JPS60133457A - Manufacutre of electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enable economical stabilization by forming an electrostatic charge generating layer made of amorphous Si on a conductive substrate by electrodeposition, and forming on this layer a charge transfer layer made of an org. photoconductor. CONSTITUTION:An amorphous silicon layer 2 is formed on a conductive substrate 1 by using said conductive substrate 1 as a cathode and electrolyzing silicon halide in a soln., contg. at least one of aprotic nonaq. solvents, such as hexahydrofuran or the like ethers, acetone or the like ketones, or propylene carbonate or pyridine, said silicon halide, such as SiHCl3, SiBr4, and a supporting salt, such as tetrabutylammonium bromide or tetraethylammonium perchlorate, in a current density of 0.5-5mA/cm<2>. As a result, a stable amorphous silicon layer 2 unchangeable against oxidation is formed on the conductive substrate 1.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application Kokuhatsu 0IJ is an example of an electrophotographic photoreceptor used in an electronic copying machine.
Those containing selenium, cadmium sulfide, and zinc oxide are widely known. However, these do not necessarily have the same properties as thermal stability and durability, and selenium and cadmium sulfide are classified as "manufactured" or "manufactured" due to their toxicity. It was a problem. Recently, amorphous silicon films have come into practical use as inorganic electrophotographic photoreceptors. This amorphous silicon photoreceptor exhibits extremely excellent characteristics such as spectral clarity, integral sensitivity, and thermal stability.

However, an amorphous silicon film is generally produced by decomposing silane, which is a silicon hydride, by glow discharge under reduced pressure. Formation using the glow discharge #l method uses expensive equipment including a photographic device, a high frequency power source, etc., and therefore the resulting product cannot be inexpensive.

Shoulder ・＋ 11 −＋
J l J--Jl knee 11/Hikiyatm: mho-1 [
The amorphous silicon film is also
It is known that In the case of this method, expensive equipment is not required as in the glow discharge method described in section 2, and thus the film can be produced at low cost. However, with the electrodeposition method, it is difficult to obtain a film with a high breakdown voltage that is thick enough to be used as an electrophotographic photoreceptor.

Purpose of invention misfired:! I] aims to provide a method for manufacturing an inexpensive electrophotographic photoreceptor using stable amorphous silicon.

Structure of the Invention The present invention involves forming an amorphous silicon layer to become a charge-generating layer on a conductive support by electrodeposition; The electrophotographic photoreceptor forms a body layer, thereby making it possible to produce a stable and inexpensive electrophotographic photoreceptor.

Example explanation J The layer structure of the photoreceptor of the present invention is shown in the drawing.

Conductive / 1112 pattern I, 1 body 1 contains nickel, titanium,
Metals or alloys such as stainless steel are used. The amorphous silicon layer 2 can be formed by electrolyzing the conductive support 1 as a cathode in a solution consisting of at least one aprotic non-aqueous solvent, silicon halogenide, and a supporting salt.

The aprotic non-aqueous solvent used in the solution described in 2.
Generally, it consists of an organic compound that has only hydrogen atoms bonded to carbon atoms, and its property as a solvent is extremely weak in releasing or accepting protons. Examples of the nonaqueous solvent include ethers such as hexahydrofuran, ketones such as acetone, propylene carbonate, pyridine, and the like. These may be used as a mixture, or may be used as a mixture with an inert aprotic solvent such as benzene or toluene.

As silicon halide, SiC% + Sz
HCQ, 3°SiBr4.5iHBr3, etc. are used.

The supporting salt is used to increase the conductivity of the electrolyte. Solutions consisting only of halogenated silicon and aprotic solvents have the lowest conductivity of 41, and such solutions require extremely high interelectrode voltages to produce a uniformly thick electrolytic deposit on the two cathodes. is not obtained. As the supporting salt, tetraalkylammonium salts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium perchlorate, and tetrabutylammonium perchlorate are used.

The materials listed in 2. above must be sufficiently dehydrated or dried before use. If dehydration or drying is insufficient, electrolytic deposits are likely to be formed as silicon oxide.
Moisture in the solvent can be removed by adsorption with molecular carbs or other dehydrating agents, or by other methods. Moisture contained in the supporting salt can be removed by vacuum drying at a temperature of 5°C to 100°C.

The electrolytic solution prepared with the chemical from which water has been removed as described above is placed in a sufficiently dry electrolytic cell, and the electrolytic solution forms a precipitate on the cathode. A conductor such as nickel, stainless steel, or titanium can be used for the cathode. The opposite electrode, the anode, is platinum.

Inert conductive materials such as all-graphite are preferred. It is desirable to place the entire electrolytic cell in an inert atmosphere such as dry nitrogen or argon to prevent moisture and oxygen from entering the electrolyte.

After energizing for a specified period of time, the cathode is removed from the electrolytic cell and placed in an easily volatile solvent such as benzene or tetrahydrofuran with the cathode surface wet with the electrolyte to avoid direct contact with the atmosphere. Kou 1'ding. Then, in the same manner, 1. ? Immediately transfer the cooled (194) to a hydrogen stream at 3OQ°C to 5○○°C and heat-treat for at least 30 minutes.

By the above two treatments, a stable amorphous silicon layer 2 which is not changed by oxidation can be obtained on the support.

In addition, the current density during electrolysis is 0.5 to 5 mA/7
is used. The heat treatment in a hydrogen stream after the electrolytic treatment is preferably at 300°C to 500°C, and 2 n01-
1:l -g IIA-&a44/L4n,'r-Fzuku:'2fATh -1-/q Oxidation tends to progress depending on the equipment, and heat treatment exceeding 5○○℃! At one degree, crystallization of crystalline silicon begins to occur.

The photoreceptor 1 is completed by forming the amorphous silicon layer 2 formed as described in 1-1 and then the electrically conductive layer 2.

Organic optical semiconductors used include organic polymer compounds and their derivatives such as poly-N-vinylcarbasol, polyvinylpyrene, and polyvinylanthracene, and organic low-molecular compounds and their derivatives such as carbazole, anthracene, anthraquinone, and trinitrofluorenone. can be mentioned. When a film of the above-mentioned organic compounds is formed on an amorphous silicon layer, these compounds can be appropriately dissolved or dispersed in an organic binder. Binder materials include polymeric materials such as polystyrene, polyester, and polycarbonate.

The organic photoconductor and the buying material are dissolved together in a solvent to form a solution, and this solution is applied in the form of a film onto the amorphous silicon layer 2 using a doctor blade or a spinner. Next, by drying the coating layer, a 41-electrode conductor layer 3 as a charge transport layer is formed.

(2) When the organic photoconductor is a compound with electron-donating properties such as BoIJ N-vinylcarbazole and JJ Rubazole, it can be used as a negatively charged electrophotographic sensitizer, such as anthraquinone, trinitrofluorenone, etc. of? In the case of a compound having an 11-child-accepting property, a positively charged electrophotographic photoreceptor can be obtained.

Below, more specific details of the present invention will be explained.

Tetrabutylammonium bromide 8I, which had been dried at 80°C for 1 hour, was added to a solvent containing 100ml of a clear solution of hexahydrofuran and benzene, which had been dehydrated by adding Molekiller sieves (3A type) and leaving them for several liters each. Add and dissolve. Next, silicon tetrachloride is added and mixed to prepare an electrolytic solution.

This electrolytic solution was placed in an electrolytic bath, and a 4 m square nickel plate whose surface had been polished with sandpaper was immersed in the electrolytic solution, facing the platinum anode plate, and energized at 32 mA for 100 minutes.

After the electricity was turned off, the nickel plate was taken out and immediately immersed in benzene for cleaning.Then, two sides of the nickel plate were wetted with benzene and then soaked in l',i purity hydrogen at 400°C for 1 hour. An amorphous silicon layer was formed on the nickel plate by heat treatment.

Next, a viscous solution of IJ-N-vinylcarbazole dissolved in toluene was applied onto the amorphous silicone film using a spinner and dried at 80°C. The thickness of the polyvinyl carnosol was about 16 μm.

In addition, -1 U (7J) Ho IJ - Instead of the N-hinylcarnoxole solution, anthraquinone and polyester resin (Toyoboso Polyester Resin) (Iron 200) were mixed and dissolved in 4-1i, l: ) luene. The resulting viscous solution was applied to an amorphous silicon film formed in the same manner as above and dried to produce a photoreceptor.

Using the photoreceptor prepared as described above, image formation was evaluated using the Carlson method. i.e. - Ichigami, I4
1: ξl-7 bile also fR+, i 1-uniform ze1l-N-
A negative charge was applied to the photoreceptor using vinyl carbazole, and a 1F charge was applied to the photoreceptor using anthraquinone. The initial surface potentials were approximately -500V and -1-500V, respectively. After charging, image exposure was performed to form an electrostatic latent image, and then toner development was performed using a magnetic brush method, and 1.sup. was transferred to transfer paper. In both cases, images with good resolution were obtained. It was done.

First, the electrophotographic photoreceptor of the present invention has an amorphous silicon layer, which is to be a charge-generating layer, formed by electrodeposition on a conductive support.Second, an organic photoconductive layer, which is to be a charge-transporting layer. The photoreceptor can be manufactured at low cost, unlike forming a 1114 quality silicon film by a vapor phase method such as the conventional GD-CVD method. Further, by selecting an organic photoconductor, it is possible to easily manufacture a photoreceptor with either positive or negative charging electrodes and 141.

Furthermore, in the electrodeposition formation of amorphous silicon, an aprotic nonaqueous solvent, 7. halogenated silicon, and a supporting salt are used as an electrolytic solution to electrolyze and form a conductive support. By heat treatment in a hydrogen stream at 300° C. to 600° C., a stable amorphous silicon film can be obtained, and a previously stable electrophotographic film can be obtained.

4. Explanation of t'/ri'li in the drawings Figure 1 shows a cross-sectional view of the electrophotographic photoreceptor in Fig. 1.

DESCRIPTION OF SYMBOLS 1... Conductive support, 2... Jl-grade silicon layer, 3... I photoconductor layer.

Claims (2)

[Claims] (1) An amorphous silicon layer to be a charge generation layer is formed on the conductive support by electrodeposition, and A method for producing an electrophotographic photoreceptor, which comprises forming a body layer. (2) In the step of forming an amorphous silicon layer, the precipitate obtained by electrolyzing the amorphous silicon layer in a negative manner is heated to 300°C to 50°C.
The method for producing an electrophotographic photoreceptor according to claim 1, characterized in that the step is heat treatment in a hydrogen stream at 0C.