, or may be raised, lowered, or raised or lowered as the a-8t layer grows. For example, in the initial stage of forming the a-8i layer, the substrate temperature is kept at a relatively low temperature T, and the a-8i layer is kept at a relatively low temperature T.
When the 8i layer grows to a certain extent, the temperature T is higher than T1F.
In order to increase the J, lii temperature, the a-8i layer is shaped tj
vL,RS! +4 and lower than T2 at the end of layer formation
', ) i Ts to Jl (lower the plate temperature, etc., a-8
I-type light guide? A li layer can be formed. Like this-
In addition, 1- is the electrical conductivity of the a-8i-based photoconductor.
Optical properties can be changed continuously in the layer thickness direction.
6ru.

In addition, since the tl\1\4'y1g degree of a-81 is slower than that of other materials, such as Se, when the layer thickness to be formed becomes thicker, the initial layer formation time is 1tll iF skeleton formation, #-1 ,*
a-8i (], (a-8i placed on the plate side) is very likely to change the characteristics at the initial stage of layer formation until the layer formation is completed, so it is possible to change the properties of the layer in the thickness direction by 14'! ;tr
In order to form an aS+ layer having a time-varying property, it is desirable that the substrate temperature be kept at 1 - 1 T from the start of layer 1 formation to the end of layer formation.

Next, after detecting that the cutting board 32 has not been heated to a predetermined temperature ν, the main pulp 46, the auxiliary pulp 45, the pulp 3
Fully open 9.40.

Next, the main pulp 46 and the flow 1 are controlled by the pulp vapor deposition tank 3.
1, the vacuum is lowered to a predetermined degree.

Next, open the flow rate regulating pulp 43 and open the cylinder 37''.
Ar gas is introduced into the deposition tank 31 until the vacuum level reaches a predetermined level, and the vacuum level is maintained at that level. The fluxes d of the 11 layers, gas and Ar gas into the vapor deposition tank 31 are appropriately determined so that a-8i-based photoconductivity having desired physical properties is formed. For example, a vapor deposition tank;
rr, suitable size 5X10-"~3X] O'torr
□ Ar gas can be replaced with He gas or the like.

After Ar gas and H gas are introduced into the young priest 31 from cylinders 37 and 38 to Z until a predetermined degree of vacuum is reached, the substrate 3 is heated by the high frequency power supply 36 at a predetermined frequency and voltage.
A high frequency is applied between 2 and silicon target: 35 to cause a discharge, and the generated Ar ions release S of the silicon target.
Sputtering is performed to form a -8i layer on the substrate 32.

In the acid 1 light of Figure 4, tl, high frequency j ('I 113
Although the above sputtering methods are listed above, a sputtering method using targeted discharge may also be adopted. In the sputtering method using high frequency application (&1', the frequency is usually 02 to 3 (III/1lTz 1
Preferably 5 to 20rV fz, father, Ho'ichi Tl\
, l1iir, density is usually 0.1-10 mA/c!
, the preferred V(is) is preferably ~57FIA/11.Also, in order to obtain sufficient power,
n 00 V (D ?lCfE I/Cf+periodical 'J
tLX is good.

The sputtering method is used for continuous growth of the ASI layer when producing the electrophotographic photoreceptor of the present invention, mainly by forming the substrate Iθ.
[Determined by ° and discharge condition Vc]1. This is one of the major factors that influences the length t1 of the formed layer. To achieve the object of the present invention, a growth rate of 81 layers is used, which is 0.5 to 100 s/sec in the case of 1lTl.
, preferably 1 to 50 people/3cc is Bokke 1,
7.

In the sputtering method, IYa is also formed by doping with impurities, similar to glow emission 11ir).
-8i photoconductivity can be adjusted to peripheral photoconductivity or p-type. The method of introducing impurities is the same in the sputtering method as in the glow discharge method, and for example, PI (=, P
A gas such as JT, +, BtHa, etc. is introduced into the aSt layer type temporary evaporation tank 31 to dope P into the a-8i layer with B as an impurity.

In addition, impurities may be introduced into the unformed a-8i layer by ion implantation. In this case, the extremely thin one surface layer of the a-3i layer is 11! Since it can be easily controlled to a conduction type with a constant f, for example,
It is advantageous because the charge retention layer of an electrophotographic photoreceptor as described in Japanese Patent No. 9-6223 can be formed extremely easily, and its characteristics can be controlled to suit the individual.

Hereinafter, the present invention will be described in detail through examples.Example 1 Using the apparatus re shown in FIG. 3, 1. An electrophotographic photoreceptor of the present invention was prepared, and an image forming process was performed to produce an image (I9).

■ Surface treatment J111 was performed using Yu's Na0I-I solution, and the surface was cleaned by thoroughly washing with water and drying to a thickness of 1 m.
rn, size I QC+nx] 7 fi of 0CIn
A V minium substrate was prepared and firmly fixed at a predetermined position of the fixing member 12 at a predetermined position in the vapor deposition tank 10 at a distance of about 1 Q Cm from the heater 13.

Next, the main pulp 29 was fully opened to exhaust the air in the vapor deposition tank 10, resulting in a degree of vacuum of about 5XIOtorr. Thereafter, the heater 13 was ignited (I7) to uniformly heat the aluminum substrate to 150"C" and maintained at this temperature.

After that, fully open the auxiliary pulp 28, and then open the cylinder】6
After fully opening the pulp 25 of the cylinder 17 and the pulp 26 of the cylinder 17,
Gradually open the flow rate regulating pulp 22 and 2:3, and supply Ar gas from cylinder 16 and 5III from cylinder 17.

Gas was introduced into the vapor deposition tank 10. At this time, the main pulp 29 is adjusted so that the degree of vacuum in the vapor deposition tank 10 is approximately 0.75 t.
It was made to be held in orr.

Next, turn on the switch of the high frequency power supply 14 and
A glow discharge was generated by applying a high frequency wave of 13.56 Mllz between the 15 and 15 layers of the ji electrode, and an a-8t layer was formed on the aluminum base plate. At this time, the glow discharge current V1 was about 5 mA/ad and the voltage was 2000 V3, and the growth rate of the a-8t layer at this time was about 4λ/sec.
Vapor deposition was performed for 15 hours to form an A-8T film with a thickness of 20 μm on the aluminum substrate.

After the completion of vapor deposition, the electrophotographic photoreceptor created in this way is
Main pulp 29, B/l/7'25, 26, flow, M'
The control valves 22 and 23 were closed, and the pulp 30 was opened instead to break the vacuum inside the deposition tank 10 and take it out to the outside. On this electrophotographic photoreceptor, e-corona discharge was applied to the A-8T photoconductive surface in the dark at a power supply voltage of 5500 V, and then image exposure was performed at an exposure dose of 15 eux·sec to form an electrostatic image. When this electrostatic image was developed with a charged toner by a cascade method and transferred and fixed onto a transfer paper, an extremely clear ηS i image with high resolution was obtained.

Such an image forming place! 1! 2) was repeatedly applied to the electrophotographic photoreceptor, and the durability of the 11-image photoreceptor was tested. The images printed on 10,000 sheets of L1 transfer paper were also of extremely good quality. There is no difference when compared with an image on a single sheet of 1'J transfer paper, and this electrophotographic photoreceptor has excellent anti-ionic and abrasion resistance.

It was found that the cleaning properties were excellent and the product was extremely durable.Blade cleaning was used as the cleaning method, and the blade was molded from urethane rubber.6=j+jf.

Next, apply the above MI electrophotographic photoreceptor) in the dark with a power supply voltage of 6000V.
Perform 1IIj team W light with a light intensity of 5 eux sec,
When an image was produced under the same conditions as when the image was produced by applying O corona discharge as described above, the image on the transfer paper was lower than that in the case of 11t.

From this real number, it was found that the electrophotograph obtained in this example, d (photoreceptor, had dependence on charge polarity).

Example 2 After forming one layer of a-S with a thickness of 20 μm on an aluminum substrate under the same conditions as in Example 1 and using the same process as in Example 1, it was taken out of the deposition tank 10, and a polycarbonate resin was placed on the a-8I layer. was applied to a dry thickness of 15μ to form an electrically insulating layer. ] It was used as an Iko photographic photoreceptor. As a primary charge on the surface of the insulating layer of this photoreceptor, a power supply voltage of 60
When corona discharge was performed at 00V for 0.2 seconds, the battery was charged to 2000V. Next, as secondary charging, e-corona discharge was performed at a power supply voltage of 5500 V, and at the same time image exposure was performed at an exposure amount of 15 eux-sec, and then the entire surface of the photoreceptor was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner charged to θ using the cascade method and transferred and fixed onto transfer paper, an extremely high quality image was obtained.3. Example 3 Same as Example 1 (2) K1 No. 3 Using the apparatus shown in the figure, an electrophotographic photoreceptor of the present invention was prepared in the following manner, and an image was formed by performing an image forming process.

The surface was treated with 10% NaOH solution, washed thoroughly with water and dried to clean the surface, resulting in a thickness of 1 r711.
n, size l Q 0771 X I Q (,'#
Prepare an L aluminum substrate and place it in glow discharge deposition tank 1.
The heater 13 is placed at a predetermined position on the fixing member 12 at a predetermined position within the evaporation tank 10. was evacuated (7) to a degree of vacuum of approximately 5 x 10 tnrr.Then, heater 3 was ignited to uniformly heat the aluminum substrate (7) to 150°C and maintained at this temperature.Then, the auxiliary valve 28 was turned on. Then, after fully opening the valve 25 of the cylinder 1G and the valve 26 of the cylinder 17, the flow control valves 22 and 23 are gradually opened to supply Ar gas from the cylinder 16 to the cylinder 17.

Gas was introduced into the vapor deposition tank 10. At this time, the main valve 29 is adjusted so that the degree of vacuum in the vapor deposition tank 10 is approximately 0.75 t.
It was made to be held in orr. In this case, while monitoring the flow meters 19 and 20, the flow control valves 22 and 23 were adjusted so that the flow rate of the gas was 10 vol$, which was the flow rate of the Ar gas.

Next, the valve 27 of the cylinder 1B is fully opened, and then the flow rate adjustment valve 24 is gradually opened so that the flow rate becomes 5j)I4.
B2H1l gas was introduced into the deposition tank 10 while controlling the gas flow rate to be 5 x 10vo/ch. At this time as well, the main pulp 29 is adjusted to bring the degree of vacuum inside the deposition tank 10 to 0.
It was maintained at 75 torr.

Next, the switch of the high frequency power supply 14 is turned on, and a high frequency of 13.561111zO is applied between the electrodes 15 and 15' to cause a glow discharge, and a
-A Si film was formed. The glow discharge current at this time is approximately 3
The voltage was 1500V at mA/ya. In addition, the growth rate of the a-8j layer in this case is approximately 4 A/see,
Vapor deposition was performed for 15 hours to form a 20μ thick a-Si layer on the aluminum substrate. After the completion of vapor deposition, the electrophotographic photoreceptor produced in this way was heated to a main pulp of 29.61 mm.
r, 4 points..., 14-section pulp 22, 23, 24, valves 25, 26, 27 were closed, and then valve 30 was opened to break the vacuum in the vapor deposition 4vI l O and taken out to the outside. On the electrophotographic photoreceptor, θ corona discharge was applied to the face of the ASL thread leading conductive layer in the dark at a power supply voltage e of 5500 V, and then an image was formed at an exposure dose of 20/ux-sec.
) Light is applied to form an electrostatic image, and the electrostatic image is developed with charged toner using a cascade method and transferred and fixed onto transfer paper (7) A very clear image was obtained. Ta.

When this image forming process was repeated (7) on the electrophotographic photoreceptor and the durability of the electrophotographic photoreceptor was tested, 1j sheets [,1 of transfer paper] were obtained. The image was very thin, and there was no difference in comparison with the image on a single sheet of transfer paper, proving that this electrophotographic photoreceptor is extremely durable.In addition, as a cleaning method, adopted blade cleaning, and the blade was molded from urethane rubber.

Next, the electrophotographic photoreceptor was subjected to corona discharge with an α source voltage of 6000 V in the dark, and then 20 eux
・Image exposure was performed with an exposure amount of see to form an m electric image. When this electrostatic image was developed using O-charged toner by a cascade method and then transferred and fixed onto transfer paper, an extremely clear image was obtained.

From this result and the previous result, it was found that the tt3: child photographic photoreceptor obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar photoreceptor.

Example 4 In Example 3, an aluminum substrate was prepared in the same manner as in Example 3, except that the flow rate of B, I (lI gas was adjusted to be 5X1.Ova/chi of the flow rate of Si & gas). thickness 2
Forming a 0μ a-8i-based photoconductor? It was made into a 6-child photographic photoreceptor.

Using this electrophotographic photoreceptor, an image was formed on a transfer paper under the same conditions and procedures as in Example 3. The image quality was better than that of Image Formation 1 and was #+1' brighter.

From this result, it can be seen that the dependence of the band polarity on the IL electrophotographic photoreceptor obtained in this example (!JC) is very poor.

However, its dependence is due to the implementation
The photographic photoreceptor melted backwards.

Example 5 After forming a 20μ thick a-S layer on an aluminum substrate under the same conditions and procedures as in Example 4,
7. Dry the polycarbonate resin on the a-8i layer to a thickness of 15 μm (coat it on the paper and form the entire 11L gas insulation layer). ,
An electrophotographic photoreceptor was obtained. As a primary charge on the surface of the insulating layer of the photoreceptor, the voltage (i 0 (O corona radiation at 10 V is applied to the 0.2 see interval -'-) fc
(1) Charged to 2000V. Next, secondary charging was performed, and at the same time corona radiation was carried out using a C power supply's internal pressure of 500 V, an image irradiation was performed using an exposure meter of 15 eux/8 ee, and then the entire surface of the photoreceptor was uniformly irradiated. te still '1
1 also formed an image. When this electrostatic image was photofixed using the cascade method, an extremely high quality image was obtained.

Example 6 Electrophotographs shown in sample shops ■ to ■ were taken under the same conditions and procedures as in Example 1, except that the substrate temperature was varied as shown in Table 1 below. A photoreceptor was prepared and image forming conditions were exactly the same as in Example 3.
When an image was formed on the transfer paper, the results shown in Table 1 below were obtained.

As can be seen from the results shown in Table 1, K that achieves the purpose of the present invention is a when the substrate temperature is in the range of 50 to 350°C.
It is necessary to form an St layer.

Table 1 ◎: Excellent ○: Good △: Can be used practically ×: Not possible Example 7 In Example 3, ;'+1; plate temperature 1! , 1 all do 1; [
As shown in Table 2 of
Example; J: under the same conditions and procedures as 1.
An electrophotographic photoreceptor represented by old yFx (!i) to O was prepared, Ii L, when an image was formed on a transfer paper under the same image forming conditions as in Example 3 (ma ρ). Lower NL
The results shown in Figure 2 were obtained.

As can be seen from the results shown in Table 2 (C), in the case of this example, -C also achieves the objective 1.1 of Ryumei.
Substrate temperature is 50~:l5 (a-8i in the range of 1"0
It is necessary to form layers.

◎: Excellent ○: Good △: Practical 1 use, 2 obtained ×: Unsatisfactory Example 8 Example 4 except that the substrate temperature was variously changed as shown in Table 3 below y% by the same conditions and procedures as ＠ −＠
When an R light body was created and an image was formed on a transfer paper under exactly the same image forming conditions as in Example 4, the following third image was formed.
The results shown in the table were obtained.

As can be seen from the results shown in Table 3, even in the case of this example, it is necessary to form the a-St layer at a substrate temperature in the range of 50 to 350°C in order to achieve the object of the present invention. need to be formed.

Table 3 ◎: Excellent ○: Good △: Can be used for practical purposes ×: Not practical M
Example 9 A glow-emitting evaporation device shown in Fig. 3 (with a wall thickness of 2 Irtn and a size of 150 x 300 mm, an aluminum cylinder was installed rotatably from inside the cylinder. A heater was attached to heat the cylinder.

Next, fully open the main valve 29 and start vapor deposition! 110
Exhaust the air inside, about 5× ] 0-51. or+-
to a degree of vacuum. After that, the heater 13 was ignited (at the same time as each cylinder was rotated at a speed of 3 revolutions for 1 U to uniformly heat the cylinder, the cylinder was raised to 150' (J) and kept at this temperature. After that, the auxiliary valve 28, then fully open the valve 25 of the cylinder 16 and the valve 26 of the cylinder 17, and then gradually open the flow adjustment valves 22 and 23 to supply At gas from the cylinder 16 to the cylinder 17.
Yosu 5il (.

Gas was introduced into the deposition mIO. At this time, adjust the main pulp 29 so that the degree of vacuum in the vapor deposition tank 1 is approximately 0.75.
The flow rate of the 0 or 5IIL gas, which is maintained at torr, becomes 10 voe% of the flow rate of the Ar gas.Next, after fully opening the valve 27 of the cylinder 18, while watching the flow meter 21, turn the flow rate adjustment valve. 24 was gradually opened, and Tl, II, and gases were introduced into the deposition tank 10 such that the flow rate was SN (10 voe% of the gas flow h1).

At this time, the main pulp 29 is adjusted so that the degree of vacuum in the vapor deposition tank IO is maintained at approximately 0.75 torr.
is.

Next, turn on the switch of the high frequency power supply 14 and
A high frequency of 13.56 Mllz was applied between WAJi 15 and WAJi 15' to generate a glow discharge, and an a-8t layer was formed on the cylinder substrate. At this time, the glow discharge current was about 3 rnA/c and the voltage was 1500V.

Also, the growth rate of the a-Si layer in this case is approximately 2.5λ/
See, and vapor deposition was performed for 23 hours to form a 20μ thick a-Si layer on the cylinder substrate. After completing the vapor deposition, the electrophotographic photoreceptor produced in this way was heated to the main pulp 29.
, flow rate adjustment valve 22゜23.24, valve 25, 26
．． Close valve 27 and open valve 30 instead to begin deposition.
] in io! (I broke the sky and took it out in the evening.

This 11 (child 11.j tribute 1a light body, Ti in the dark
C) Corona discharge was performed on the surface of the a-3i photoconductive layer at 551'l OV, and then 20eux-8
An electrostatic image is formed by performing image exposure with exposure h1'' of ec, and this electrostatic image is developed with charged toner by the custard method [7] When transferred and fixed on transfer paper L7, an extremely clear image is obtained. was raped.

After repeating this image forming process 2, and testing the durability of the electrophotographic photoreceptor, it was found that the image formed on the 10,000th sheet of transfer paper was The quality of the image was also extremely high, and there was no difference in comparison with the image on the first sheet of transfer paper, proving that this electrophotographic photoreceptor was extremely durable at X7. ~Teke blade cleaning was adopted, and the blade was molded from urethane rubber.

Next, with respect to the electrophotographic photoreceptor described in item 1, the power supply voltage was 6
000V (recorona discharge, then 20 eux
・Image exposure was carried out with a light intensity of sec, and the image was produced under the same conditions as when the image was produced using O corona discharge as described above. It was lower than that.

From this experiment, it was found that the electrophotographic photoreceptor used in this example had a dependence on charging polarity.

Example 1O In Example 3, the amount of B doped into the formed aSr layer was determined as shown in Table 4 below by varying the B2 gas flow rate with respect to Sin and the gas flow I7L. An electrophotographic photoreceptor designated as Sample A@-@ was prepared under the same conditions as in Example 3, except that the conditions were controlled to various values.

When these were used to form an image on transfer paper under the same image forming conditions as in Example 3, the results shown in Table 4 were obtained. As is clear from these results, it is desirable that B be doped in the a-8t layer in an amount in the range of 10' to 10 atomic% for an electrophotographic photoreceptor that can be used practically. Yes, yes.

(): Shun O: Good ×:
Example 11 An electrophotographic photoreceptor of the present invention was prepared as described below using the apparatus shown in FIG. 4, and both results were achieved! An image was produced by performing phosphoric acid treatment.

Surface treatment was performed using a solution of 1000 Al of Mo on an aluminum substrate with a thickness of 1 mm and a size of lOcmX], □crn, which was cleaned by thoroughly washing with water and drying to clean the surface. - Prepare a substrate and place a heater at a predetermined position of the fixing member 33 at a predetermined position in the vapor deposition tank 31, about 10C1rL apart from the heater 34 for 1 yen.
It was fixed at -4.

Further, it was separated from the polycrystalline/recon target 35 with a purity of 5 nines by about 8.5 CI71. Next, the air in the vapor deposition tank 31 is evacuated to create a vacuum of about 1×10 torr. After that, the heater 34 is ignited to uniformly heat the board.
After that, the auxiliary valve 45 was fully opened and the valve 49 of the cylinder 3B was fully opened, and the flow rate adjustment valve 44 was gradually opened and the main nozzle (adjusted with the lube 46) While doing so, fill cylinder 38 with gas,
The degree of vacuum in the vapor deposition tank 31 is 5.5 x 10' torr.
Then, after fully opening the valve 39, the flow rate adjustment valve 43 was opened.
While watching the 70-meter 41, gradually open the vapor deposition tank 31.
Make sure that the vacuum inside is 5 x 10'torr.
After introducing r gas into the deposition tank 31, the high-frequency power source 36 was turned on, and 13.5% was introduced between the aluminum substrate and the polycrystalline silicon target.
A high frequency wave of 6 MIIz, I KV was applied to generate a discharge, and the formation of an a-S 1 layer on the aluminum substrate was started. The growth rate of the a-8 layer at this time is approximately 21/se
The test was conducted continuously for 30 hours.

The thickness of the resulting aS1 layer was 20 tt.

The electrophotographic photoreceptor of the present invention prepared in this warm state was subjected to 0 corona discharge at a power supply voltage of 550 (l V) in the dark, and then imagewise exposed at a charge of 15/IIX"8ee to form an electrostatic image. This electrostatic image was developed by a cascade method using a toner loaded with M, and then VC transfer fixation was performed on a transfer paper, and an extremely clear and high quality image was obtained.

Example 20 In Example 11, the flow rate of Jf and gas was varied with respect to the flow rate of Ar gas, and the H buds doped in the a-8 layer formed are shown in Table 5 below. Electrophotographic photoreceptors with φ values and samples KO~0 were prepared in the same manner as in Example 11, except that the values were controlled to various values as shown.

Using these, the same image forming strip F'l as in Example 11 was prepared.
When an image was formed on a transfer paper using the following method, the results shown in Table 5 were obtained. As is clear from these results, as a practical electrophotographic photoreceptor, a
Preferably, H is doped into the -8 layer in an amount ranging from 10 to 40 atomic percent.

O: Violation ○: Good △: Practically usable ×: Not possible Example 21 The electrophotographic photoreceptors prepared in Examples 1, 3 and 4 were placed in a high-temperature and humid atmosphere at a temperature of 40° C. and a humidity of 90 RH. I left it alone. After 96 hours, temperature 23°0, humidity 50R
Immediately after being taken out into a H% atmosphere, images were formed on transfer paper using the conditions and procedures used in each example for each photoreceptor, and clear and high-quality images were obtained. Ta.

Based on this result, is this invention possible? It has been demonstrated that the LL photographic photoreceptor has excellent moisture resistance as well.

Example 22 Created using I7 in exactly the same manner as Example 1. is? For Niko photoreceptor -C1 in the dark, power supply tri F'60 (
e-corona discharge at 10V, then 20 eux-s
A static image is formed by imagewise exposure with an AC exposure amount, and the static VT image is developed using a liquid developer in which a charged toner is dispersed in an isoparaffinic hydrocarbon wood solvent, and is then printed on a transfer paper. The image U on the transfer paper thus obtained was extremely high in resolution and clear.
It was of high quality.

Furthermore, in order to test the solvent resistance (liquid development resistance) of the electrophotographic photoreceptor, the above image forming process was repeatedly applied.
Image J on the previous transfer paper: When the image on the 10,000th transfer paper was compared, no difference was observed, demonstrating that the electrophotographic photoreceptor of the present invention has excellent solvent resistance. As a cleaning method for the photoreceptor, a blade cleaning method was applied, and a blade made of urethane rubber was used.

[Brief explanation of the drawing]

2111 and 2 are schematic structural cross-sectional views showing examples of preferred embodiments of the electrophotographic photoreceptor of the present invention, and FIGS. 3 and 4 are respectively for manufacturing the electrophotographic photoreceptor of the present invention. FIG. 2 is a schematic explanatory diagram showing an example of a device for ■, 5... Electrophotographic photoreceptor, 2.6... Support;
3, 7... Photoconductive layer, 8... Surface coating layer, 4, 9...
・Free surface, 10.31... Vapor deposition tank, 14.36...
High frequency power supply applicant: Canon Co., Ltd.

Claims (1)

[Claims] A method for producing an electrophotographic photoreceptor having a support and a photoconductive layer made of amorphous silicon, which comprises exposing the layer-forming surface of the support to glow discharge. Method.