EP0241033A1 - Membre photosensible composé d'une couche transporteuse de charge et d'une couche génératrice de charge - Google Patents

Membre photosensible composé d'une couche transporteuse de charge et d'une couche génératrice de charge Download PDF

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Publication number
EP0241033A1
EP0241033A1 EP19870105274 EP87105274A EP0241033A1 EP 0241033 A1 EP0241033 A1 EP 0241033A1 EP 19870105274 EP19870105274 EP 19870105274 EP 87105274 A EP87105274 A EP 87105274A EP 0241033 A1 EP0241033 A1 EP 0241033A1
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EP
European Patent Office
Prior art keywords
layer
photosensitive member
carbon
gas
reaction chamber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19870105274
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German (de)
English (en)
Inventor
Hideo Hotomi
Izumi Osawa
Mitsutoshi Nakamura
Shuji Iino
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Minolta Co Ltd
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Minolta Co Ltd
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Publication date
Priority claimed from JP8313086A external-priority patent/JPS62238571A/ja
Priority claimed from JP8313186A external-priority patent/JPS62238572A/ja
Priority claimed from JP8313386A external-priority patent/JPS62238574A/ja
Application filed by Minolta Co Ltd filed Critical Minolta Co Ltd
Publication of EP0241033A1 publication Critical patent/EP0241033A1/fr
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08214—Silicon-based
    • G03G5/08235—Silicon-based comprising three or four silicon-based layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/07—Polymeric photoconductive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08214—Silicon-based
    • G03G5/08221—Silicon-based comprising one or two silicon based layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08214—Silicon-based
    • G03G5/08278—Depositing methods
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08285—Carbon-based

Definitions

  • This invention relates to a photosensitive member and, more particularly, to a photosensitive member in electrophotography.
  • amorphous silicon produced by a plasma vapor deposition (referred to as a plasma-CVD hereinafter) for a photosensitive member, especially for electrophotography.
  • the photosensitive material a-Si has various spectacular properties. However, its use raises a problem that, because of a large specific inductive capacity epsilon of approximately 12, a-Si essentially needs to form a film with a minimum thickness of approximately 25 microns in order for the photosensitive member to have a sufficient surface potential.
  • a-Si photosensitive members by the plasma CVD process is a time-consuming operation with the a-Si film formed at a slow rate of deposition, and, moreover, the more difficult it becomes to obtain s-Si films of uniform quality, the longer it takes for the films to be formed. Consequently, there is a high probability that an a-Si photosensitive member in the use causes defects in images, such as white spot noise, besides other defects including an increase in cost of the raw material.
  • the a-Si photosensitive material exhibits defects in adhesivity to the substrate, in corona resistance and resistance to environment and also chemicals.
  • an organic plasma-polymerized film can be made from any of gaseous organic compounds, such as ethylene gas, benzene and aromatic silane, (one reference in this respect is the Journal of Applied Polymer Science 1973, 17 (885-892) contributed by A.T. Bell, M. Shen et al.), but any such organic plasma-polymerized film produced by a conventional method has been in use only where its insulation property is required to be good. Films of this kind have been regarded as insulators having electrical resistance of approximately 10160hm cm, such as an ordinary polyethylene film, or at the least as materials practically similar to an insulator in the application.
  • the Japanese Patent KOKAI No. 61761/1985 made public a photosensitive member coated with a surface protective layer which is a carbon insulation film resembling diamond with a film thickness of 500 angstrom - 2 microns.
  • This thin carbon film is designed to improve a-Si photosensitive members with respect to their resistance to corona discharge and mechanical strength.
  • the polymer film is very thin and an electric charge passes within the film by a tunnel effect, the film itself not needing an ability to transport an electric charge.
  • the publication lacked a description relating to the carrier-transporting property of the organic plasma-polymerized film and the topic matter failed to provide a solution to the essential problems of a-Si in the foregoing description.
  • the Japanese Patent KOKAI No. 214859/1984 made public the use of an overcoating layer of an organic transparent film with thickness of approximately 5 microns which can be made from an organic hydrocarbon monomer, such as ethylene and acetylene, by a technique of plasma polymerization.
  • the layer described therein was designed to improve a-Si photosensitive members with respect to separation of the film from the substrate, durability, pinholes, and production efficiency.
  • the publication lacked a description relating to the carrier-transporting property of the organic plasma-polymerized film and the topic matter failed to provide a solution to the essential problems of a-Si in the foregoing description.
  • the Japanese Patent KOKAI No. 46130/1976 made public a photosensitive member utilizing n-vinylcarbazole, wherein an organic plasma-polymerized film with thickness of 3 microns - 0.001 microns was formed at the surface by a technique of glow discharge.
  • the purpose of this technique was to make bipolar charging applicable to a photosensitive member of poly-n-vinylcarbazole, to which otherwise only positive charging had been applicable.
  • the plasma- polymerized film is produced in a very thin layer of 0.001 microns - 3 microns and used by way of overcoating.
  • the polymer layer is very thin, and it is not considered necessary for it to have an ability for the transportation of an electric charge.
  • the publication lacked a description relating to the carrier transporting property of the polymer layer and the topic matter failed to provide a solution to the essential problems of a-Si-in the foregoing description.
  • the Japanese Patent KOKAI No. 63541/1985 made public a photosensitive member wherein an a-Si layer is undercoated by an organic plasma-polymerized film resembling diamond with a thickness of 200 angstrom 2 microns.
  • the organic plasma-polymerized film is designed to improve the adhesivity of the a-Si layer to the substrate.
  • the polymer film can be made very thin and an electric charge passes within the film by a tunnel effect, the film itself not needing an ability to transport an electric charge.
  • the publication lacked a description relating to the carrier transporting property of the organic plasma-polymerized film and the topic matter failed to provide a solution to the essential problems of a-Si in the foregoing description.
  • the Japanese Patent KOKAI No. 28161/1984 made public a photosensitive member wherein on a substrate an a-Si film is laid and thereupon an organic plasma- polymerized film is superimposed.
  • the organic plasma-polymerized film is used as an undercoat, the insulation property thereby being utilized, and also has the functions of blocking, improving the adhesivity, or preventing the separation of the photosensitive coat.
  • the polymer layer is very thin (e.g. less than 5 micron meter, preferably less than 1 micron meter). Such a thin layer does not cause any problems such as increase of surface potential (residual potential) even if it has insufficient charge transportability, because the residual potential is controlled at a lower level by the increase of the electric potential at an undercoat layer by repeated use and the enlargement of pass of carrier thereby (tunnel effect). Therefore, this polymer layer can be used as an undercoat layer but cannot be used as a carrier transporting layer.
  • this prior art does not refer to carrier transportability due to an a-C layer, and it does not dissolve the essential problem caused by an a-Si as aforementioned.
  • the Japanese Patent KOKAI No. 38753/1984 made public a technique whereby an organic plasma polymerized thin film with a thickness of 10 - 100 angstrom is formed from a mixed gas composed of oxygen, nitrogen and a hydrocarbon, by a technique of plasma polymerization and thereupon an a-Si layer is formed.
  • Said organic plasma-polymerized film is used as an undercoat utilizing the insulation property of the polymer and also has the functions of blocking or preventing the separation of the photosensitive coat.
  • the polymer film can be made very thin and an electric charge passes within the film by a tunnel effect, the film itself not needing an ability to transport an electric charge.
  • the publication lacked a description relating to the carrier transporting property of the organic plasma-polymerized film and the topic matter failed to provide a solution to the essential problems of a-Si in the foregoing description.
  • Japanese Patent KOKAI No. 148326/81 discloses a production of a plasma-CVD thin layer comprising a pre-decomposition of gas and a pre-polymerization.
  • Si compounds are only exemplified in the Examples.
  • the Japanese Patent KOKAI No. 136742/1984 described a semiconductor device wherein on a substrate an organic plasma-polymerized layer with thickness of approximately 5 microns was formed and thereon a silicon layer was superimposed. Said organic plasma-polymerized layer was designed to prevent the aluminum, the material forming the substrate, from diffusing into the a-Si, but the publication lacked description relating to the method of its fabrication, its quality, etc. The publication also lacked a description relating to the carrier transporting property of the organic plasma-polymerized layer and the topic matter failed to provide a solution to the essential problems of a-Si in the foregoing description.
  • the Japanese Patent KOKAI No. 60447/1981 made public a method of forming an organic photoconductive layer by plasma polymerization.
  • the publication lacked description relating to the applicability of the invention to electrophotography.
  • the description in the publication dealt with said layer as a charge generating layer or a photoconductive layer and the invention described thereby differs from the present invention.
  • the topic matter failed to provide a solution to the essential problems of a-Si in the foregoing description.
  • Japanese Patent KOKAI No. 120527/78 discloses a production of a posi-type radial sensitive layer by a plasma polymerization of hydrocarbon and halogenized hydrogen. This is a production of posi-type resist material by cross-linkage using an electron-ray, X-ray, X-ray or a-ray, which is not applied to an electrophotosensitive member.
  • the a-C layer has been used for an undercoat layer or an overcoat layer, which does not need a carrier transportability, and is used under the recognition that the organic polymer film is an insulator. Therefore, the film is only used as a thin film at most 5 micron meter or so, and a carrier passes through the film due to a tunnel effect. Where the tunnel effect cannot be expected, the film can be used only at such a thin thickness that a residual potential is practically negligible.
  • the primary object of this invention is to provide a photosensitive member which is free from the above-mentioned defects, good in electric charge-transporting properties and electrical chargeability, and ensures formation of satisfactory images.
  • Another object of this invention is to provide a photosensitive member which is capable of assuming a sufficient surface potential even when the thickness of the layer is small.
  • Another object of this invention is to provide a photosensitive member which can be fabricated at low cost and in a short time.
  • Another object of this invention is to provide a photosensitive member which has an amorphous carbon layer (referred to as an a-C layer hereinafter) which is good in resistances to corona discharge, acids, humidity and heat, and in stiffness.
  • an a-C layer referred to as an a-C layer hereinafter
  • a photosensitive member which comprises an electrically conductive substrate, a charge generating layer, and a charge transporting layer comprising amorphous carbon containing hydrogen, in which the saturated carbon and unsaturated carbon exist in a specific ratio.
  • the first object of the present invention is to provide a photosensitive member comprising:
  • the second object of the present invention is to provide a photosensitive member comprising:
  • the third object of the present invention is to provide a photosensitive member comprising:
  • a photosensitive member according to the present invention essentially consists of at least a. charge generating layer and a charge transporting layer.
  • the charge transporting layer is composed of an amorphous carbon layer (a-C layer) containing hydrogen.
  • the hydrogen content of the a-C layer is 20 - 67 atomic %, preferably 40 - 67 atomic %, most preferably 45 - 65 atomic %. If the hydrogen content is less than 20 atomic %, a sufficient transportability cannot be obtained, whereas being more than 67 atomic %, the properties and productivity of the a-C layer lower.
  • the a-C layer of the present invention contains carbon atoms having various kinds of bond such as a single bond (free radical), double bond or triple bond, and some of them are bonded with hydrogen and others are not bonded with hydrogen.
  • the ratio of the number of unsaturated carbon (n 1 ) to the number of saturated carbon (n 2 ) is from 1 : 20 to 1 : 0.5 in the a-C layer.
  • the unsaturated bonds include double bond and/or triple bond.
  • n 1 is 1
  • n 2 is preferably from 20 to 0.5 as aforementioned, more preferably from 10 to 1.0, most preferably from 5 to 1.5.
  • n 2 is more than 20 (at n l being 1), the a-C layer is an insulator, which cannot be used as a charge transporting layer, because in the photosensitive member having such an a-C layer as a charge transporting layer the surface potential (electrified charge) is not reduced even by the irradiation of light, so that the photosensitive member is charged up immediately by repeated-use.
  • n 2 is less than 0.5 (n 1 being 1), that is, when the unsaturated carbons are surplus, the electrical resistance of the layer fairly decreases, so the photosensitive member having such an a-C layer becomes so worse in the chargeability that it cannot function as a photosensitive member.
  • n 2 when the value of n 2 is more than 0.5 (as n 1 is 1), the specific resistance becomes more than about 10 11 ohms.cm, and the mobility of the carrier increases to about 10 -7 cm 2 /(v.sec.) or more to give an excellent charge transportability.
  • the ratio of the number of unsaturated carbon atoms bonding with hydrogen atoms (n 3 ) to the number of unsaturated carbon atoms not bonding with hydrogen atoms (n 4 ) is 1 : 4 to 1 : 0.2.
  • the a-C layer is suitable for a charge transporting layer in case that, when assuming n 3 is I., n 4 is from 4 to 0.2, preferably from 2 to 0.5, and most preferably from 1.25 to 0.88. If the n 4 is more than 4, though the chargeability increases, the photosensitive member exhibits poor electrophotographic properties due to the reduction of photosensitivity.
  • n 4 is less than 0.2, the chargeability of the photosensitive member reduced, so that the photosensitivity is almost lost. If the ratio of n- : n4 is controlled within 1 : 4 to 1 : 0.2 the specific resistance of a-C layer becomes more than about 10 ohms.cm, and the mobility of the carrier increases to about 10-7 cm 2 /(V.sec.) or more to give an excellent charge transportability.
  • the ratio of the number of carbon atoms bonding with hydrogen (n 5 ) to the number of carbon atoms not bonding with hydrogen (n 6 ) is 1 : 0.5 to 1 : 0.14, wherein the saturated carbon include neo-carbon radical ("neo-carbon radical" means a carbon atom bonding other four carbon atoms), methine radical, methylene radical or methyl radical.
  • neo-carbon radical means a carbon atom bonding other four carbon atoms
  • methine radical methine radical
  • methylene radical or methyl radical methine radical
  • the a-C layer becomes a high electroresistible layer containing methine radical, methylene radical or methyl radical in a comparatively large amount, so that a suitable transportability cannot be obtained.
  • a photosensitive member having such a layer as a charge transporting layer hardly shows photosensitivity so as to become worse in a carrier injection and a transportability.
  • the n 6 is larger than 0.5, neo-carbon radical comparatively increases so as to reduce the resistance of the layer , so that a photosensitive member having such a layer as a charge transporting layer cannot give a sufficient charge potential.
  • n 6 is more than 0.14 (as n 5 is 1)
  • the specific resistance becomes more than about 10 11 ohms.cm
  • the mobility of the carrier increases to about 10 -7 cm 2 /(V.sec.) or more to give an excellent charge transportability.
  • the number of the whole carbon atoms means the total of the number of the unsaturated carbon and the number of the saturated carbon atoms.
  • an a-C layer having the number of saturated carbon atoms of 40 to 90 % based on the whole number of carbon atoms is preferable.
  • an a-C layer having the number of unsaturated carbon atoms of 5 to 50 % based on the whole number of carbon atoms is preferable.
  • the thickness suitable for an a-C layer ranges 5-50 microns, the preferable range being 7-30 microns.
  • the surface potential becomes lower and the images can not be copied in a sufficient density if the thickness is below 5 microns, whereas the productivity is impaired if the thickness exceeds 50 microns.
  • An a-C layer exhibits good transparency and a relatively high dark resistance, and has such a good charge transporting property that, even when the layer thickness exceeds 5 microns as described above, it transports the carrier without causing a charge trap.
  • Organic compounds for the production of a-C layer may not be always gas, but may be liquid or solid materials providing that the materials can be vaporized through melting, vaporization, sublimation, or the like when heated or vacuumed.
  • a hydrocarbon for this purpose may be selected from among, for example, methane series hydrocarbons, ethylene series hydrocarbons, acetylene series hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc. The mixture thereof may be used. Further, these hydrocarbons can be mixed.
  • methane series hydrocarbons are:
  • aromatic hydrocarbons examples are:
  • a-C layer When the a-C layer is formed according to the present invention, two kinds of the above organic compounds or more may be co-used as a mixture.
  • Various kinds of copolymer (block copolymer, graft copolymer and so on) are produced in the a-C layer so as to improve the hardness and adhesive property. If an alkane hydrocarbon (CnH2n+2) is used, i-C layer, which has a Vickers hardness of not less than 2000, i.e. diamond like supper hardness, and an electric resistance of 10 9 ohm.cm can be obtained. However, in this case as a plasma condition a high temperature, lower pressure and high power must be employed with the application of direct bias to the substrate.
  • inert gas such as H 2 , Ar, N, He and the like is suitable.
  • a-C layer of the present invention various kinds of plasma method such as direct current, high frequency, low frequency or micro wave plasma method are applicable.
  • an electromagnetic wave X-ray, laser light etc.
  • various i-C layers different in properties can be obtained from the same monomer. For instance, using low frequency plasma method (frequency is from tens Hz to hundreds KHz), a-C layer having a high hardness can be obtained.
  • a-C layer is preferably formed by a method similar to the above in the aspect of device cost and process saving.
  • the charge generating layer of a photosensitive member according to the invention is not restricted to any particular materials; the layer may be produced by, for example, amorphous silicon (a-Si) (which may contain hetero elements, e.g., H, C, O, S, N, P, B, a halogen, and Ge to change the property, and also may be a multilayer), Se, Se-As, Se-Te, CdS, or a resin containing inorganic substances such as a copper phthalocyanine and zinc oxide and/or organic substances such as a bisazo pigment, triallylmethane dye, thiazine dye, oxazine dye, xanthene dye, cyanine colorant, styryl colorant, pyrilium dye, azo pigment, quinacridone pigment, indigo pigment, perylene pigment, polycyclic quinone pigment, bis-benzimidazole pigment, indanthrone pigment, squalelum pigment, and phthlocyan
  • phthalocyanine pigments may be used as a charge generating material.
  • the phthalocyanines may be vapor depositable, and may include monochloroaluminum monochlorophthalocyanine (AlClPc(Cl)), titanil phthalocyanine (TiOPc), metal free phthalocyanine (H 2 Pc), aluminum monochlorophthalocyanine (AlClPc) , zinc phthalocyanine (ZnPc), magnesium phthalocyanine ' (MgPc) and the like.
  • AlClPc(Cl) monochloroaluminum monochlorophthalocyanine
  • TiOPc titanil phthalocyanine
  • H 2 Pc aluminum monochlorophthalocyanine
  • AlClPc aluminum monochlorophthalocyanine
  • ZnPc zinc phthalocyanine
  • MgPc magnesium phthalocyanine '
  • Inorganic compounds used as a charge generating materials may include Al 2 O 3 , CaO, CeO, CeO 2 , CdO, Cr 2 O 3 , CuO, Cu 2 0, Fe 2 0 3 , In 2 O 3 , M g O, MnO 2 , MoO 3 , NiO, PbO, SiO, SiO 2 , SnO 2 , Ta 2 0 5 , TiO, Ti0 2 , Ti 2 0 3 , WO 3 , Y 2 O 3 , ZnO, Zr0 2 , Z nS, CdS, CdSe, CdTe, PbS, ZnSe, MgF 2 and the like.
  • AlClPc(Cl), TiOPc or H 2 Pc as a phthalocyanine pigments, and ZnS, A1 2 0 3 or SiO as an inorganic compound may be used in combination.
  • Examples of the most preferable combinations are AlClPc(Cl) with ZnS, and TiOPc with ZnS.
  • the charge generating layer may be of any material that is capable of absorbing light and generating a charge carrier with a very high efficiency.
  • the charge generating layer may be produced by a conventional method, for example, a method of coating a suitable binder resin dispersing the powder of the above materials, plasma method and the like. If the charge transporting layer is formed by the plasma method, it is preferable to produce the charge generating layer by the plasma method because of the device cost and the process saving. In the case that the charge generating layer is produced by a conventional method, it is preferable to use the aforementioned inorganic materials, dyes or pigments which are previously coated with an organic material by plasma polymerization. When these inorganic materials, dyes or pigments are dispersed in a resin, dispersibility, resistivity to a solvent, and prevention of spoilage will be achieved.
  • a charge generating layer according to the invention can be formed at any position in a photosensitive member, that is, for example, it can be formed at any of the top-most, intermediate and lowest layers.
  • the thickness of the layer must in general be set such that a light of 550 nm can be absorbed 90% or more, though depended on the kind of the material used, especially its spectral absorption characteristic, light source for exposure, purpose, etc. With a-Si as the material the thickness must be within the range of 0.1 - 3 microns.
  • heteroatoms other than carbon and hydrogen, can be incorporated into the material constituting said a-C charge transporting layer.
  • atoms in Group III in the periodic table or halogen atoms can be incorporated.
  • atoms in Group V in the periodic table or alkali metal atoms can be incorporated.
  • atoms of Si, Ge, an alkali earth metal, or an chalcogen can be incorporated.
  • Figs. 1 through 12 illustrate embodiments of the present invention, each in schematic sectional representation of models, wherein (1) denotes a substrate, (2) an a-C layer as a charge transporting layer, and (3) a charge generating layer.
  • (1) denotes a substrate
  • (3) a charge generating layer When a photosensitive member of the model shown in Fig. 1 is positively charged and then exposed to image light, a charge carrier is generated in the charge generating layer (3) and the electron neutralizes the surface charge while the positive hole is transported to the substrate (1) under guarantee of a good charge-transporting charcteristic of the a-C layer (2).
  • the photosensitive member shown in Fig. 1 is negatively charged, contrarily the electron is transported through the a-C layer (2).
  • the photosensitive member illustrated in Fig. 2 is an example wherein an a-C layer (2) forms the topmost layer. When it is positively charged, the electron is transported through the a-C layer (2) and, when negatively charged, the hole is transported through the a-C layer (2).
  • Fig.3 illustrates an embodiment of a photosensitive member of the present invention, in which on a substrate .(1) a charge transporting layer (2), a charge generating layer (3) and then a charge transporting layer (2) are formed in this order.
  • Figs. 4 through 6 illustrate the same photosensitive members as Figs. 1 through 3, except that each additionally has a surface-protective overcoat (4) with thickness in the range of 0.01 - 5 microns, which, in keeping with the operating manner of the respective photosensitive member and the environment where it is used, is designed to protect the charge generating layer (3) or the charge transporting a-C layer (2) and to improve the initial surface potential as well.
  • Any suitable material in public knowledge can be used to make the surface protective layers. It is desirable, in the practice of this invention, to make them by a technique of organic plasma polymerization from the viewpoint of manufacturing efficiency, etc.
  • An a-C layer embodying the invention can also be used for this purpose. Heteroatoms, when required, can be incorporated into the protective layer (4).
  • Figs. 7 through 9 illustrate the same photosensitive members as Figs. 1 through 3, except that each additionally has an undercoat (5) with a thickness in the range of 0.01 - 5 microns which functions as an adhesion layer or a barrier layer. Depending on the substrate (I) or the process which it undergoes, this undercoat helps adhesion and prevents injection. Any suitable material in public knowledge can be used to make the undercoat. In this case, too, it is desirable to make them by a technique of organic plasma polymerization. An a-C layer according to the present invention can also be used for the purpose.
  • the photosensitive members shown by Figs. 7 through 9 can also be provided with an overcoat (4) as illustrated by Figs. 4 through 6 (see Figs. 10 through 12).
  • the surface properties may be improved by the radiation of plasma of oxygen, hydrogen, inert gases, gases for a dry-etching (e.g. halogenized carbons) and/or nitrogen etc.
  • a dry-etching e.g. halogenized carbons
  • a photosensitive member of the present invention has a charge generating layer and a charge transporting layer. Therefore the production requires at least two processes.
  • an a-Si layer produced by equipment for glow discharge decomposition is used as the charge generating layer
  • the same vacuum equipment can be used for plasma polymerization, and it is naturally preferable in such cases to produce the a-C charge transporting layer, the surface-protective layer, the barrier layer, etc., by plasma polymerization.
  • the charge transporting layer of the photosensitive member is produced by the so-called pl.asma-polymerizing reaction, that is, for example:
  • Fig. 13 illustrates an equipment for the production of a photosensitive member of the present invention, which is a capacitive coupling type plasma CVD equipment. Exemplifying a photosensitive member having a plasma polymerized polyethylene layer as a charge transporting layer, the production thereof is explained according to Fig. 3.
  • the numerals (701) - (706) denote No. 1 tank through No. 6 tank which are filled with a feedstock (a compound in the vapor phase at normal temperatures) and a carrier gas, each tank connected with one of six regulating valves No. 1 through No. 6 (707) - (712) and one of six flow controllers No. 1 through No. 6 (713) - (718).
  • FIG. 7 (719) - (721) show vessels No. 1 through No. 3 which contain a feedstock which is a compound either in the liquid phase or in the solid phase at normal temperatures, the temperature of each vessel being capable of being controlled to, for example, a room temperature to 150° C or from -50°C to a room temperature by means of one of three heaters No. 1 through No. 3 (722) - (724).
  • Each vessel is connected with one of three regulating valves No. 7 through No. 9 (725) - (727) and also with one of three flow controllers No. 7 through No. 9 (728) - (730).
  • each electrode with a heater (737) for heating the electrode.
  • Said power-applying electrode is connected to a high frequency power source (739) with a matching box (738) for high frequency power interposed in the connection circuit, to a low frequency power source (741) likewise with a matching box (740) for low frequency power, and to a direct current power source (743) with a low-pass filter (742) interposed in the connection circuit, so that by a connection-selecting switch (744) the mechanism permits application of electric power with a different frequency.
  • the pressure in the reaction chamber can be adjusted by a pressure control valve (745), and the reduction of the pressure in the reaction chamber can be carried out through an exhaust system selecting valve (746) and by operating a diffusion pump (747) and an oil-sealed rotary vacuum pump (748) in combination or by operating a cooling-elimination device (749), a mechanical booster pump (750) and an oil-sealed rotary vacuum pump in combination.
  • a pressure control valve (745) The pressure in the reaction chamber can be adjusted by a pressure control valve (745), and the reduction of the pressure in the reaction chamber can be carried out through an exhaust system selecting valve (746) and by operating a diffusion pump (747) and an oil-sealed rotary vacuum pump (748) in combination or by operating a cooling-elimination device (749), a mechanical booster pump (750) and an oil-sealed rotary vacuum pump in combination.
  • the exhaust gas is discharged into the ambient air after conversion to a safe unharmful gas by a proper elimination device (753).
  • the piping in the exhaust system is equipped with pipe heaters at intervals in the pipe lines so that the gases which are vaporized forms of feedstock compounds in the liquid or solid state at normal temperatures are prevented from condensing or congealing in the pipes.
  • reaction chamber is equipped with a heater (751) for heating the chamber, and an electrode therein are provided with a conductive substrate (752) for the purpose.
  • Fig. 13 illustrates a conductive substrate (752) fixed to a grounding electrode (735), but it may be fixed to the power-applying electrode (736) and to both the electrodes as well.
  • Fi g. 14 is a schematic view of a resistance-heating type vapor deposition equipment for a preparation of charge generation layer by a vacuum vapor deposition.
  • the equipment includes vacuum chamber (101), substrate holder (102), substrate (103), shutter (104), boats (105) and (106), outlet for discharge (107) and electrodes (108).
  • the charge generating layer of the present invention may be made by the following processes.
  • the boats (105) and (106) which contain phthalocyanine pigments and inorganic compounds respectively are set up to the electrodes (108), and the substrate (103) is to the substrate holder (102).
  • the vacuum chamber (101) is vacuumed through the outlet (107) by a vacuum pump (not illustrated in Fig. 14).
  • the amount of the materials deposited on the substrate (103) from the boats (105) and (106) can be controlled by the shutter (104).
  • a shield (not shown in Fig. 14) may be provided between the boats (105) and (106) to prevent mutual influence in the temperature of the each boat.
  • the condition of the vapor deposition such as the degree of the vacuum pressure, boat temperature, evaporation time, amount of pigments and inorganic compounds and others may be selected according to a variation, a thickness of layer, a ratio of the pigments to the inorganic compounds and others for a desired charge generating layer.
  • a charge generating layer and a charge transporting layer can be continuously formed by incorporating a vapor deposition equipment as shown in Fig. 14 into a glow discharge decomposition equipment as shown in Fig. 13.
  • the reaction chamber for the production of photosensitive member is preliminarily decreased to a level in the range of about 10 to 10 -6 Torr by the diffusion pump, the degree of vacuum is checked, and then the gas absorbed in the equipment is removed. Simultaneously, by the heater for electrode, the electrode and the conductive substrate fixed to the opposing electrode are heated to a given temperature.
  • connection-selecting switch is put in position for, for example, the high frequency power source so that high frequency power is supplied to the power-applying electrode.
  • An electrical discharge begins between the two electrodes and an a-C layer in the solid state is formed on the conductive substrate with time.
  • the ratios of n 1 /n 2 , n 3 /n 4 and n 5 /n 6 specified in the embodiments of the present invention are controlled by applying a bias electric power of 10 V to 1 KV from the direct electric power source (743) though depended on other production conditions. That is, the number of controlled carbon, the number of saturated carbon bonding with hydrogen, and the number of the unsaturated carbon bonding with hydrogen atoms in an a-C layer are decreased by applying a high bias electric power, and the hardness of the a-C layer itself can be increases by the same.
  • the a-C charge transporting layer formed by the above process is excellent in a transmittance, a dark resistance, and a transportability of charge carrier remarkably.
  • the polarity of this layer may be controlled to P or N type by introducing B 2 H 6 gas from No. 4 tank (704) or PH 3 gas from No. 5 tank (705) to increase the charge transportability.
  • the charge generating layer (3) may be produced by introducing H 2 gas from No. 2 tank (702) and SiH 4 gas from No. 3 tank (703) as a layer essentially consisting of a-Si.
  • the gas may be introduced into the chamber (733) to cause plasma-polymerization.
  • the a-C layer is made from organic compounds having a high boiling point
  • these compounds are previously coated on the surface of the substrate, and then plasma of a carrier gas or others are irradiated on the substrate to polymerize them (so-called plasma-polymerization).
  • electromagnetic wave such as laser beam, ultraviolet, X-ray or electron beam may be irradiated alone or as a supplement (photo-assist method), or the assistance of magnetic field or bias direct electric field may be effectively used.
  • the photo-assist method is effective to quicken the deposition rate of the a-C layer, to shorten the production time and to increase the hardness of the a-C layer.
  • the main application of the a-C layer of the present invention is to a charge transporting layer as aforementioned, the a-C layer of the present invention may be used for an overcoat layer having a charge transportability. Even in the case that the a-C layer of the present invention is applied to an overcoat layer alone, an excellent durability, of course, can be achieved without increase of residual potential.
  • the internal pressure of the reaction chamber (733) was adjusted to 0.5 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 3 x 50 x 50 mm, was preliminarily heated up to 250°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 150 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately four hours, there was formed a charge transporting layer with a thickness of approximately 5.5 microns on the conductive substrate (752).
  • the ratio of the number of unsaturated carbon (n l ) to the number of saturated carbon (n 2 ) was 1 : 4.
  • the dark resistance of the layer was less than 1 x 10 12 ohm cm and the ratio of the dark resistance to the light resistance was more than 102 - 10 4 . Therefore, it is understandable that this plasma polymerized polyethylene layer can be used as a photosensitive member for electrophotography.
  • the power application from the high frequency power source (739) was stopped for a time and the reaction chamber was vacuumized inside.
  • SiH 4 gas from No. 3 tank (703) and H 2 gas from No. 2 tank (702) were, under output pressure gage reading of 1 K g/cm 2 , led into the mass flow controllers (715) and. (714). Then, the mass flow controllers were set so as to make SiH 4 flow at 90 sccm and H 2 flow at 210 sccm, and the gases were allowed into the reaction chamber. After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.
  • the circuit to the high frequency power source (739) was supplied and a 30 W power (frequency: 13.56 MHz) was applied to the electrode (736) to generate glow discharge. After 10 minutes of glow discharge, there was formed an a-Si:H charge generating layer with a thickness of 1 micron.
  • the photosensitive member produced according to the above processes (I) and (II) was evaluated in its chargeability and sensitivity using the tester for photosensitive member as illustrated in Fig. 15.
  • the sample of the photosensitive member produced (35) was put on the scanning table (37), and fixed by the shield cover (36).
  • the scanning table (37) was moved to the charged area (52), and a high electric power supplied from the direct high electric power (40) of +7.7 K V was applied to the charger (42) to generate corona discharge on the surface of the photosensitive member, and then the scanning table (37) was moved to the discharge area (51).
  • the surface potential of the corona discharged sample was sensed by the transparent electrode (48) to be indicated on the surface potential meter (49), and then put out on the recorder (50).
  • the photosensitive member of the above showed an excellent chargeability.
  • the shutter (47) was opened to irradiate the light from the halogen lump (43), which was reflected on the mirror (44), on the surface of the charged sample (35).
  • the irradiation was effected through the transparent electrode (48), and the change of the surface potential by the irradiation was put out on the recorder (50) as well as the electric current at the same time was sensed by the photo-electric current monitor (38).
  • the photosensitive member of the above showed a half-reduced exposure value E 1/2 of about 0.6 lux.sec for an initial surface potential (V O ) of -500 volt.
  • a drum type of a photosensitive member was made in the same manner as the Example 1 excepting that the electric power of 250 W, the flow ratio of C 2 H 4 of 300 sccm, and the flow ratio of H 2 of 650 sccm were used as the condition of the production for the. charge transporting layer, and the electric power of 250 W, SiH 4 of 180 sccm and H 2 of 500 sccm were used as the condition for the charge generating layer.
  • a simulation test for a copying process was made using a tester of drum type photosensitive member (not shown). There was obtained a stable static electric property even after the repeat of 50000 times of full copying process (charge - exposure - transferring and charge for removal - erasing).
  • the polyethylene membrane thus obtained was an insulator having an electric resistance of about 10 16 ohm cm.
  • the obtained photosensitive member had no photosensitivity and was charged up by several times use, which could not be applied to an electrophotography.
  • Example 1 Using the equipment in Example 1 as varying the conditions such as the plasma condition, plasma polymerizing polyethylene layers were produced. However, it was impossible to make an a-C layer having n 2 of less than 0.5 as well as one having n 6 of more than 0.5, when assuming that n 1 or n 5 is 1 (the layer was changed to give a layer having n 2 being more than 1). Even if such a layer could be produced, a charge generating layer could not be formed on the layer, or the polyethylene layers became so soft or sticky that they could not be used as materials for a photosensitive member.
  • a photosensitive member comprising an a-Si layer alone on an aluminum substrate was produced in a similar manner as in the Example 1, which a-Si layer was formed for 3.25 hours at the thickness of 6.5 micron meters.
  • the obtained photosensitive member had a half reduced-exposure value E 1/2 of about 2.7 lux.sec for an initial surface potential (Vo) of -100 V, and a sufficient chargeability could not be obtained at plus polarity.
  • the internal pressure of the reaction chamber (733) was adjusted to 0.6 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50mm, was preliminarily heated up to 200°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 50 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 1.5 hours, there was formed a charge transporting layer with a thickness of approximately 10 microns on the conductive substrate (752).
  • the ratio (n l :n 2 ) in the obtained a-C layer was 1:1.43.
  • the power application from the high frequency power source (739) was stopped for a time and the reaction chamber was vacuumized inside.
  • SiH 4 gas from No. 4 tank (704) and H 2 gas from No. 2 tank (702) were, under output pressure gage reading of 1 K g/cm 2 , led into the mass flow controllers (716) and (714). Then, the mass flow controllers were set so as to make SiH 4 flow at 90 sccm and H 2 flow at 210 sccm, and the gases were allowed into the reaction chamber. After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.
  • the circuit to the high frequency power source (739) was supplied and a 30 W power (frequency: 13.56 MHz) was applied to the power-applying electrode (736) to generate glow discharge. After 10 minutes of glow discharge, there was formed an a-Si:H charge generating layer with a thickness of 1 micron.
  • the mass flow controllers were set so as to make C 2 H 4 flow at 55 sccm, CH 4 flow at 100 sccm and H 2 flow at 120 sccm, and the gases were allowed into the reaction chamber (733). After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 0.8 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50mm, was preliminarily heated up to 250°C, and while the gas flows and the internal pressure were stabilized. it was connected to the high frequency power source (739) and 200 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 4 hours, there was formed a charge transporting layer with a thickness of approximately 6 p on the conductive substrate (752). The ratio (n 1 :n 2 ) in the obtained a-C layer was 1:7.8.
  • a charge generating layer was formed according to Example 2 (II) to give a photosensitive member.
  • This photosensitive member had an E 1/2 of 1.2 lux.sec. for an initial surface potential ( V o) of -520 volt.
  • V o initial surface potential
  • the mass flow controllers were set so as to make C 2 H 4 flow at 60 sccm, CH 4 flow at 60 sccm, and H 2 flow at 100 sccm, and the gases were allowed into the reaction chamber (733). After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 2.0 Torr.
  • the electrically conductive substrate (752) which was an cylindrical aluminum substrate of 2 x 50 x 50mm, was preliminarily heated up to 200°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 180 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 3 hours, there was formed a charge transporting layer with a thickness of approximately 5.5 microns on the conductive substrate (752).
  • the ratio (n l :n 2 ) in the obtained a-C layer was 1:1.22.
  • a charge generating layer was formed on the above a-C layer in the same manner as in Example 2(II) to give a photosensitive member.
  • reaction chamber (733) was vacuumized inside to a high level of approximately 10 -6 Torr, and then by opening No. 6 and No. 7 regulating valves (712) and (725), H 2 gas from No. 6 tank (706) under output pressure gage reading of 1 Kg/cm 2 , and stylene gas from No. 1 vessel (719) that was heated at about 20°C by No. 1 heater (722) were led into mass flow controllers (718) and (728). Then, the mass flow controllers were set so as to make H 2 flow at 30 sccm and stylene flow at 60 sccm, and the gases were allowed into the reaction chamber (733).
  • the internal pressure of the reaction chamber (733) was adjusted to 0.4 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50 mm, was preliminarily heated up to 150°C, and while the gas flows and the internal pressure were stabilized, it was connected to the low frequency power source (736) and 150 watts power (frequency: 30 KHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 40 minutes, there was formed a charge transporting layer with a thickness of approximately 9 p on the conductive substrate (752) .
  • the ratio (n 1 :n 2 ) of the obtained a-C layer was 1:0.61.
  • a charge generating layer was formed in the same manner as in Example 2(II) to give a photosensitive layer.
  • titanil phthalocyanine was deposited on an aluminum substrate under a vacuum of not more than 1 x 10 -5 Torr, and the boat temperature of 400 to 600°C.
  • the obtained titanyl phthalocyanine layer had a thickness of 600 angstrom.
  • a-C layer was formed in the same manner as in the process of Example 5 ( I ) to give a photosensitive member.
  • the charge transporting layer produced by the same manner as the above was formed on the charge generating layer made of amorphous Se-Te and Se-As having a thickness of 1.2 micron meter each.
  • the obtained photosensitive member had excellent properties for electrophotography.
  • the internal pressure of the reaction chamber (733) was adjusted to 1.6 Torr by the pressure controlling valve.
  • the electrically conductive substrate (752) which was an aluminum plate of 3 x 50 x 50mm, was preliminarily heated up to 270°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power sourse (739), which was preveously contacted with the selection switch (744) and 250 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 18 hours, there was formed a charge transporting layer with a thickness of approximately 15 p on the conductive substrate (752).
  • the hydrogen content of the obtained a-C layer was 26 atomic % based on the total amount of the carbon atoms and the hydrogen atoms from the analysis of metal ONH using EMGA-1300 (available from Horiba Seisakusho).
  • the ratio (n 1 : n 2 ) of the a-C layer was 1 : 47 from a solid NMR analysis, a FTIR analysis, and an elemental analysis.
  • the photosensitive member obtained showed high maximum charged potential of -1490 V, but E 1/2 of 1.3 K lux sec., which indicates that an a-C layer having a ratio (n 1 : n 2 ) of 1 : more than 20 cannot be used for a photosensitive member.
  • the internal pressure of the reaction chamber (733) was adjusted to 0.5 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50 mm, was preliminarily heated up to 250°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 100 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately four hours, there was formed a charge transporting layer with a thickness of approximately 6 microns on the conductive substrate (752).
  • the ratio of the number of unsaturated carbon atoms (n 3 ) bonding with hydrogen to the number of unsaturated carbon stoms (n 4 ) not bonding with hydrogen was 1 : 0.89.
  • the dark resistance of the layer was less than about 1 x 10 12 n.cm and the ratio of the dark resistance to the light resistance was more than 10 2 - 10 4 . Therefore, it is understandable that this plasma polymerized polyethylene layer can be used as a photosensitive member for electrography.
  • the power application from the high frequency power source (739) was stopped for a time and the reaction chamber was vacuumized inside.
  • SiH 4 gas from No. 3 tank (703) and H 2 gas from No. 2 tank (702) were, under output pressure gage reading of 1 K g/cm 2 , led into the mass flow controllers (715) and (714). Then, the mass flow controllers were set so as to make SiH 4 flow at 90 sccm and H 2 flow at 210 sccm, and the gases were allowed into the reaction chamber. After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.
  • the circuit to the high frequency power source (739) was supplied and a 30 W power (frequency: 13.56 MHz) was applied to the power-applying electrode (736) to generate glow discharge. After 10 minutes of glow discharge, there was formed an a-Si:H charge generating layer with a thickness of 1 micron.
  • a plasma polymerized polyethylene layer having a ratio of n3: n 4 of 1 : 0.18 with a thickness of 5.5.micron meter was obtained in the same manner as in Example 7 excepting that the flow rates of C 2 H 4 and H 2 were 100 sccm and 180 sccm respectively, the internal pressure of the reaction chamber was 1.2 Torr, applied power was 230 watts, and reaction time was 5 hours at the production of a-C layer.
  • the a-Si layer with a thickness of 1 micron meter was formed in the same manner as in Example 7.
  • the internal pressure of the reaction chamber (733) was adjusted to 1.5 Torr by the pressure controlling valve (745).
  • the electrically conductive substrate (752) which was an aluminum plate of 3 x 50 x 50 mm, was preliminarily heated up to 180°C , and while the gas flows and the internal pressure were stabilized, it was connected to the low frequency power source (741), which was previously contacted with the selection switch (744) and 120 watts power (frequency: 35 KHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 2 hours and 40 minutes, there was formed a charge transporting layer with a thickness of approximately 15 microns on the conductive substrate (752). After the layer-formation, the power applying was stopped, the control valve was closed, and then the reaction chamber (733) was sufficiently discharged.
  • the obtained a-C layer was analyzed with ONH analysis using EMGA-1300 (available from Horiba Seisakusho).
  • the content of the hydrogen atom in the a-C layer was 23 atomic % based on the total amount of the hydrogen atoms and the carbon atoms, and the ratio (n 3 : n 4 ) of the a-C layer was 1 : 5.2.
  • H 2 gas from No. I tank (701) and SiH 4 gas from No. 6 tank (706) were, under output pressure gage reading of 1 K g/cm 2 , led into the mass flow controllers (713) and (718). Then, the mass flow controllers were set so as to make H2 flow at 200 scc m and SiH 4 flow at 100 sccm, and the gases were allowed into the reaction chamber (733). After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 0.8 Torr.
  • the photosensitive member thus obtained showed a high maximum charged potential of -800 V, but a half-reduced exposure value E 1/2 of 17 lux.sec, which means the photosensitivity remarkably decreases in the case of the ratio (n 3 :n 4 ) being 1 : more than 4.
  • the internal pressure of the reaction chamber (733) was adjusted to 0.8 Torr.
  • the electrically conductive substrate (752), an aluminum plate of 2 x 50 x 50mm, was preliminarily heated up to 200°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 85 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 1.2 hours, there was formed a charge transporting layer with a thickness of approximately 10 microns on the conductive substrate (752).
  • the ratio (n 3 :n 4 ) of the obtained a-C layer was 1:1.27.
  • the power application from the high frequency power source (739) was stopped for a time and the reaction chamber was vacuumized inside.
  • the circuit to the high frequency power source (739) was supplied and a 30 W power (frequency: 13.56 MHz) was applied to the power-applying electrode (736) to generate glow discharge. After 10 minutes of glow discharge, there was formed an a-Si:H charge generating layer with a thickness of 1 micron.
  • the mass flow controllers were set so as to make C 2 H 4 flow at 45 sccm , CH4 flow at 100 sccm, and H2 flow at 120 accm, and the gases were allowed into the reaction chamber (733). After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50mm, was preliminarily heated up to 250°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 250 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 5 hours, there was formed a charge transporting layer with a thickness of approximately 6 p on the conductive substrate (752). The ratio (n 3 :n 4 ) in the obtained a-C layer was 1:0.52.
  • a charge generating layer was formed in the same manner as in Example 2(11) to give a photosensitive member.
  • the mass flow controllers were set so as to make C 2 H 4 flow at 60 4 sccm, CH 4 flow at 60 sccm, and H 2 flow at 100 sccm, and the gases were allowed into the reaction chamber (733). After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 1.5 Torr.
  • the ratio (n 3 :n 4 ) of the obtained a-C layer was 1:2.1.
  • a charge generating layer was formed on the a-C layer in the same manner as in Example 2(I I ) to give a photosensitive member.
  • reaction chamber (733) was vacuumized inside to a high level of approximately 10 -6 Torr, and then by opening No. 6 and.No. 7 regulating valves (712) and (725), H 2 gas from No. 6 tank (706) under output pressure gage reading of 1 Kg/cm 2 , and stylene gas from No. 1 vessel (719) that was heated at about 50°C by No. 1 heater (722) were led into mass flow controllers (718) and (728). Then, the mass flow controllers were set so as to make H 2 flow at 30 sccm and stylene flow at 50 sccm, and the gases were allowed into the reaction chamber (733).
  • the internal pressure of the reaction chamber (733) was adjusted to 0.5 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50 mm, was preliminarily heated up to 150°C, and while the gas flows and the internal pressure were stabilized, it was connected to the low frequency power source (736) and 150 watts power (frequency: 30 K H z) was applied to the power-applying electrode (736). After plasma polymerization for approximately 50 minutes, there was formed a charge transporting layer with a thickness of approximately 8 microns on the conductive substrate (752).
  • the ratio ⁇ n 3 :n 4 ) of the a-C layer was 1:0.33.
  • a charge generating layer was formed on the a-C layer according to the same manner as in Example 2(11) to give a photosensitive member.
  • titanyl phthalocyanine was deposited on an aluminum substrate under a vacuum of not more than 1 x 10 -5 Torr, and a boat temperature of 400 to 600°C.
  • the obtained titanyl phthalocyanine layer had a thickness of 600 angstrom.
  • an a-C layer was formed in the same manner as in the process of Example 11 (I) to give a photosensitive member.
  • the charge transporting layer produced by the same manner as the above was formed on the charge generating layer made of amorphous Se-Te and Se-As having a thickness of 1.2 micron meter each.
  • the obtained photosensitive member had excellent properties for electrophotography.
  • the internal pressure of the reaction chamber (733) was adjusted to 0.5 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50 mm, was preliminarily heated up to 250°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 100 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately four hours, there was formed a charge transporting layer with a thickness of approximately 6 microns on the conductive substrate (752).
  • the ratio of the number of saturated carbon atoms (n 5 ) to the number of saturated carbon atoms (n 6 ) not bonding with hydrogen (n 5 :n 6 ) was 1 : 0.29.
  • the dark resistance of the layer was less than about 5 x 10 12 ⁇ . cm and the ratio of the dark resistance to the light resistance was more than 10 - 10 4 . Therefore, it is understandable that this plasma polymerized polyethylene layer can be used as a photosensitive member for electrophotography.
  • the power application from the high frequency power source (739) was stopped for a time and the reaction chamber was vacuumized inside.
  • the circuit to the high frequency power source (739) was supplied and a 30 W power (frequency: 13.56 MHz) was applied to the power-applying electrode (736) to generate glow discharge. After 10 minutes of glow discharge, there was formed an a-Si:H charge generating layer with a thickness of 1 micron.
  • the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.
  • the electrically conductive substrate (752), an aluminum plate of 2 x 50 x 50mm, was preliminarily heated up to 200°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 90 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 1.5 hours, there was formed a charge transporting layer with a thickness of approximately 9 microns on the conductive substrate (752).
  • the ratio (n 5 :n 6 ) of the obtained a-C layer was 1:0.21.
  • the power application from the high frequency power source (739) was stopped for a time and the reaction chamber was vacuumized inside.
  • SiH 4 gas from No. 4 tank (704) and H 2 gas from No. 2 tank (702) were, under output pressure gage reading of 1 K g/cm 2 , led into the mass flow controllers (716) and (714). Then, the mass flow controllers were set so as to make SiH 4 flow at 90 sccm and H 2 flow at 210 sccm, and the gases were allowed into the reaction chamber. After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.
  • the circuit to the high frequency power source (739) was supplied and 30 W power (frequency: 13.56 MHz) was applied to the power-applying electrode (736) to generate glow discharge. After 10 minutes of glow discharge, there was formed an a-Si:H charge generating layer with a ' thickness of 1 micron.
  • the mass flow controllers were set so as to make C 2 H 4 flow at 60 sccm, CH 4 flow at 100 sccm and H 2 flow at 120 accm, and the gases were allowed into the reaction chamber (733). After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 0.8 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50mm, was preliminarily heated up to 250°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 200 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 4 hours, there was formed a charge transporting layer with a thickness of approximately 6 p on the conductive substrate (752). The ratio (n S :n 6 ) of the a-C layer was 1:0.39.
  • a charge generating layer was formed on the a-C layer in the same manner as in Example 2(II) to give a photosensitive member.
  • the mass flow controllers were set so as to make C 2 H 4 flow at 55 sccm, CH 4 flow at 60 sccm, and H 2 flow at 100 sccm, and the gases were allowed into the reaction chamber (733). After the respective flows had stabilized, the internal pressure of the reaction chamber (733) was adjusted to 1.5 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50mm, was preliminarily heated up to 250°C, and while the gas flows and the internal pressure were stabilized, it was connected to the high frequency power source (739) and 200 watts power (frequency: 13.56 MHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 5 hours, there was formed a charge transporting layer with a thickness of approximately 5 microns on the conductive substrate (752).
  • the ratio (n5:n6) of the obtained a-C layer was 1:0.18.
  • a charge generating layer was formed on the a-C layer in the same manner as in Example 2(II) to give a photosensitive member.
  • reaction chamber (733) was vacuumized inside to a high level of approximately 10 -6 Torr, and then by opening No. 6 and No. 7 regulating valves (712) and (725), H 2 gas from No. 6 tank (706) under output pressure gage reading of 1 K g/c m2 , and stylene gas from No. 1 vessel (719) that-was heated at about 50°C by No. 1 heater (722) were led into mass flow controllers (718) and (728). Then, the mass flow controllers were set so as to make H 2 flow at 30 sccm and stylene flow. at 50 sccm, and the gases were allowed into the reaction chamber (733).
  • the internal pressure of the reaction chamber (733) was adjusted to 0.3 Torr.
  • the electrically conductive substrate (752) which was an aluminum plate of 2 x 50 x 50 mm, was preliminarily heated up to 150°C, and while the gas flows and the internal pressure were stabilized, it was connected to the low frequency power source (736) and 150 watts power (frequency: 30 KHz) was applied to the power-applying electrode (736). After plasma polymerization for approximately 35 minutes, there was formed a charge transporting layer with a thickness of approximately 8 microns on the conductive substrate (752).
  • the ratio (n 5 :n 6 ) of the obtained a-c layer was 1:0.15.
  • a charge generating layer was formed on the a-C layer in the same manner as in Example 2(II) to give a photosensitive member.
  • titanyl phthalocyanine was deposited on an aluminum substrate under a vacuum of not more than 1 x 10 -5 Torr, and a boat temperature of 400 to 600°C.
  • the obtained titanyl phthalocyanine layer had a thickness of 600 angstrom.
  • an a-C layer was formed in the same manner as in the process of Example 17 ( I ) to give a photosensitive member.
  • the charge transporting layer produced by the same manner as the above was formed on the charge generating layer made of amorphous Se-Te and Se-As having a thickness of 1.2 micron meter each.
  • the obtained photosensitive member had excellent properties for an electrophotography.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Photoreceptors In Electrophotography (AREA)
EP19870105274 1986-04-09 1987-04-09 Membre photosensible composé d'une couche transporteuse de charge et d'une couche génératrice de charge Withdrawn EP0241033A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP8313086A JPS62238571A (ja) 1986-04-09 1986-04-09 感光体
JP83133/86 1986-04-09
JP83131/86 1986-04-09
JP8313186A JPS62238572A (ja) 1986-04-09 1986-04-09 感光体
JP83130/86 1986-04-09
JP8313386A JPS62238574A (ja) 1986-04-09 1986-04-09 感光体

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EP0241033A1 true EP0241033A1 (fr) 1987-10-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3451066A1 (fr) * 2017-09-01 2019-03-06 Canon Kabushiki Kaisha Élément photosensible électrophotographique et appareil électrophotographique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3956525A (en) * 1973-06-20 1976-05-11 Matsushita Electric Industrial Co., Ltd. Method of improving the reusability of an electrophotographic photosensitive plate
US4366208A (en) * 1979-10-23 1982-12-28 Tokyo Shibaura Denki Kabushiki Kaisha Process for forming photoconductive organic film
DE3430940A1 (de) * 1983-08-23 1985-03-14 Sharp K.K., Osaka Photorezeptor fuer die elektrophotographie
EP0151754A2 (fr) * 1984-02-14 1985-08-21 Energy Conversion Devices, Inc. Procédé de fabrication d'un élément photoconducteur

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3956525A (en) * 1973-06-20 1976-05-11 Matsushita Electric Industrial Co., Ltd. Method of improving the reusability of an electrophotographic photosensitive plate
US4366208A (en) * 1979-10-23 1982-12-28 Tokyo Shibaura Denki Kabushiki Kaisha Process for forming photoconductive organic film
DE3430940A1 (de) * 1983-08-23 1985-03-14 Sharp K.K., Osaka Photorezeptor fuer die elektrophotographie
EP0151754A2 (fr) * 1984-02-14 1985-08-21 Energy Conversion Devices, Inc. Procédé de fabrication d'un élément photoconducteur

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF APPLIED POLYMER SCIENCE, vol. 17, 1973, New York H.KOBAYASHI et al. "Formation of an Amorphous Powder During the Polymerization of Ethylene in a Radio-Frequency Discharge" pages 885-892 * Page 885 ; page 888, line 43- page 891 * *
PATENT ABSTRACTS OF JAPAN, unexamined applications, section P, vol. 8, no. 137, June 26, 1984 THE PATENT OFFICE JAPANESE GOVERNMENT page 128 P 282 * JP - A - 59-38 753 ( TOKYO SHIBAURA DENKI K.K. ) * *
PATENT ABSTRACTS OF JAPAN, unexamined applications, section P, vol. 9, no. 86, April 16, 1985 THE PATENT OFFICE JAPANESE GOVERNMENT page 29 P 346 * JP - A - 59-214 859 ( SANYO DENKI K.K. ) * *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3451066A1 (fr) * 2017-09-01 2019-03-06 Canon Kabushiki Kaisha Élément photosensible électrophotographique et appareil électrophotographique
US10338486B2 (en) 2017-09-01 2019-07-02 Canon Kabushiki Kaisha Electrophotographic photosensitive member and electrophotographic apparatus

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