JP2889461B2 - Electrophotographic photoreceptor and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and more particularly to an electrophotographic photosensitive member for a semiconductor laser beam printer and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, laser beam printers using an electrophotographic system have rapidly spread as output terminals for personal computers, word processors and the like. An organic photoconductor having infrared sensitivity is used as a photoconductor used in the laser beam printer. However, there is a problem that the durability and the printing durability are insufficient, although the infrared sensitivity and the charging characteristics are excellent. On the other hand, a photoreceptor having amorphous silicon as a long-life photoreceptor has been developed and put into practical use. However, amorphous silicon has low optical absorption in a wavelength region of 780 nm of a generally used semiconductor laser, and as a result, amorphous silicon The sensitivity of the silicon photoreceptor rapidly decreases in a wavelength region longer than 750 nm, and the light of the semiconductor laser is not completely absorbed by the photoconductive layer. As a result, a wood-gray pattern appears on the image due to interference with the surface reflected light, which impairs image quality.

As a countermeasure against this, Japanese Patent Laid-Open Publication No.
It has been proposed to provide an anti-reflection layer as disclosed in No. 1, but it was difficult to completely erase it.
Further, periodic irregularities may be provided on the surface of the substrate (Japanese Patent Application Laid-Open No. 60-168156), or fine and irregular irregularities may be randomly provided (Japanese Patent Application Laid-Open Nos. 62-69272 and 63-2091).
2) It has been proposed to reduce specular reflection of laser light on a substrate and reduce interference. According to this method, there is a problem that the irregularities on the surface of the substrate are enlarged after the formation of the amorphous silicon, and the surface of the photoreceptor becomes rough, leading to a reduction in resolution and cleaning properties or the generation of defects. As a substrate of the amorphous silicon photoreceptor, a high-quality aluminum substrate is used to prevent film defects [Japanese Patent Laid-Open Nos. 61-9546 and 61-95].
47, T.R. Fukuda, S .; Shirai, K .; Sa
itoh & H. Ogawa, Optoelectr
onics, vol 4 , p273 (1989)], resulting in high costs. The film defect causes image quality defects such as black spots and white spots, and particularly causes a lack of reliability because many of them appear by repeated copying and printing.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-sensitivity, highly reliable, long-life electrophotographic photosensitive member at a low cost by eliminating the drawbacks of such an amorphous silicon electrophotographic photosensitive member. It is in. Another object of the present invention is to provide an electrophotographic photoreceptor for a laser beam printer capable of outputting high-quality prints with high resolution and no interference pattern.

[0005]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems, and as a result, has smoothed the surface of the intermediate layer coated on the surface of the roughened conductive substrate. By doing so, an electrophotographic photoreceptor suitable for a laser beam printer with high image quality, high resolution and no interference pattern is obtained, and an intermediate layer is formed on a roughened conductive substrate by a coating method. By using the difference between the thin film growth process in the dry process and the thin film formation in the wet process depending on the underlying shape, the influence of the underlying on the image characteristics of the photoconductor can be minimized or completely eliminated. The inventors have found that they can be eliminated, and have completed the present invention.

Namely, the electrophotographic photoreceptor of the present invention, a conductive substrate having a rough surface, an intermediate layer, hydrogen, halogen,
A photoconductive layer mainly composed of amorphous silicon containing at least one element selected from Group III elements and Group V elements of the periodic table , wherein the photoconductive layer is formed of hydrogen, c
Logen, group III element, group V element, carbon, nitrogen
Contains at least one element selected from oxygen and oxygen
Layer consisting mainly of amorphous silicon
Rogen, from Group III elements of the Periodic Table and from Group V elements
Amorphous containing at least one selected element
It becomes silicon germanium and a layer mainly, wherein a surface in said <br/> between layers is smoother than the surface of the conductive substrate. In the electrophotographic photoreceptor of the present invention, the surface of the conductive substrate has fine irregularities of 0.05 to 5 μm, and the intermediate layer is a dried and cured product of one or more of a silicon compound, a titanium compound and a zirconium compound. And the intermediate layer is preferably formed by a coating method. These compounds preferably have one or both of an alkoxy group and a chelate ring of acetylacetone (acetylacetonato ring).

In the electrophotographic photoreceptor of the present invention, a charge injection preventing layer may be provided between the intermediate layer and the photoconductive layer, and an antireflection layer is provided on the surface side of the photoconductive layer. It is desirable to provide a surface layer on the surface. As the charge injection blocking layer, the antireflection layer and the surface layer, only one of them, or two or all of them can be provided simultaneously. Each layer except the photoconductive layer of the electrophotographic photosensitive member is preferably formed from the following layers. That is, the charge injection blocking layer is made of amorphous silicon containing at least one element selected from the group consisting of hydrogen, halogen, group III element, group V element, carbon, nitrogen and oxygen. The surface layer is an amorphous silicon layer containing at least one element selected from the group consisting of hydrogen, halogen, Group III element, Group V element, carbon, nitrogen, and oxygen, or hydrogen, halogen, Group III element in the periodic table. An amorphous carbon layer containing at least one element selected from Group III elements and Group V elements.

Hereinafter, the present invention will be described in detail. 1 to 3 show longitudinal sectional views of the electrophotographic photosensitive member of the present invention. FIG. 1 shows an intermediate layer 2 having a surface smoother than that of a conductive substrate 1.
And a photoconductor in which a photoconductive layer 3 mainly composed of amorphous silicon is sequentially laminated. In FIG. 2, a surface layer 5 is provided on the charge injection blocking layer 4 and the photoconductive layer 3 between the intermediate layer 2 and the photoconductive layer 3, and the surface layer 5 can be replaced with an antireflection layer. . Further, in FIG. 3, amorphous silicon and / or amorphous 2-layer structure of the carbon (5a, 5b) is a provided a photosensitive member surface layer 5 made of is shown, Ru replace a surface layer 5a antireflective layer this to be able to also.

In the present invention, either a conductive support or an insulating support may be used as a support constituting the conductive substrate. Examples of the conductive support include metals such as stainless steel, aluminum, nickel, and chromium, and alloys thereof. Among the stainless steels, those formed of Cr-Ni-containing steel generally called austenitic stainless steel can be used. Furthermore, a conductive support composed of at least molybdenum, chromium, manganese, tungsten or titanium on the surface of a conductive support made of austenitic stainless steel is preferably used. These conductive layers can be formed by a plating process, a sputtering method, or an evaporation method. Alternatively, an aluminum substrate having a conductive layer formed using chromium, titanium, tungsten, or molybdenum as a main component can be used. Furthermore, a conductive support made of molybdenum, tungsten, or titanium can be used. As the insulating support, polyester,
Polymer films or sheets of polyethylene, polycarbonate, polystyrene, polyamide, polyimide, etc.,
Glass, ceramic and the like can be mentioned. In the case where an insulating support is used, at least a surface in contact with another layer is subjected to a conductive treatment. Conductive treatment, in addition to the conductive metal,
It is performed by forming a metal film on an insulating support by using gold, silver, copper, or the like by a vapor deposition method, a sputtering method, or an ion plating method.

In the present invention, as the conductive substrate having a rough surface, a substrate whose surface is polished more smoothly by changing the roughness of the abrasive from coarse particles to fine particles by buff polishing, grindstone polishing or the like can be used. . The surface of the substrate may be clouded by fine streaks. Further, a conductive substrate having fine irregularities on its surface by grinding, sandblasting, honing, or the like can be preferably used. The pitch of the irregularities may be regular or irregular and random. The surface roughness after polishing or unevenness is Rmax of 0.1.
The range of from 0.5 to 5 μm is suitable, preferably from 0.1 to 5 μm.
3 μm. The thickness of the conductive substrate is 0.5 to 5
A range of 0 mm is appropriate, and preferably 1 to 20 mm.

The intermediate layer of the present invention is formed from at least one dry cured product of a silicon compound, a titanium compound, and a zirconium compound. Examples of a silicon compound suitable for forming the intermediate layer include, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane ,
γ-methacryloxypropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N
-(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, diphenyldimethoxysilane, phenyl Silane coupling agents such as trimethoxysilane, diphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, and tetra-n-propoxysilane; silicate compounds such as tetramethylglycolsilicate, tetraethylglycolsilicate, methylpolysilicate, and ethylpolysilicate; In addition, a commercially available silicon hard coat can be used. These silicon compounds may contain silica sol.

As the titanium compound suitable for forming the intermediate layer, an organic derivative of orthotitanic acid such as orthotitanate and polyorthotitanate, a titanium chelate compound, a titanium coupling agent and the like can be used. . The orthotitanate is represented by the following general formula (I). R ₁ , R ₂ , R ₃ and R ₄ in the formula may be the same or different and include a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, i-butyl group, hexyl group, octyl group, nonyl group, cetyl group, stearyl group, cyclohexyl group, phenyl group, tolyl group, a hydrocarbon residue such as a benzyl group, It may be a hydrocarbon group having a substituent such as a hydroxyl group or a substituted amino group. As specific examples of the orthotitanate, preferably, tetramethyl orthotitanate, tetraethyl orthotitanate, tetra n-propyl orthotitanate, tetraisopropyl orthotitanate, tetra n-butyl orthotitanate, tetraisobutyl orthotitanate, 2-ethylhexyl orthotitanate Titanate, nonyl orthotitanate, cetyl orthotitanate, stearyl orthotitanate, cresyl orthotitanate, diisopropyl-bis-triethanolaminotitanate, and the like.

The polyortho titanate is represented by the following general formula (II).

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrocarbon residue as exemplified in the general formula (I), and n is 2
It means the above integer. Examples of the polyortho titanate include polybutyl titanate and polycresyl titanate, and polymers of the above orthotitanate.

The titanium chelate compound is represented by the following general formula (III). Ti (L) _n X _4-n (III) (wherein, L represents a ligand of oxygen coordination, X represents an ester residue, and n represents an integer of 1 to 4.) As hexanediol, glycol such as octanediol, β-diketone such as acetylacetone, lactic acid, malic acid, tartaric acid, hydroxycarboxylic acid such as salicylic acid,
Examples include ligands of oxygen-containing compounds coordinated to titanium, such as keto acid esters such as acetoacetic ester, keto alcohols such as diacetone alcohol, and amino alcohols such as triethanolamine. As specific examples of the titanium chelate compound, preferably, bishexanediolatobisisopropoxytitanium, bisoctanediolatobisisopropoxytitanium, bisacetylacetonatobisisopropoxytitanium, bisacetylacetonatotitanium oxide, polyacetylacetonato Titanium, lactato titanium, lactato ethoxy titanium, lactato ammonium titanate, ammonium acetylacetonatolactotitanate, triethanolaminatatotitanium and the like can be mentioned.

As the titanium coupling agent, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropoxy titanium tri (dioctyl pyrophosphate), tetraisopropyl titanate bis (dioctyl phosphite), tetraoctyl titanate bis (ditridecyl) Phosphite), tetra [2,2-di- (allyloxymethyl) butyl] titanate bis (ditridecyl phosphite), oxoethylenedioxytitanium bis (dioctyl pyrophosphate), ethylenedioxytitanium bis (dioctyl pyrophosphate), etc. No.

As the zirconium compound suitable for forming the intermediate layer, zirconium alkoxide (zirconate ester), zirconium complex, zirconium chelate compound and the like can be used. Examples of the zirconium alkoxide include zirconium tetra n-propoxide, zirconium tetra n-butoxide and the like,
Examples of the zirconium complex include zirconium trifluoroacetylacetone. Examples of the ligand of the zirconium chelate compound include the ligand of the oxygen-containing compound represented by the above-mentioned symbol L. As specific examples of the chelate compound, preferably, tetrakisacetylacetonatozirconium, bisacetylacetonatobisbutoxyzirconium, acetylacetonatotrisbutoxyzirconium, acetoacetatotetrakisethylzirconium, acetoacetatobutoxytrisethylzirconium, acetoacetate Tatobisbutoxybisethylzirconium, acetoacetatoethyltrisbutoxyzirconium, lactatotetrakisethylzirconium,
Lactatobisbutoxybisethylzirconium, acetoacetatobisacetylacetonatobisethylzirconium, acetoacetatoacetylacetonatotrisethylzirconium, lactatobisacetylacetonatobisethylzirconium and the like.

[0017] Among the above group IV compounds of the periodic table,
An alkoxide compound in which an alkoxy group is substituted for a group IV element (acid ester of a group IV element), a chelate compound in which acetylacetone is coordinated with a group IV element to form an acetylacetona ring, or an alkoxide in which an acetylacetona ring is formed Compounds and the like are preferably used. The Group IV compounds can be used alone or as a mixture of two or more. In the formation of the intermediate layer, it can be used as a mixture with a binder resin for reasons such as improvement in adhesiveness and control of the resistance value.
Acids and alkalis may be added.

The intermediate layer can be formed by an appropriate method such as spray coating, dip coating, knife coating, roll coating and the like. That is, after applying the coating liquid of the Group IV compound, the mixture is dried and cured while being left or heated at a temperature of room temperature to 250 ° C., thereby forming an intermediate layer made of a dried and cured product of the Group IV compound. . The drying and curing treatment may be performed in the air, in a nitrogen stream, or in a vacuum after evaporating the solvent. Further, while changing the concentration of the Group IV compound in the coating solution stepwise or continuously, the coating solution can be applied a plurality of times to give the intermediate layer a concentration gradient. Further, a plurality of intermediate layers may be formed with or without a concentration gradient. On the other hand, in order to manufacture a photoreceptor free of interference patterns and image quality defects, it is necessary to make the surface of the formed intermediate layer smoother than the conductive substrate. The surface roughness has a relative relationship with the conductive substrate, and it is difficult to clearly describe the surface roughness.
In particular, the thickness is preferably 1.0 μm or less. When the intermediate layer is formed by the above-described coating method, the surface can be easily finished to be smooth, and finally, the surface of the photoconductor becomes smooth. The thickness of the intermediate layer is set arbitrarily.
3 μm or less, and particularly preferably in the range of 0.1 to 1 μm.

The electrophotographic photosensitive member of the present invention has a photoconductive layer on the intermediate layer. Optionally, a charge injection blocking layer between the intermediate layer and the photoconductive layer, and an antireflection layer and / or
Alternatively, it is desirable to provide a surface layer. The charge injection blocking layer contains at least one of hydrogen, halogen, a group III element, a group V element, carbon, nitrogen, and oxygen in order to improve adhesion to a substrate or a photoconductive layer and charge injection blocking ability. It is made of amorphous silicon. Whether to use a Group III element or a Group V element as an additive element
It is determined by the charging polarity of the photoconductor. The thickness of the charge injection blocking layer is suitably in the range of 0.01 to 10 μm, preferably 0.1 to 10 μm. In the present invention, an auxiliary layer such as an adhesive layer may be further provided between the charge injection blocking layer and the conductive substrate. This auxiliary layer is made of, for example, amorphous silicon containing at least one kind of carbon, nitrogen, oxygen and the like. Carbon, nitrogen, and amorphous silicon
A-SiC _x , a-SiN _y , a-Si containing oxygen
In the case of O _z , the contents x, y and z are each 0.01 <
x <0.5, 0.01 <y <0.3, 0.01 <z <
A range of 0.5 is preferred. The thickness of the auxiliary layer is 0.1 to 3 μm
The range of m is preferred.

[0020]

[0021] In the present invention, the photoconductive layer, hydrogen, halogen, a group III element, a group V element, carbon, amorphous silicon containing at least one of nitrogen and oxygen
A layer mainly composed of amorphous silicon germanium containing at least one of hydrogen, halogen, a group III element and a group V element (hereinafter referred to as an a-Si layer) ; It has a stacked structure consisting of a called SiGe layer). The a-Si layer has high photosensitivity in the visible light range, and the a-SiGe layer
It has high light sensitivity in a long wavelength region of up to 800 nm.
Therefore, by combining them, high light sensitivity is exhibited over a long wavelength range from visible light to 800 nm. The laminated structure of both is usually composed of an a-Si layer and an a-SiGe
Although the order of the layers is as follows, the a-Si layer and the a-SiGe layer may be stacked in the reverse order, or the a-SiGe layer may be sandwiched between the a-Si layers.

The a-Si layer according to the combination with the a-SiGe layer comprises at least one of hydrogen and halogen.
Formed mainly of amorphous silicon containing
And impurity elements such as Group III elements such as boron.
Or a group V element such as phosphorus or
Improve load retention. In particular, halogens reduce dark decay
It is effective. Hydrogen and / or halogen content
Is suitably in the range of 3 to 40 atomic%. Group III
The content of the element or group V element depends on the charging polarity of the photoconductor,
Determined by the required spectral sensitivity, 0.01-1000
A range of ppm is appropriate. The thickness of the a-Si layer is 1 to 1
A range of 00 μm is preferred. The a-Si layer has a band.
In order to improve electrical properties, reduce dark decay, improve sensitivity, etc.
It is also possible to add elements such as carbon, nitrogen and oxygen to
You. On the other hand, in the a-SiGe layer, the atomic ratio of germanium to silicon is preferably in the range of 0.01 to 1. The thickness of the a-SiGe layer is appropriately in the range of 0.1 to 50 μm, and preferably 0.5 to 20 μm. The a-SiGe layer may contain about 1 to 50 atomic% of halogen for improving photoconductivity. Further, in order to reduce dark decay, residual potential, and light fatigue, a group III element such as boron or a group V element such as phosphorus is contained . In that case, for example, the content of boron with respect to silicon and germanium is determined by the amounts of silicon and germanium and the charging polarity of the photoreceptor.
The range is suitably from 0.1 to 1000 ppm, preferably from 0.1 to 1000 ppm.
1 to 100 ppm. The phosphorus content is determined by the amounts of silicon and germanium and the charging polarity of the photoreceptor, but is suitably in the range of 0.01 to 100 ppm, preferably 0.01 to 10 ppm. further,
For the same purpose as described above, at least one of carbon, nitrogen and oxygen may be contained.

In the present invention, it is desirable to provide an antireflection layer on the surface side of the photoconductive layer. The thickness and refractive index of the antireflection layer may be adjusted so that the minimum value of the reflection spectrum is adjusted to the wavelength of the light source to be used. The film thickness may be λ (2m + 1) / 4n (where λ: wavelength of the light source, m: 0, 1, 2,...) Where n is the refractive index, and the refractive index is the refractive index of the photoconductive layer. it is sufficient to approximate the n ₁ of the square root (n ₁ ^1/2). This refractive index can be varied from about 4 to 2 depending on the content of carbon, nitrogen and oxygen with respect to silicon. The antireflection layer may have a role of a charge injection blocking layer or may have a function of a surface protection layer. The film thickness is suitably in the range of 0.01 to 5 μm, preferably 0.1 to 2 μm. When the film thickness is less than 0.01 μm, the minimum value of the reflection spectrum cannot be sufficiently obtained. On the other hand, when the film thickness is more than 5 μm, the peak width of the reflection spectrum becomes narrow, and the production of the photoconductor becomes difficult. It becomes difficult from the point of thickness distribution and the like.

In the present invention, it is desirable to provide a surface layer on the uppermost layer of the photoreceptor. This surface layer may be composed of an amorphous silicon layer containing at least one of hydrogen, halogen, a group III element, a group V element, carbon, nitrogen and oxygen, or may be composed of hydrogen, a halogen, a group III element and a group V element. It is composed of an amorphous carbon layer containing at least one element. The group III element and the group V element are selected according to the charging polarity in order to improve the charge holding ability and reduce the residual potential. Further, carbon, nitrogen, and oxygen can be added in order to improve light transmittance and charge retention ability. Further, a halogen such as fluorine may be added for the purpose of preventing the deposits on the corotron. These amorphous silicon layers and / or amorphous carbon layers may be stacked in multiple layers. FIG. 3 shows an example thereof, in which the surface layer 5 has a two-layer structure of a first surface layer 5a and a second surface layer 5b. When the surface layer is an amorphous carbon layer containing hydrogen and / or halogen, a large amount of hydrogen or halogen contained in the layer contains chain-like CH ₂ -bonds, -C (halogen) ₂ -in the layer. bond or increase the branched -CH ₃ bond, since that would impair the hardness of the resulting layer, the amount of hydrogen and / or halogen in the layer is required to be less than 50 atomic%. The thickness of the surface layer is appropriately in the range of 0.01 to 10 μm, preferably 0.1 to 5 μm. The surface layer preferably has a contact angle with pure water droplets of 60 ° or more, and more preferably 80 ° or more. The surface hardness is Vickers hardness of 500 kg / m.
m ² or more, more preferably 1000 kg / mm ² or more.

Next, a method for forming each of the layers provided on the intermediate layer will be described. Each layer formed on the intermediate layer can be formed by means such as a glow discharge decomposition method by a plasma CVD method, a sputtering method, an ion plating method, and a vacuum evaporation method, and the glow discharge decomposition method is particularly preferable. At that time, as the raw material gas, a photoconductive layer and an auxiliary layer formed as needed,
In the case of the charge injection blocking layer and the antireflection layer, a main raw material gas containing silicon is used, and in the case of a surface layer, the main raw material gas containing silicon or the main raw material gas containing a hydrocarbon or a halogen-substituted product thereof is used. Used.

In the case of forming amorphous silicon or amorphous carbon by the glow discharge decomposition method, a gaseous raw material may be introduced into a reduced pressure vessel to generate a glow discharge. As the raw material gas, a mixed gas of the main raw material gas and a raw material gas containing an additional element as necessary is used. Hydrogen gas or an inert gas such as helium, argon, or neon can be further mixed with the mixed gas as a carrier gas. Glow discharge decomposition may employ either direct current or alternating current discharge. In addition, the film forming conditions are a frequency of 5 GHz or less (when forming an amorphous carbon layer,
0.1 to 2.45 GHz, preferably 5 to 20 MHz),
Reactor internal pressure 10 ^{-5 to} 10 Torr (0.001 to 133
3 Pa) [When an amorphous carbon layer is formed, 0.1.
1 to 5 Torr (13.3 to 667 Pa)], a discharge power of 10 to 3000 W, and a substrate temperature of 30 to 300 ° C. (30 to 400 ° C. when an amorphous carbon layer is formed). It can be set appropriately by adjustment.

When amorphous silicon or a layer mainly composed of amorphous silicon is formed, silanes, in particular, silane (SiH ₄ ) and / or disilane (Si ₂ H ₆ ) are used as a main source gas containing silicon. In the present invention, the source gas mixed with the main source gas containing silicon includes hydrogen, halogen, carbon, and nitrogen (one of Group V elements 1).
Species), oxygen, and gases containing additional elements such as Group III elements and Group V elements are used.

As the source gas containing hydrogen, hydrogen gas is usually used, but if the main source gas and / or the mixed gas contains hydrogen, it may not be particularly necessary to add hydrogen gas. Source gases containing halogen include SiF ₄ ,
SiCl ₄ , SiHF ₃ , SiHCl ₃ , SiH
It can be used ₂ F _2, SiH ₂ Cl ₂ or the like. As the raw material gas for containing carbon, nitrogen and oxygen, the raw material gas containing carbon includes hydrocarbons such as methane, ethane, propane and acetylene, and halogenated hydrocarbons such as CF ₄ and C ₂ F _6. As a source gas containing nitrogen, N ₂ simple gas, NH ₃ , N
A gas of a nitrogen hydride compound such as ₂ H ₄ or HN ₃ can be used. Further, in a source gas containing oxygen, O ₂ , N
₂ O, CO, CO _{2 and the} like can be used. As a source gas containing a Group III element, a gas containing B, Al, Ga, In, or the like can be used, and typically, diborane (B ₂ H ₆ ) is used. In addition, as the source gas containing the group V element, in addition to the above-mentioned gas containing nitrogen, P, A
A gas containing s, Sb, or the like can be used. Typically phosphine (PH ₃ ) or ammonia (NH ₃ )
Is mentioned. In order to form the a-SiGe layer, a germanium-containing gas such as germanium tetrahydride (GeH ₄ ) or a germanium halide-containing gas such as germanium tetrafluoride (GeF ₄ ) can be used.

The following are used as main raw materials for forming the amorphous carbon layer. That is, as a raw material of the main carbon, a paraffinic hydrocarbon represented by the general formula C _n H _{2n + 2} such as methane, ethane, propane, butane, and pentane; and a general formula C such as ethylene, propylene, butylene, and pentene General formula C _n H such as olefinic hydrocarbon, acetylene, allylene, butyne and the like represented by _n H _2n
Linear or branched aliphatic hydrocarbons such as acetylene-based hydrocarbons represented by _2n-2 , cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, alicyclic hydrocarbons such as cyclohexene, Examples include aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and anthracene, and hydrocarbon-substituted products thereof. When the amorphous carbon layer contains halogen, for example, carbon tetrachloride, chloroform, carbon tetrafluoride, trifluoromethane, chlorotrifluoromethane, dichlorodifluoromethane, bromotrifluoromethane, perfluoroethane, perfluoropropane and the like Halogenated hydrocarbons can be used. These carbon raw materials may be in a gaseous state, a solid state, or a liquid state at room temperature. Further, as a raw material gas mixed with a main raw material gas containing a hydrocarbon or a halogen-substituted product thereof as necessary, the above-mentioned gas containing nitrogen, oxygen, a group III element, a group V element and the like can be mentioned.

[0030]

The present invention will be described in more detail with reference to Examples , Reference Examples and Comparative Examples. REFERENCE EXAMPLE 1 A cylindrical substrate made of aluminum having an Rmax of 0.5 μm was used as a substrate, and a two-layer structure of an intermediate layer made of a zirconium compound and a silicon compound, a charge injection blocking layer, a photoconductive layer, and amorphous silicon nitride was formed on the substrate. An amorphous silicon photoreceptor having a surface layer having a thickness of 0.25 μm was prepared in the following manner. 2 parts by weight of tetrakisacetylacetonatozirconium, γ-acryloxypropyltrimethoxysilane (trade name: KBM50
3, Shin-Etsu Chemical Co., Ltd.) 1 part by weight and isopropanol 2
A solution consisting of 0 parts by weight is applied on the cylindrical substrate,
After drying at 50 ° C. for 2 hours, an intermediate layer having an average thickness of 0.6 μm was formed. The surface roughness of the formed intermediate layer is Rmax 0.0
It was 5 μm.

Next, capacitively coupled plasma CVD for cylinders
By exhausting the inside of the reactor sufficiently and introducing a mixed gas of silane, hydrogen and diborane to perform glow discharge decomposition,
A charge injection blocking layer having a thickness of 4 μm was formed on the intermediate layer. The film forming conditions at that time were as follows. 100% silane gas: 180cm ³ / min 100% hydrogen gas flow rate: 90cm ³ / min 200ppm hydrogen dilution diborane flow rate: 90cm ³ /
min Reactor internal pressure: 133.3 Pa (1.0 Torr) Discharge power: 200 W Discharge time: 60 min Discharge frequency: 13.56 MHz Substrate temperature: 250 ° C. The discharge frequency and substrate temperature under the following film forming conditions for each layer are as described above. Fixed to the value.

After the formation of the charge injection blocking layer, the inside of the reactor is sufficiently evacuated, and a mixed gas of silane, hydrogen and diborane is introduced to decompose by glow discharge. A conductive layer 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 / m
in Reactor internal pressure: 133.3 Pa (1.0 Torr) Discharge power: 300 W Discharge time: 200 min

After the formation of the photoconductive layer, the inside of the reactor is sufficiently evacuated, and a mixed gas of silane, hydrogen and ammonia is introduced and glow discharge decomposition is performed. One surface layer was formed. The film forming conditions at that time were as follows. 100% silane gas flow rate: 20 cm ³ / min 100% hydrogen gas flow rate: 180 cm ³ / min 100% ammonia gas flow rate: 30 cm ³ / min Reactor internal pressure: 66.7 Pa (0.5 Torr) Discharge power: 50 W Discharge time: 30 min

After the formation of the first surface layer, the inside of the reactor is sufficiently evacuated, and a mixed gas of silane, hydrogen and ammonia is introduced to decompose by glow discharge. A 1 μm second surface layer was formed. The film forming conditions at that time were as follows. 100% silane gas flow rate: 15 cm ³ / min 100% hydrogen gas flow rate: 180 cm ³ / min 100% ammonia gas flow rate: 43 cm ³ / min Reactor internal pressure: 66.7 Pa (0.5 Torr) Discharge power: 50 W Discharge time: 20 min

The electrophotographic photosensitive member manufactured as described above was mounted on a semiconductor laser printer (XP-9; manufactured by Fuji Xerox Co., Ltd.) and an image test was performed. At that time, a polyurethane resin blade was used for the cleaner device. Magnetic brush development was performed using a two-component developer. The obtained image was clear and no fog was observed. There were no black or white spots. However, some interference patterns were observed.

[0036]

REFERENCE EXAMPLE 2 A cylindrical austenitic stainless steel polished with a grindstone having a surface roughness of Rmax 0.8 μm (SU
Using S316), an amorphous silicon photoreceptor in which an intermediate layer made of the following zirconium compound and silicon compound, an n-type charge injection blocking layer, a photoconductive layer, and a surface layer are sequentially provided on the substrate is as follows. Produced. Bisacetylacetonatobisisopropoxytitanium and γ
-Acryloxypropyltrimethoxysilane (trade name:
The KBM503) in a weight ratio of 1: except for using 1, ginseng
In the same manner as in Example 1 , an intermediate layer having a surface roughness Rmax of 0.05 μm and an average film thickness of 1.0 μm was formed.

Next, the inside of the reactor was sufficiently evacuated, and a mixed gas of silane, hydrogen and ammonia was introduced to decompose by glow discharge.
A charge injection blocking layer made of μm amorphous silicon nitride was formed. The film forming conditions at that time were as follows. 100% silane gas flow rate: 60 cm ³ / min 100% hydrogen gas flow rate: 100 cm ³ / min 100% ammonia gas flow rate: 60 cm ³ / min Reactor internal pressure: 133.3 Pa (1.0 Torr) Discharge power: 200 W Discharge time: 30 min

After the formation of the charge injection blocking layer, a photoconductive layer was formed in the same manner as in Reference Example 1 except that a mixed gas was introduced at a diborane concentration of 0.1 ppm relative to silane. Then, a film thickness of 0.6 was formed on the photoconductive layer under the following film forming conditions.
A surface layer made of μm amorphous silicon carbide was formed. 100% silane gas flow rate: 50 cm ³ / min 100% ethylene gas flow rate: 50 cm ³ / min 200 ppm Hydrogen diluted diborane gas flow rate: 100 cm ³
/ Min Reactor internal pressure: 133.3 Pa (1.0 Torr) Discharge power: 100 W Discharge time: 30 min

[0040]

Example 1 In the same manner as in Reference Example 2 , an intermediate layer, a charge injection blocking layer and a photoconductive layer were formed on an austenitic stainless steel substrate.
A layer made of amorphous silicon germanium having a thickness of 2 μm and a germanium content of 20 atomic% was formed on the photoconductive layer. The film forming conditions at that time were as follows. 100% silane gas flow rate: 160 cm ³ / min 100% hydrogen gas flow rate: 160 cm ³ / min 50% germane gas flow rate: 80 cm ³ / min Reactor internal pressure: 133.3 Pa (1.0 Torr) Discharge power: 200 W Discharge time: 30 min A surface layer was formed on the amorphous silicon germanium layer in the same manner as in Reference Example 2 .

COMPARATIVE EXAMPLE A cylindrical substrate made of aluminum having a surface roughness Rmax of 2.0 μm was used as a substrate, and no intermediate layer was formed.
An amorphous silicon photoconductor was manufactured in the same manner as in Reference Example 1 .

Each of the electrophotographic photosensitive members produced as described above was subjected to a negative charging laser beam printer (XP-11;
(Manufactured by Fuji Xerox Co., Ltd.). The results are summarized in Table 1. The evaluation criteria shown in Table 1 are as follows. a. Interference fringes ◎: No interference pattern was observed at all ：: Almost no interference pattern was observed △: Some interference pattern was observed b. Resolution ◎: The image was clear. な か っ: There was no problem in practical use. X: The image was unclear. C. White point / Black point ◎: No fog was observed at all, no black or white spots were observed. ○: No fog was observed, but some black or white spots were generated. X: Fog was observed, black points or white was observed. A point has also occurred

[0044]

[Table 1] The photoconductor of the comparative example in which the intermediate layer was not formed did not show interference fringes, but had a large surface roughness of the photoconductor, insufficient resolution, and image quality defects.

[0045]

The electrophotographic photoreceptor of the present invention comprises a conductive substrate having a rough surface, an intermediate layer, a layer mainly composed of amorphous silicon, and a layer mainly composed of amorphous silicon germanium.
And a surface of the intermediate layer is smoother than a surface of the conductive substrate. As a result, the electrophotographic photoreceptor of the present invention, as a photoreceptor for a laser beam printer, can reduce the specular reflection of laser light on a substrate. High resolution, no interference pattern, and high quality print output. In particular, when the intermediate layer is formed by a coating method, the surface of the photoconductor can be easily smoothed, so that image quality defects such as black spots and white spots do not occur, and a highly reliable electrophotographic photoconductor can be obtained. It can be manufactured at low cost.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of the electrophotographic photosensitive member of the present invention.

FIG. 2 shows another longitudinal sectional view of the electrophotographic photosensitive member of the present invention.

FIG. 3 shows another longitudinal sectional view of the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Conductive base, 2 ... Intermediate layer, 3 ... Photoconductive layer, 4 ... Charge injection prevention layer, 5 ... Surface layer or antireflection layer, 5a ... First surface layer or antireflection layer, 5b ... Second Surface layer.

──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03G 5/00-5/16

Claims (11)

(57) [Claims] And 1. A conductive substrate having a rough surface, and the intermediate layer,
A hydrogen, a halogen, a photoconductive layer composed mainly of amorphous silicon containing at least one element selected from periodic table Group III element and a group V element, the optical guide
The electric layer is composed of hydrogen, halogen, group III element of the periodic table,
Group elements, carbon, nitrogen and oxygen
Mainly amorphous silicon containing at least one kind
Layers, hydrogen, halogens, Group III elements of the periodic table and
Contains at least one element selected from the group V elements
Amorphous silicon germanium-based layer
It consists of a electrophotographic photosensitive member, wherein the surface of the intermediate layer is smoother than the surface of the conductive substrate. 2. The electrophotographic photoreceptor according to claim 1, wherein the surface of the conductive substrate has fine irregularities of 0.05 to 5 μm. 3. The electrophotographic photoreceptor according to claim 1, wherein the intermediate layer is made of one or more dry cured products of a silicon compound, a titanium compound and a zirconium compound. 4. The electrophotographic photoreceptor according to claim 3, wherein the silicon compound, titanium compound or zirconium compound has an alkoxy group. 5. The electrophotographic photosensitive member according to claim 3, wherein the titanium compound or the zirconium compound has an acetylacetonato ring. 6. The electrophotographic photoreceptor according to claim 3, wherein the titanium compound or the zirconium compound has an alkoxy group and an acetylacetonato ring in a molecule. 7. The electrophotographic photosensitive member according to claim 1, wherein a charge injection blocking layer is provided between the intermediate layer and the photoconductive layer. 8. The charge injection blocking layer is made of amorphous silicon containing at least one element selected from the group consisting of hydrogen, halogen, Group III element, Group V element, carbon, nitrogen and oxygen. 7. The electrophotographic photosensitive member according to 7. 9. An electrophotographic photosensitive member according to any one of claims 1-8 provided with the antireflection layer on the surface side of the photoconductive layer. 10. An amorphous silicon layer containing at least one element selected from the group consisting of hydrogen, halogen, a group III element, a group V element, carbon, nitrogen and oxygen in the uppermost layer, or hydrogen, Halogen, Periodic Table III
The electrophotographic photoreceptor according to any one of claims 1 to 9 , wherein a surface layer made of an amorphous carbon layer is provided with at least one element selected from Group V elements and Group V elements. 11. The method for producing an electrophotographic photosensitive member according to any one of claims 1 to 10, the intermediate layer is characterized by being formed by a coating method.