JPH0882947A - Electrophotographic photoreceptor, its production and image forming method - Google Patents

Abstract

PURPOSE: To provide an electrophotographic photoreceptor provided with at least a photoconductive layer and a surface layer on the electrically conductive substrate able to be formed at a low temp., having an org. photoconductive layer which has a high hardness, is excellent in wear resistance, optical and electrical characteristics and has a surface having oxidation resistance and being low-frictional and having a low energy, and to provide a method to produce the electrophotographic photoreceptor and also an image forming method using the photoreceptor. CONSTITUTION: This electrophotographic photoreceptor has a surface layer 3 of amorphous germanium contg. nitrogen or further contg. a group III or V element and/or halogen.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor having a photoconductive layer, a method for producing the same, and a method for forming an image using the photoreceptor.

[0002]

2. Description of the Related Art In recent years, electrophotographic photoconductors provided with a photoconductive layer containing amorphous silicon as a main component,
The one provided with an organic photoconductive layer is used. Amorphous silicon photoconductors have higher hardness than selenium-based photoconductors and organic photoconductors, and are superior in thermal stability and chemical stability. On the other hand, organic photoconductors are selenium-based photoconductors and amorphous silicon photoconductors. Compared with the photoconductor, it is excellent in electrical properties such as charging property, dark decay, infrared sensitivity, etc., and is used as a low-cost photoconductor.

However, when both the amorphous silicon photoconductor and the organic photoconductor are used in the electrophotographic process, ozone is generated in the charging step, the photoconductor is oxidized, and further, nitrogen oxide is adsorbed and water vapor is generated. Due to the adsorption or the like, the electric resistance of the surface of the photoconductor is lowered, and a lateral flow of charged electric charges occurs. In the exposure process, a lateral flow of the electrostatic latent image occurs, so
It cannot be used as an electrophotographic photoreceptor as it is. Further, in the step of cleaning the residual toner after the transfer of the developed image, a filming phenomenon in which fine particles used for the toner and the external additive adhere to the surface of the photoconductor is apt to occur, causing fogging, stains, and white spots on the image, This causes deterioration of image quality. Furthermore, organic photoreceptors can be used over a long period of time,
Cleaning blade, carrier, toner, etc.
There is a drawback that abrasion occurs and the life is shorter than that of the selenium type photoconductor and the amorphous silicon photoconductor.

On the other hand, a-SiN _x and a-Si are formed on the surface of the photoconductor having the amorphous silicon photoconductive layer.
Amorphous silicon-based materials such as C _x and a-SiO _x , carbon-based materials such as a-C: H and a-C: H and F such as amorphous carbon and diamond carbon, organic-based materials (for example, silicone-based resin), etc. However, it is difficult to construct an electrophotographic photosensitive member without losing the characteristics of amorphous silicon at all.

Further, by superimposing an a-Si: H photoconductor having a Si ₃ N ₄ surface layer on the organic photoconductor, the sensitivity of the organic photoconductor is made to be a generalized color. It has been proposed to improve durability (Japanese Patent Laid-Open No. 58-80647).
(See the official gazette). However, at the interface between the organic photoconductor and the a-Si: H photoconductor, it is difficult to inject the photogenerated carriers that are generated and moved by the mutual photoconductor into another layer to make them transportable. It was difficult to obtain an a-Si photoconductor at a low temperature according to the heat resistance of the organic photoconductor.

An organic photoreceptor having a hard surface layer made of a carbon-based material such as amorphous carbon such as aC: H or aC: H or F or diamond carbon is disclosed in Japanese Patent Laid-Open No. 1-22.
Although proposed in Japanese Patent Publication No. 19755, the surface layer is liable to have insufficient adhesiveness with the organic photoconductive layer, and cracks and cracks due to difference in hardness are likely to occur. Moreover, if the film is formed at a low temperature, the hardness becomes insufficient. Further, since the surface layer is active, there are problems that discharge products such as ozone and nitrogen oxides are generated and adsorbed on the surface layer, or image quality is deteriorated due to adhesion of toner.

In order to prevent the adsorption of discharge products, the photoconductor is heated to keep it in a dry state at all times, or the surface of the photoconductor is treated with an abrasive or the like to prevent foreign matters from adhering thereto. Was needed. The method of constantly heating the photoconductor is wasteful of energy, and there is a problem in use such that it takes a long time to be usable after the power is turned on to the copying machine or the printer. Also, if the photoconductor temperature is raised, the temperature inside the developing machine will be 45 in the summer and high temperature areas.
Since the temperature is higher than 0 ° C., the developer is blocked and the conveyance becomes uneven, and as a result, image defects such as white streaks and black streaks are likely to occur. Further, the restriction on the use of low-temperature fixing toner or the like runs counter to the recent demand for energy saving.

Further, the hard surface material has an extremely small amount of wear during cleaning, but when the amorphous silicon photoconductor is manufactured by the plasma CVD method, it is 1
It is difficult to completely suppress the occurrence of hemispherical projection defects of 0 μm or more, and when the substrate of the infrared laser printer photoconductor is roughened, unevenness occurs on the surface. Even after polishing, the polishing is likely to be localized, which causes white spots and black spots. In recent printers, the required specifications for black dots are particularly strict,
The occurrence of black spots of 0.1 mm is also a problem compared to conventional copiers. Therefore, the method of cleaning by polishing has a problem in reliability in long-term use.

Further, in order to solve the image blurring at high humidity, the conventional a-SiN _x film raw material is changed to SiH ₄ and NH _3.
Therefore, an a-SiN _x film having excellent water repellency, which is changed to SiH ₄ , H ₂ and N ₂ and has a relation of elemental bond amount in the film of Si-N>Si-H> N-H, is proposed. (Japanese Patent Laid-Open No. 5-
150532, JP-A-5-188618). However, it has been reported that ammonia can be synthesized by high-frequency discharge with an N ₂ / H ₂ gas ratio of 4: 1 (Chemical Society of Japan, 5,880,1989). in this way,
The use of SiH ₄ , H ₂ and N ₂ results in NH ₃
The result is the same as when using a substrate, and a film suitable for the surface layer cannot be obtained unless the substrate temperature is 300 ° C. or higher. At such a high temperature, the characteristics of the photoconductive layer deteriorate, and the substrate is heated by high temperature. There is a problem in that it is deformed and the dimensional accuracy is reduced. In addition, a-Si using SiH ₄ , H ₂ and N ₂ gas
Since the N _x film has a high hydrogen content, there is a problem that it is inferior in oxidation resistance and lacks in temporal stability.

[0010]

Therefore, the present invention solves the above problems, enables the production of a photoreceptor at a low temperature, has high hardness and excellent abrasion resistance, and has excellent optical characteristics and electrical characteristics. Another object of the present invention is to provide an electrophotographic photoreceptor having a surface layer having a low frictional force surface and a low energy surface which does not cause adhesion of purified products of corona discharge and toner filming and which is a low energy surface. .

Another object of the present invention is to provide an electrophotographic photosensitive member having a photoconductive layer which does not require a drum heater, facilitates cleaning of residual toner, and can be downsized at low cost. Further, the present invention is to provide an electrophotographic photoreceptor having a photoconductive layer that has sufficient resistance to ultraviolet rays and organic solvents, has a long life, is highly reliable, and can realize high-quality image quality. It is what Furthermore, the present invention is intended to provide a method for producing a photoconductor having the above characteristics, and an image forming method using the photoconductor.

[0012]

The present invention makes it possible to solve the above problems by adopting the following configuration. (1) An electrophotographic photoreceptor having at least a photoconductive layer and a surface layer on a conductive substrate, wherein the surface layer is made of amorphous germanium containing nitrogen.

(2) The electrophotographic photosensitive material according to the above (1), wherein the absorbance of the infrared spectrum stretching vibration of the surface layer has a relationship of (nitrogen-hydrogen bond)> (germanium-hydrogen bond). body. (3) The surface layer has a contact angle with pure water of 85 ° to 140 °.
The electrophotographic photosensitive member according to the above (1) or (2), characterized in that

(4) The electrophotographic photosensitive member according to any one of (1) to (3) above, wherein the surface layer contains a Group III element or a Group V element. (5) The electrophotographic photoreceptor according to any one of (1) to (4) above, wherein the surface layer contains halogen. (6) The electrophotographic photoreceptor according to any one of the above (1) to (5), wherein an intermediate layer is provided between the surface layer and the photoconductive layer.

(7) The electrophotographic photosensitive member according to the above (1), wherein the photoconductive layer is an organic photoconductive layer. (8) The electrophotographic photosensitive member according to (1) above, wherein the photoconductive layer is made of at least amorphous silicon. (9) The electrophotographic photoreceptor according to (7) or (8) above, wherein the photoconductive layer comprises a charge generation layer and a charge transport layer.

(10) In a method for producing an electrophotographic photosensitive member, which comprises a step of forming at least a photoconductive layer on a conductive substrate and a step of forming a surface layer, a germanium hydride gas and / or a germanium halide gas are used. And a method of producing a surface layer by using nitrogen gas as a raw material and decomposing it by a glow discharge method while heating the substrate temperature in the range of 80 to 300 ° C. to form a surface layer. (11) The method for producing an electrophotographic photosensitive member according to the above (10), wherein a Group III element or a Group V element and / or a halogen component is added to the raw material.

(12) In the image forming method, comprising the steps of charging the image forming member, forming a latent image on the image forming member, and developing the latent image on the image forming member.
An image forming method using the photoconductor according to any one of (1) to (9).

[0018]

1 to 7 are schematic sectional views of an electrophotographic photosensitive member which is one specific example of the present invention. FIG. 1 shows a photoconductor in which a photoconductive layer 2 and a surface layer 3 are laminated on a conductive substrate 1.
FIG. 2 shows a photoconductor in which a charge injection blocking layer 4 is provided between the conductive substrate 1 and the photoconductive layer 2 of FIG. FIG. 3 shows a photoconductor in which the photoconductive layer 2 of FIG. 2 is separated into a charge generation layer 5 and a charge transport layer 6. FIG. 4 shows the photoreceptor of FIG. 2 in which an intermediate layer 7 is provided between the photoconductive layer 2 and the surface layer 3. Figure 5
Is the same as the photoconductive layer 2 in the photoconductor of FIG.
And a charge transport layer 6 separated from each other. FIG. 6 shows FIG.
In the above photoreceptor, the intermediate layer 7 is separated into a first intermediate layer 8 and a second intermediate layer 9. FIG. 7 is a photoreceptor in which the charge trap layer 10 is provided between the photoconductive layer 2 and the first intermediate layer 8 in the photoreceptor of FIG.

Examples of the conductive substrate used in the present invention include metals such as aluminum, stainless steel, nickel and chromium, and alloys thereof. Alternatively, an insulative substrate whose surface has been subjected to a conductive treatment may be used. As the insulating substrate, polyester, polyethylene, polycarbonate, polystyrene, polyamide,
Examples thereof include polymer films or sheets of polyimide or the like, glass, ceramics, and the like, and at least the surface of these insulating substrates in contact with other layers is subjected to a conductive treatment. Conductivity treatment is carried out by the above metal, gold, silver,
A film of copper or the like is formed by a vapor deposition method, a sputtering method, an ion plating method, or the like.

The conductive substrate used in the present invention is formed of Cr-Ni containing steel which is austenitic stainless steel, and a conductive layer containing Mo, Cr, Mn, W or Ti as a main component is formed on the surface thereof. Those are preferable. These conductive layers can be formed by a plating method, a sputtering method, an evaporation method, or the like. In addition, the conductive substrate used in the present invention is made of Cr, Ti, W or M on an aluminum substrate.
What formed the electroconductive layer which has o as a main component can be used. Further, a conductive substrate made of Mo, W, Ti or the like can be used.

The thickness of the conductive substrate is 0.5 to 50 mm,
A range of 1 to 20 mm is suitable. As the conductive substrate used in the present invention, a substrate whose surface has been subjected to uneven treatment by sandblasting, honing, buffing, grinding stone polishing or the like can be used. Further, while changing the roughness of the abrasive from coarse particles to fine particles, it can be repeatedly polished and smoothed before use. The surface roughness of Rs is suitably in the range of 5S to 0.02S, preferably 0.5S to 0.03S. The surface may be a perfect mirror surface or may be cloudy due to thin streaks, but it is smooth as a whole, and no convex part remains on the boundary surface of the cutting pitch in lathe cutting. is necessary. In particular, in the case of an organic photoconductive layer, Rs in the range of 3S to 0.05S is preferably used.

If desired, a charge injection blocking layer can be provided on the conductive substrate. As the charge injection blocking layer,
Dried and solidified alkoxide or acetylacetone chelate compound, anodized metal oxide, or
Amorphous silicon to which a Group III element or a Group V element is added can be used. Whether a Group III element or a Group V element is used as an additive is determined by the charge polarity of the photoconductor. The charge injection blocking layer may contain at least one of nitrogen, oxygen, carbon and halogen in addition to the Group III element or the Group V element. The thickness of the charge injection blocking layer is 0.1 to 10 μm.
m, preferably 0.1 to 5 μm.

An auxiliary layer functioning as an adhesive layer may be provided between the conductive substrate and the charge injection blocking layer. The auxiliary layer can be formed of, for example, amorphous silicon containing at least one element of nitrogen, carbon and oxygen. The film thickness is 0.01 to 5 μm, preferably 0.1.
A range of 1 to 1 μm is suitable.

In the present invention, a photoconductive layer mainly composed of amorphous silicon containing hydrogen and / or halogen, or an organic photoconductive layer can be used. The amorphous silicon photoconductive layer of the present invention has a hydrogen and / or halogen content of 3 to 40 atom%, preferably 5 to 2
A range of 0 atom% is suitable. The amorphous silicon photoconductive layer of the present invention preferably contains a Group III element or a Group V element as an impurity element for controlling conductivity. The amount of addition is determined by the charge code of the photoconductor and the required spectral sensitivity, and is used in the range of 0.01 to 1000 ppm.

Elements such as nitrogen, carbon, and oxygen can be further added to the amorphous silicon photoconductive layer of the present invention for the purpose of improving chargeability, reducing dark decay, and improving sensitivity. Furthermore, germanium and / or tin can be added for the purpose of sensitizing the infrared wavelength region. The amorphous silicon photoconductive layer of the present invention may be configured by separating the charge generation layer and the charge transport layer. The film thickness of the photoconductive layer is preferably 1 to 100 μm, preferably 5 to 60 μm.

The organic photoconductive layer of the present invention may also be a single layer, or the charge generation layer and the charge transport layer may be separated. A single layer in which the charge generating material and the charge transporting material are dispersed in the binder resin, a charge generating layer formed by dispersing the charge generating material in the binder resin, or a uniform film of the charge generating material by vapor deposition or the like. A laminated photoconductive layer in which a charge transport layer in which a charge transport material is dispersed in a binder resin is provided on the formed charge generation layer can be used.

Examples of usable organic photoconductors include a pigment-dispersed charge generating material obtained by dispersing a polymer semiconductor such as polyvinylcarbazole and trinitrofluorenone, a bisazo pigment, a phthalocyanine pigment, a squarium pigment, or the like in a polymer material, and It is possible to use a low molecular weight dispersion type charge transport material in which a phenylamine type or pyrazoline type low molecule is dispersed in a polymer material.

Examples of the binder resin used here include thermoplastic resins having a glass transition point of 150 ° C. or higher, thermosetting resins such as unsaturated polyester and melamine among polyester, polycarbonate, polyarylate, and polystyrene. , Polyurethane, polyacrylic urethane,
A cross-linking resin such as an epoxy resin, a heat resistant resin such as polyimide, polysulfone, or a silicone resin can be used. The film thickness of the organic photoconductive layer is 1 to 100 μm, preferably 5 to 5, like the amorphous silicon photoconductive layer.
A range of 60 μm is suitable.

The surface layer, which is a feature of the present invention, contains amorphous germanium containing nitrogen as a main component, and contains germanium hydride and / or germanium halide gas, and a source gas containing nitrogen gas, or the above gas containing III gas. It is manufactured using a source gas to which a group element or a group V element component is added. The nitrogen atomic ratio (N / Ge) to germanium in the surface layer is suitably in the range of 0.5 to 1.3, preferably 0.7 to 1.2.

The Group III element and the Group V element used here are selected according to the charging polarity of the photoconductor, and if the photoconductor is positively charged, the Group V element is selected, and if the photoconductor is negatively charged, the group V element is selected. No. III
Contains a group element. The content of the group V element is 0.1
100 ppm, content of Group III element is 0.01 to 10
A range of 000 ppm is suitable. Further, when controlling the resistance of the surface layer, a group III element may be contained in the case of positive charging polarity, and a group V element may be contained in the case of negative charging.

In particular, when a Group III element component is contained, the gas to be used may be 100% of the same component,
It may be diluted with nitrogen. When a Group III element is contained, the range of 10 to 10,000 ppm is suitable for germanium, and if it is less than 10 ppm, there is no effect.
If it exceeds 0000 ppm, the wettability of the surface increases and the change over time increases, which is not preferable. When a Group V element is contained, the gas to be used may be a 100% gas of the same component or may be diluted with nitrogen. The group V element is preferably in the range of 1 to 10000 ppm with respect to germanium.
If it exceeds 00 ppm, the wettability of the surface increases and the change over time increases, which is not preferable.

Further, the surface layer may contain oxygen and / or carbon for the purpose of controlling charge injection blocking property, improving surface hardness and the like. The thickness of the surface layer is 0.01-5 μ
m, preferably 0.1 to 3 μm.
If it is less than 0.01 μm, the charge injection blocking property is insufficient and 3
When it exceeds μm, the residual charge becomes high and the stability of the repeated potential becomes poor.

The intermediate layer may be provided to improve the adhesion between the photoconductive layer, particularly the organic photoconductive layer and the surface layer. The intermediate layer is made of amorphous silicon containing carbon, oxygen or nitrogen, and / or a group III element or a group V element, and may be formed in a plurality of layers. The first intermediate layer on the side of the photoconductive layer has a carbon, oxygen, or nitrogen atom concentration lower than the atomic concentration of the second intermediate layer on the side of the surface layer, and has the atomic ratio to silicon atoms (silicon / carbon or oxygen or nitrogen). ), The range of 0.1 to 1.0 is suitable, and the film thickness is 0.1.
A range of 01 to 0.1 μm is suitable.

The Group III element or Group V element of the intermediate layer is selected according to the charging polarity of the photoconductor. When functioning as a charge injection blocking layer, a positively charged group V element is selected, and a negatively charged group III element is selected.
The amount of the group V element is 0.1 to 100 ppm, and the amount of the group III element is 0.01 to 10000 ppm. When it is used as resistance control, it is positively charged and has the II
Group I elements, Group V elements when negatively charged are selected.
The intermediate layer may contain oxygen and / or carbon for the purpose of controlling charge injection blocking property, improving surface hardness, and the like.

A charge trap layer may be provided on the photoconductive layer or between the photoconductive layer and the intermediate layer in order to prevent image blurring due to lateral charge flow at the interface with the surface layer. The charge trap layer is made of a group III element and / or a group V element.
It can be composed of amorphous silicon containing at least one group element. The group III element or the group V element is selected according to the charging polarity of the photoconductor, and the group III element is selected when the photoconductor is positively charged, and the group V element is selected when it is negatively charged.
A group element is selected. The amount of Group V element is 0.01 to 10
In the range of 00 ppm, the amount of group III elements is 5 to 10,000
It is appropriately set in the range of ppm according to the film thickness. The thickness of the charge trap layer is 0.01 to 10 μm, preferably 0.
A range of 1-5 μm is suitable.

Next, a method of forming each of the above layers on the conductive substrate will be described. The organic photoconductive layer is formed by a spray coating method or a dipping method. The amorphous silicon photoconductive layer formed on the conductive substrate may be formed by the glow discharge decomposition method by the plasma CVD method, the sputtering method, the ion plating method, the vacuum deposition method or the like, like the surface layer and other layers. it can.

The glow discharge decomposition method will be described below as an example. As a raw material gas, a gas containing an additive element is added to the above main raw material gas and used as a mixed gas. If necessary, hydrogen or an inert gas such as helium, argon or neon can be used as a carrier gas. For the glow discharge decomposition method, either direct current discharge or alternating current discharge may be adopted, and the conditions for forming the amorphous silicon film excluding the formation of the surface layer and the organic photoconductive layer are a frequency of 0 to 5 GHz and a reactor. Internal pressure 0.001 to 1333P
a (10 ^{-5 to} 10 Torr), discharge power 10 to 3000
W, and the substrate temperature can be appropriately set in the range of 30 to 300 ° C.

The surface layer was prepared by using GeH as a source gas.
₄ gas, GeH ₃ F, GeH ₂ F ₂ , GeHF ₃ , Ge
A germanium halide gas such as F ₄ and nitrogen gas are used. The gas containing germanium may be a 100% germanium compound gas or a gas diluted with nitrogen. The (Ge: N) ratio of the gas containing the germanium component is preferably in the range of 1: 1 to 1: 5 in terms of molar ratio.

The conditions for forming the surface layer are that the substrate temperature is 80 to 3
The temperature is 00 ° C, preferably 100 to 300 ° C. When the photoconductive layer is an organic photoconductive layer, the substrate temperature is 50 to 2
It is in the range of 00 ° C, preferably 100 to 200 ° C. The frequency is 0 to 5 GHz, and the internal pressure of the reactor is 0.1 to 1333.
Pa and discharge power of 100 to 3000 W are suitable. If the substrate temperature is lower than 80 ° C., the desired properties as a surface layer cannot be obtained, and if it exceeds 300 ° C., the film-forming property tends to deteriorate, and particularly in the case of an organic photoreceptor, the temperature exceeds 20 ° C. Therefore, the characteristics are likely to deteriorate.

The film quality of the a-GeN _x surface layer depends on the absorption of stretching vibration of the infrared absorption spectrum in the relationship of N-H> Ge-H. The surface layer having this relationship is not oxidized for a long period of time, but having the relationship of N-H <Ge-H is not preferable because the wettability of the surface is lowered and the physical properties of the surface layer change with time. The contact angle of the surface layer with pure water is 85 ° to 120 °, preferably 95 ° to 12 °.
A range of 0 ° is suitable. When the contact angle is less than 85 °, image blurring due to adhesion of corona discharge products and image quality deterioration due to toner filming are likely to occur. In addition, G
The composition ratio of e and N (in the film) is preferably in the range of 1: 0.5 to 1: 1.3.

As a source gas for forming the surface layer in the present invention, germanium hydride such as GeH ₄ , Ge ₂ H ₆ or the like,
Hydrogen halide such as GeH ₃ F, GeH ₂ F ₂ , GeHF ₃ , GeF ₄ and N ₂ are used.

Raw Material Containing Group III Element Used in the Present Invention
The gas is typically diborane (B₂H₆) Is listed
But B_FourH_Ten, B_FiveH₉, B_FiveH₁₁In addition to A
lH ₃Etc. can also be used. In addition, group V element moth
As a source gas containing gas, PH₃, AsH₃, SbH
₃, BiH₃Etc. can typically be used.

The carbon-containing source gas used in the present invention includes paraffin hydrocarbons represented by the general formula C _n H _{2n + 2} such as methane, ethane, propane and pentane; ethylene, propylene, butylene, pentene and the like. General formula C _n H
_2n olefinic hydrocarbons; acetylene, arylene, butyne and other general formulas C _n H _2n-2 acetylene hydrocarbons and other aliphatic hydrocarbons; cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptene, Examples thereof include alicyclic hydrocarbons such as cyclobutene, cyclopentene, and cyclohexene; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, anthracene, and their substitution products. These hydrocarbons may have a branched structure or may be a halogen-substituted product. For example, halogenated hydrocarbons such as carbon tetrachloride, chloroform, carbon tetrafluoride, trifluoromethane, chlorotrifluoromethane, dichlorodifluoromethane, bromotrifluoromethane, perfluoroethane and perfluoropropane can be used.
The carbonization raw materials listed above may be gaseous at room temperature, solid, or liquid. When it is in a solid or liquid state, it is vaporized before use. As the source gas containing oxygen, O ₂ , N ₂ O, CO, CO ₂ or the like can be used.

[0044]

EXAMPLES Next, the present invention will be described in more detail by showing examples and comparative examples. Example 1 A cylindrical base body made of Al having a thickness of 4 mm and a surface roughness Rmax of 0.05 μm was used, on which a p-type charge injection blocking layer, an amorphous silicon photoconductive layer and two layers were formed. An a-SiN _x intermediate layer having a thickness of 0.3 μm,
Further, an amorphous silicon photoconductor in which a surface layer having a film thickness of 0.3 μm was sequentially provided was manufactured.

First, after exhausting the inside of the reactor sufficiently, a mixed gas of silane gas, hydrogen gas and diborane gas is introduced to decompose by glow discharge, thereby forming a charge injection blocking layer having a film thickness of 2 μm on the cylindrical substrate. Formed. The film forming conditions at that time were as follows. 100% Silane gas flow rate: 180 cm ³ / min 100% Hydrogen gas flow rate: 90 cm ³ / min 200 ppm Hydrogen diluted diborane gas flow rate: 90 cm ³ / min Reaction vessel internal pressure: 133.3 Pa Discharge power: 200 W Discharge time: 60 minutes Discharge frequency: 13. 56 MHz substrate temperature: 250 ° C. (Note that the discharge frequency and the substrate temperature were fixed to the above values in the following layer production conditions.)

After the charge injection blocking layer is formed, the inside of the reactor is sufficiently evacuated, and then a mixed gas of silane gas, hydrogen gas and diborane gas is introduced to perform glow discharge decomposition to form a film on the charge injection blocking layer. An amorphous silicon photoconductive layer having a thickness of 20 μm was formed. The film forming conditions at that time were as follows. 100% Silane gas flow rate: 180 cm ³ / min 100% Hydrogen gas flow rate: 162 cm ³ / min 20 ppm Hydrogen diluted diborane gas flow rate: 18 cm ³ / min Reaction vessel internal pressure: 133.3 Pa Discharge power: 200 W Discharge time: 200 minutes

After the photoconductive layer was formed, the inside of the reactor was sufficiently evacuated, and then a mixed gas of SiH ₄ gas and nitrogen gas was introduced to perform glow discharge decomposition to form a film having a thickness of 0 on the photoconductive layer. A first intermediate layer of 0.15 μm was formed. The film forming conditions at that time were as follows. 100% SiH ₄ gas flow rate: 20 cm ³ / min 100% nitrogen gas flow rate: 100 cm ³ / min Reaction vessel internal pressure: 66.6 Pa Discharge power: 300 W Discharge time: 10 minutes

After the production of the first intermediate layer, the inside of the reactor was sufficiently evacuated, then the mixed gas ratio of SiH ₄ gas and nitrogen gas was changed and introduced, and the glow discharge was decomposed to obtain the first intermediate layer. A second intermediate layer having a thickness of 0.15 μm was formed on the layer. The film forming conditions at that time were as follows. 100% SiH ₄ gas flow rate: 20 cm ³ / min 100% nitrogen gas flow rate: 150 cm ³ / min Reaction vessel internal pressure: 66.6 Pa Discharge power: 300 W Discharge time: 10 minutes

After the production of the second intermediate layer, the inside of the reactor was sufficiently evacuated, and then a mixed gas of GeH ₄ gas and nitrogen gas was introduced to carry out glow discharge decomposition to form a gas on the second intermediate layer. A surface layer having a film thickness of 0.1 μm was formed. The film forming conditions at that time were as follows. 100% GeH ₄ gas flow rate: 20 cm ³ / min 100% nitrogen gas flow rate: 150 cm ³ / min Reaction vessel internal pressure: 66.6 Pa Discharge power: 300 W Discharge time: 20 minutes

The surface layer of the amorphous silicon electrophotographic photosensitive member produced as described above has a contact angle with pure water of 97.
°, the (Ge: N) ratio in the surface layer is 1: 1.2, the amount of hydrogen is 8 atom%, and the absorbance of the infrared spectrum stretching vibration is N−H> Ge−H (relative ratio). Had 3: 1). The atomic ratio is X-ray photoelectron spectroscopy (XPS).
The amount of hydrogen is measured using an infrared spectrophotometer (FT-I
R) was used to measure the absorption intensity of stretching vibrations of NH and Ge-H, and the amount of hydrogen was determined by a conventional method. This photoreceptor was incorporated into a Fuji Xerox XP-11 printer modified for experiments and a print test was conducted. This printer had no drum heater and cleaning was blade cleaning. The charging potential was 470 V and the residual potential was 40 V, and the electrical characteristics were stable even when repeated. A one-component developer was used as the developer, and magnetic brush development was performed. The obtained image was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to toner filming on the surface of the photoconductor were not recognized.

[Embodiment 2] An amorphous silicon photoconductor in which an n-type charge injection blocking layer, an amorphous silicon photoconductive layer and a surface layer having a thickness of 0.5 μm are sequentially provided on the same cylindrical base body made of Al as in Embodiment 1. The body was made. First, the interior of the reactor was sufficiently evacuated, and then a mixed gas of silane gas and nitrogen gas was introduced to decompose by glow discharge to form a charge injection blocking layer having a film thickness of 1 μm on the cylindrical substrate.
The film forming conditions at that time were as follows. 100% Silane gas flow rate: 20 cm ³ / min 100% Nitrogen gas flow rate: 50 cm ³ / min Reaction vessel internal pressure: 66.6 Pa Discharge power: 300 W Discharge time: 30 minutes

After the charge injection blocking layer was prepared, the inside of the reactor was sufficiently evacuated, and then a mixed gas of silane gas, hydrogen gas and diborane gas was introduced and glow discharge decomposed to form a film on the charge injection blocking layer. An amorphous silicon photoconductive layer having a thickness of 20 μm was formed. The film forming conditions at that time were as follows. 100% Silane gas flow rate: 180 cm ³ / min 100% Hydrogen gas flow rate: 178 cm ³ / min 20 ppm Hydrogen diluted diborane gas flow rate: 2 cm ³ / min Reaction vessel internal pressure: 133.3 Pa Discharge power: 300 W Discharge time: 200 minutes

After the photoconductive layer was formed, the inside of the reactor was thoroughly evacuated, and then a mixed gas of GeH ₄ gas and nitrogen gas was introduced to decompose by glow discharge, whereby a film thickness of 0 was formed on the photoconductive layer. A surface layer of 0.5 μm was formed. The film forming conditions at that time were as follows. 50% hydrogen diluted GeH ₄ gas flow rate: 20 cm ³ / min 100% nitrogen gas flow rate: 200 cm ³ / min Reaction vessel internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 10 minutes

The surface layer of the amorphous silicon electrophotographic photosensitive member produced as described above has a contact angle of 10 with pure water.
0 ° and the (Ge: N) ratio in the surface layer is 1: 1.2
5, the amount of hydrogen is 5 atomic%, the absorbance of infrared spectrum stretching vibration is a relationship of NH> Ge-H (relative ratio is 3: 1)
Had. This photoreceptor was subjected to a print test in the same manner as in Example 1. The charging potential was −520 V and the residual potential was −50 V, and the electrical characteristics were stable even after repeated use. The obtained image was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to toner filming on the surface of the photoconductor were not recognized.

Example 3 An amorphous silicon photoreceptor was prepared in the same manner as in Example 2 except that the surface layer was doped with boron. The conditions for forming the surface layer were as follows. 50% Hydrogen diluted GeH ₄ gas flow rate: 20 cm ³ / min 1000 ppm Nitrogen diluted B ₂ H ₆ gas flow rate: 200 cm ³ / min Reaction vessel internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 10 minutes

The surface layer of the amorphous silicon electrophotographic photosensitive member produced as described above has a contact angle of 97 with pure water.
°, the (Ge: N) ratio in the surface layer is 1: 1.2, the amount of hydrogen is 10 atom%, and the absorbance of the infrared spectrum stretching vibration is N−H> Ge−H (relative ratio). Had 3: 1). This photoreceptor was subjected to a print test in the same manner as in Example 1. The charging potential is -560V and the residual potential is -2.
It was 0 V, and the electrical characteristics were stable even after repeated use. The obtained image was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to toner filming on the surface of the photoconductor were not recognized.

Example 4 In Example 2, after producing the photoconductive layer, the reactor was thoroughly evacuated, and then a mixed gas of silane gas, ethylene gas and hydrogen diluted B ₂ H ₆ gas was introduced to perform glow discharge. By disassembling, an intermediate layer having a film thickness of 0.5 μm was formed on the cylindrical substrate. The film forming conditions at that time were as follows. 100% Silane gas flow rate: 180 cm ³ / min 100% Ethylene gas flow rate: 180 cm ³ / min 200 ppm Hydrogen diluted B ₂ H ₆ gas flow rate: 180 cm ³ / min Reaction vessel internal pressure: 133.3 Pa Discharge power: 200 W Discharge time: 10 minutes

After preparation of the intermediate layer, the reactor was thoroughly evacuated,
Then GeH ₄ , GeF ₄ , and nitrogen diluted B ₂ H ₆
By introducing the mixed gas of and decomposing the glow discharge,
A surface layer having a thickness of 0.3 μm was formed on the photoconductive layer.
The film forming conditions at that time were as follows. 50% hydrogen diluted GeH ₄ gas flow rate: 10 cm ³ / min 100% GeF ₄ gas flow rate: 5 cm ³ / min 1000 ppm Nitrogen diluted B ₂ H ₆ gas flow rate: 200 cm ³ / min Reaction vessel internal pressure: 66.6 Pa Discharge power: 400 W discharge Time: 5 minutes

The surface layer of the amorphous silicon electrophotographic photosensitive member manufactured as described above has a contact angle of 11 with pure water.
0 °, the (Ge: N) ratio in the surface layer is 1: 1.0,
The amount of hydrogen was 5 atom%, and the absorbance of infrared spectrum stretching vibration had a relationship of NH> Ge-H (relative ratio was 3: 1). This photoreceptor was subjected to a print test in the same manner as in Example 1. The charging potential is -540V and the residual potential is -2.
It was 0 V, and the electrical characteristics were stable even after repeated use. The obtained image was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to toner filming on the surface of the photoconductor were not recognized.

[Embodiment 5] A charge injection blocking layer, a charge generation layer and a charge transport layer were sequentially laminated on an Al cylindrical substrate having a thickness of 1 mm, and a film was formed on an organic photoreceptor having a total thickness of 20 μm. A surface layer having a thickness of 0.3 μm was prepared. The charge injection blocking layer is
A acetylacetone alkoxide compound of zirconium and a silane coupling agent were dissolved in a solvent in a weight ratio of 1: 1 and applied, and then dried and cured to obtain a layer having a thickness of 1 μm.

Next, the charge generation layer was formed by immersing a phthalocyanine pigment in a solution in which a polyvinyl butyral resin was dispersed at a weight ratio of 5: 2 to form a layer having a thickness of 0.1 μm. Further, the charge transport layer is formed of a triphenylamine-based N, N′-diphenyl-based polycarbonate resin.
N, N'-bis (3-methylphenyl)-(1,1'-
Biphenyl) -4,4'diamine as a hole transport molecule is immersed in a solution dispersed at a weight ratio of 3: 2 to have a thickness of 20 μm.
Layers were formed by coating.

Then, this organic photoreceptor was placed in a vacuum container and heated to 150 ° C. while being evacuated. Then, a mixed gas of hydrogen-diluted GeH ₄ gas and nitrogen gas is introduced,
A surface layer having a thickness of 0.5 μm was formed by glow discharge decomposition. The film forming conditions at that time were as follows. 50% hydrogen diluted GeH ₄ gas flow rate: 20 cm ³ / min Nitrogen gas flow rate: 200 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 10 min Discharge frequency: 13.56 MHz Substrate temperature: 150 ° C. In the production of each layer below, the discharge frequency and the substrate temperature were fixed to the above values.)

The surface layer of the organic electrophotographic photosensitive member produced as described above has a contact angle with pure water of 97 °, and the (Ge: N) ratio in the surface layer is 1: 1.1. The amount of hydrogen is 10 atomic%, and the absorbance of infrared stretching vibration is NH
> Ge-H relationship (relative ratio 3: 1). A print test was conducted in the same manner as in Example 1. The charging potential was −540V and the residual potential was −40V. Moreover, the electrical characteristics were stable even after repeated use. Then, a one-component developer was used as the developer, and development was performed by the magnetic brush development method. The image obtained was clear and no fog was observed. After printing 100,000 sheets, neither image blurring nor toner filming phenomenon on the surface of the photoreceptor was observed, and image unevenness was not observed.

Example 6 An intermediate layer and a surface layer were formed on the same organic photoreceptor as in Example 5. Then, a mixed gas of monogermane gas and nitrogen gas was introduced and decomposed by glow discharge to form an intermediate layer having a film thickness of 0.1 μm on the photoconductive layer. The film forming conditions at that time were as follows. 50% hydrogen diluted GeH ₄ gas flow rate: 10 cm ³ / min Nitrogen gas flow rate: 100 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 200 W Discharge time: 10 min

Then, a film thickness of 0.3 is formed on the intermediate layer.
A μm surface layer was formed. The film forming conditions at that time were as follows. 50% hydrogen diluted GeH ₄ gas flow rate: 10 cm ³ / min Nitrogen gas flow rate: 200 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 10 min

The contact angle of the surface of the electrophotographic photosensitive member produced as described above with pure water was 97 °, the (Ge: N) ratio in the surface layer was 1: 1.15, and the amount of hydrogen was It is 8 atomic%, and the absorbance of infrared spectrum stretching vibration is NH> Ge-
It had an H relationship (relative ratio 3: 1). Using this photoreceptor, a print test was conducted in the same manner as in Example 1. The charging potential was −550V and the residual potential was −50V. Moreover, the electrical characteristics were stable even after repeated use. The image obtained was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to toner filming on the surface of the photoconductor were not observed.

Example 7 An electrophotographic photosensitive member was produced in the same manner as in Example 6 except that the surface layer was doped with boron. The conditions for forming the surface layer were as follows. 50% hydrogen diluted GeH ₄ gas flow rate: 20 cm ³ / min Nitrogen gas diluted 1000 ppm B ₂ H ₆ gas flow rate: 200 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 10 min

The surface of the electrophotographic photosensitive member produced as described above has a contact angle with pure water of 100 °, a (Ge: N) ratio in the surface layer of 1: 1.0, and an amount of hydrogen. Is 10 atom%
And the absorbance of infrared stretching vibration is N−H> G
It had an e-H relationship (relative ratio 3: 1). Using this photoreceptor, a print test was conducted in the same manner as in Example 1. The charging potential was −550V and the residual potential was −30V. Moreover, the electrical characteristics were stable even after repeated use. The image obtained was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to filming of toner on the surface of the photoconductor were not observed.

[Embodiment 8] A mixture gas of GeH ₄ gas, GeF ₄ gas and nitrogen diluted B ₂ H ₆ gas is introduced onto the intermediate layer of the same organic photoreceptor as in Embodiment 5 to decompose by glow discharge. Thus, a surface layer having a film thickness of 0.3 μm was formed. The film forming conditions at that time were as follows. 50% Hydrogen diluted GeH ₄ gas flow rate: 5 cm ³ / min 100% GeF ₄ gas flow rate: 5 cm ³ / min Nitrogen gas dilution 1000 ppm B ₂ H ₆ flow rate: 200 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 400 W Discharge time : 5min

The surface of the electrophotographic photosensitive member produced as described above has a contact angle with pure water of 110 °, a (Ge: N) ratio in the surface layer of 1: 1.1, and an amount of hydrogen. Is 5 atomic%, and the absorbance of infrared spectrum stretching vibration is NH> Ge
It had a -H relationship (relative ratio 3: 1). Using this photoreceptor, a print test was conducted in the same manner as in Example 1.
The charging potential was −580V and the residual potential was −20V.
Moreover, the electrical characteristics were stable even after repeated use. The image obtained was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to toner filming on the surface of the photoconductor were not observed.

[0071]

EFFECTS OF THE INVENTION By adopting the above constitution, the present invention has high hardness and excellent wear resistance, has a low wear force surface and a low energy surface, and has good oxidation resistance and electrical characteristics. It has become possible to provide a photoconductor having good optical characteristics and capable of obtaining good images over a large number of sheets.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

FIG. 5 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

FIG. 6 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

FIG. 7 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

Claims (12)

[Claims] 1. An electrophotographic photoreceptor having at least a photoconductive layer and a surface layer on a conductive substrate, wherein the surface layer is made of amorphous germanium containing nitrogen. 2. The electrophotographic photosensitive member according to claim 1, wherein the absorbance of infrared spectrum stretching vibration of the surface layer has a relationship of N-H> Ge-H. 3. The surface layer has a contact angle with pure water of 85 °.
3. The electrophotographic photosensitive member according to claim 1, which is in the range of 140 °. 4. The electrophotographic photosensitive member according to claim 1, wherein the surface layer contains a Group III element or a Group V element. 5. The electrophotographic photoreceptor according to claim 1, wherein the surface layer contains halogen. 6. An intermediate layer is provided between the surface layer and the photoconductive layer, according to any one of claims 1 to 5.
The electrophotographic photosensitive member according to the item. 7. The electrophotographic photosensitive member according to claim 1, wherein the photoconductive layer is an organic photoconductive layer. 8. The electrophotographic photosensitive member according to claim 1, wherein the photoconductive layer is made of at least amorphous silicon. 9. The electrophotographic photoreceptor according to claim 7, wherein the photoconductive layer comprises a charge generation layer and a charge transport layer. 10. A method for manufacturing an electrophotographic photosensitive member, comprising: a step of forming at least a photoconductive layer on a conductive substrate; and a step of forming a surface layer, wherein a germanium hydride gas and / or a germanium halide gas are used. Also, a method for producing an electrophotographic photosensitive member, characterized by using nitrogen gas as a raw material, decomposing by a glow discharge method while heating the substrate temperature in the range of 80 to 300 ° C. to form a surface layer. 11. The method for producing an electrophotographic photosensitive member according to claim 10, wherein a Group III element or a Group V element and / or a halogen component is added to the raw material. 12. An image forming method comprising: a step of charging an image forming member; a step of forming a latent image on the image forming member; and a step of developing a latent image on the image forming member. An image forming method using the photoconductor according to any one of the items.