US3904409A - Photoconductive body for electrophotography and the method of manufacturing the same - Google Patents
Photoconductive body for electrophotography and the method of manufacturing the same Download PDFInfo
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- US3904409A US3904409A US804142A US80414269A US3904409A US 3904409 A US3904409 A US 3904409A US 804142 A US804142 A US 804142A US 80414269 A US80414269 A US 80414269A US 3904409 A US3904409 A US 3904409A
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- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 105
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims description 74
- 238000000576 coating method Methods 0.000 claims description 74
- 239000000126 substance Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 230000001747 exhibiting effect Effects 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims 3
- 229910052946 acanthite Inorganic materials 0.000 claims 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 30
- 230000035945 sensitivity Effects 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 13
- 238000005036 potential barrier Methods 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 79
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 25
- 239000008187 granular material Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 239000010949 copper Substances 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 239000000370 acceptor Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 230000005532 trapping Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910018219 SeTe Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000011591 potassium Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- FESBVLZDDCQLFY-UHFFFAOYSA-N sete Chemical compound [Te]=[Se] FESBVLZDDCQLFY-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
Classifications
-
- 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
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/142—Inert intermediate layers
- G03G5/144—Inert intermediate layers comprising inorganic material
-
- 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
-
- 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
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0384—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including other non-monocrystalline materials, e.g. semiconductor particles embedded in an insulating material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S148/00—Metal treatment
- Y10S148/064—Gp II-VI compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S148/00—Metal treatment
- Y10S148/12—Photocathodes-Cs coated and solar cell
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- ABSTRACT A photoconductive body for electrophotography and methods of manufacturing the same.
- the present invention provides a high sensitivity photoconductive powder of CdS or CdSe by activating powder particles with a surface treatment to provide a potential barrier susceptible to the light, to improve trap level of the surface of the particles and to increase the quantum cfficiency of the particles.
- An object of this invention is to obtain a highsensitivity, high-resolution power, and highly durable electrophotographic photosensitive plate best suited for use in methods for'electrophotography, particularly those described in US. applications Ser. Nos. 563.899 filed July 8, i966 and 571,538 filed Aug. 10, 1966.
- the above-mentioned methods for electrophotography feature the formation of a high contrast electro static image by applying a uniform primary electrical charge to the insulating surface of a photosensitive plate having a highly insulating layer in close adherence thereto, by removing the said charge by either applying an electrical charge opposite in polarity to that of the primary charge or by AC corona discharge simulta neously with an exposure, and then by illuminating the entire surface with light.
- This'proeess is superior to the method known as the Carlson method in sensitivityQin durability of photosensitive plate for repeated use, and in economy.
- the photosensitive plate used in this process comprises a highly-insulating layer, a photoconductive layer, and an electrically conductive or insulating base.
- a photosensitive plate comprising four layers including one more insulating layer on a electrically conductive base, or a'photosensitive plate including layers above and/or below the photoconductive layer transparent to radiation to which the:photoconductive layer is sensitive, can also be'used.
- the performance such as image quality. and sensitivity, is determined depending on the photoconductive material and plate structural condition.
- semiconductors such as amorphous selenium, which have a sufficiently high resistance, that is, have an insulation of more than 10 Q-cm in darkness, are required in the photosensi tive plate in order to maintain electrostatic charges on its surface. Therefore, highly sensitive layers having'the distinct characteristic of a p-type semiconductor or an n-type semiconductor as a result of mixing highly sensitive photoconductive bodies such as CdS, CdSe, crystalline, Se, SeTe. Te or impurities and forming donors or acceptors, cannot be used practically because they have a large dark decay or attenuation.
- the photosensitive plate has an insulating layer on its surface and, based on some internal physical phenomena not yet clear, such highly sensitive substances such-as CdS and crystalline Se can be employed as the photosemiconductors, that is, mixing of impurities can be made with more freedom.
- This enables easier selection of p-type semiconductors and n-type semiconductors sensitizing materials.
- photosensitive plates far superior in sensitivity to those of Carlson process can be obtained by using semiconductors of either type. i
- more-speedy and more-sensitive photosensitive plates are required at present. This invention was developed to meet this requirement.
- a photosensitive layer made by bonding pulverized photoconductive substance for electrophotograpy with a resin the photoconductive characteristic is determineddepending mainly on the potential barrier that exists on-the surface of the powder granules and between the'granules. Therefore, in order to obtain a highly sensitive photosensitive layer, such powder, whose granule surface potential barrier changes rapidly with incident light, must be used.
- the photoconductive characteristic is formed by the trap ping of the exciting carriers as determined by the trap level within the photosensitive layer.
- Such trap level exists mostly on the surface of the powdered particles so that the suitable treatment of the surface of the particles would produce new trapping ability.
- This invention attains the purpose of providing high sensitivity powder granules of sulfides or selenide or cadmium by activating the powder granules with a surface treatment by a novel method.
- the conventional ideas of quantum efficiency that have been applied to the so-called photoconductive cells that used monocrystals or sintered layers are not applicable to photosensitive plates for electrophotography, because the quantum efficiency of these photoconductive cells is measured by conducting photoelectric current into an external circuit through an electrode attached to the photoconductive cell, the electrode having a socalled ohmic contact, whereas in a photosensitive plate for electrophotography an electrode having an ohmic contact is not used and the quantum efficiency must be considered in the interior of the photosensitive layer.
- the conventional method to increase the life of the exciting carrier used in sensitizing the photoconductive cell results in a quantum efficiency of at most 1.
- a drastic increase in the sensitivity of the photosensitive .layer may be expected by applying the said mechanism ,to the photosensitive layer to increase the quantum efficiency of the photosensitive layer to a value for larger than l.
- n-p-n hook transistor This is an n-pn junction having a thin p-type layer between n-type layers.
- the 2-11 junction becomes. for example, forward biased and the n-p junction becomes reverse biased.
- the intermediate thin p-type layer serves as the so-called potential barrier to electrons.
- the positive hole and electron produced are separated from each other by the strong electric field of reverse bias, and the electron moves towards the n-type layer and the positive hole to the p-type layer.
- the positive hole that has moved towards the p-type layer is held by the valence bond of the p-type layer and main tained in that section.
- the 1)- type layer corresponds to the flood gate and the action by which the incident light sends positive holes into the ptype layer corresponds to opening the flood gate. As a result. more water flows out of the dam the larger the opening of the flood gate.
- Y is quantum efficiency, o e the electroconductivity of the n-type layer on the forward bias side.
- Lpe the diffusion distance of positive holes within the said layer.
- w the thickness of the said layer. Therefore, when 0" e.Lpe is far greater than 0' pm. the quantum efficiency is far greater than I.
- An object of this invention is to increase the sensitivity of photosensitive plates for electrophotography, particularly the type of photosensitive plate comprising three layers and utilizing the persistent internal polarization. based on the above-mentioned viewpoint.
- At least one layer ofp-njunction is employed in this invention as photoconductive fine particles.
- the external ptype semiconductor is a barrier to electrons so as to increase the dark resistance of the photosensitive layer and to retain surface potential, and the acceptor compensating the free electrons at the i-layer plays the role of trapping positive holes produced by the incident light rays. Since the i-layer is in close contact with the barrier of the p-layer, the positive charge of the trapped positive holes will substantially lower the barrier so that the barrier of the player, the positive charge of the trapped positive holes will substantially lower the barrier so that the barrier of the p-layer is varied very sensitively and photoconduetivity becomes very sensitive.
- FIG. I is a cross sectional view of a photosensitive member having a photoconductive layer formed by dispersing a photoconductive powder of the present invention into a binder;
- FIG. 2 is a cross sectional view of one example of a photoconductive powder of the present invention.
- FIG. 3 is a characteristic curve of the photosensitive plate as shown in FIG. 1.
- FIG. I shows a photosensitive plate comprising highly insulating transparent film (polyester, fluorine resin. etc. having a resistivity of Q-cm) I, an electrically conductive or insulating base 2, and a photocnductive layer 3 formed between the above-mentioned film I and the base 2 by binding the abovementioned photoconductive fine particles with a binder 4 such as epoxy resin or vinyl acetate.
- a binder 4 such as epoxy resin or vinyl acetate.
- a junction similar to a p-n-p or n-p-n junction is formed towards the direction in which an electrical field is applied and an effect similar to a p-n-p or n-p-n diode is produced. Electrical charge flows rapidly when the photosensitive plate is exposed to light under a certain critical voltage and the electrical charge persists even when a voltage drop has occurred.
- the particles thereof are sintered in a suitable circumference to form Cd vacancies on the surface of the particles or suitably surface treated to add Cu or Ag as an acceptor on the surface, and, by compensating free electrons from donors on the surface, a semiinsulating ilayer is formed externally of n-type layer.
- the particles thereof are sintered in a suitable circumference to make the same Cd rich or surface treated suitably so as to add halogen, indium, gallium etc. on the surface to form an i-layer.
- the dried block was broken into pieces the size of beans, placed in a quartz tube, and sintered for 30 minutes at 600C in nitrogen ambient atmosphere.
- the sintered product was completely washed with pure water by repeated tilt washing, dried, and then passed through a sieve of 325 mesh to obtain a bright yellow powder.
- Solution B 0.2 g of silver nitrate was dissolved in a small amount of water. 100 cc of boiling water was added to the solution followed by the addition of 0. 166g of Rochell salt. The solution was boiled for some time. The grey turbid liquid thus obtained was filtered while hot, and the filtrate was used as the solution B.
- EXAMPLE 2 In a method for preparing photoconductive powder having a p-type surface layer by making copper adhere to the surface of n-type CdS powder by reduction,
- the precipitate was washed completely with pure water by tilt washing and then completely dried in a vacuum desiccator at 60C. After drying, the precipitate was crushed by a ball mill for about 5 hours.
- the powder obtained in (4) was placed in a quartz tube and sintered for 60 minutes at 600C in nitrogen ambient atmosphere. Then activated powder photoconductive substance was obtained.
- EXAMPLE 3 ln a method for preparing photoconductive powder having a p-type surface layer by substituting Cd of the surface of powder granule of n-type CdS with copper by means of substitution reaction, to the powder obtained by the steps (1) through (3) of the Example l was added a solution prepared by dissolving 0.1 cc of sulfuric acid of 96 percent or more concentration and 0.002 g of copper sulfate in 200 cc of pure water. The mixture was subjected to agitation for about 10 hours in a closed-type rotary agitator. washed completely with pure water by tilt washing and dried at about 100C. The dried powder was placed in a quartz tube and sintered for minutes at 600C in nitrogen ambient atmosphere. Activated photoconductive powder was obtained.
- EXAMPLE 5 ZnO for electrophotography available on the market was treated in 40-atmospheric-pressure hydrogen at 700C to increase the electrical conductivity.
- the ZnO granules were dropped in vacuum continuously from a container maintained at about C and evaporated with Se. This evaporation was repeated several times. Then the granules were dispersed into acrylic resin, and the suspension was applied to a metal plate to a thickness of about 50a. The metal plate was then charged by negative corona discharge and an optical image was projected on the metal plate. An electrostatic pattern having a contrast of 300 V was obtained.
- EXAMPLE 6 In a method for preparing n-p-n type photoconductive substance powder of CdS or CdSe, powder having a p-type surface layer obtained by the methods described in the Examples 1 through 4 was mixed with pure water. The mixture received filtration. A small amount of the aqueous solution of a fusing agent (for example. a 0.l mol aqueous solution of cadmium chloride and 1.0 mol aqueous solution of ammonium chloride) was poured on the precipitate to moisten it. and the excessive solution was suction-filtered. The powder was dried. and then sintered for 60 minutes at 600C in nitrogen ambient atmosphere, and n-p-n-type photoconductive powder was obtained.
- a fusing agent for example. a 0.l mol aqueous solution of cadmium chloride and 1.0 mol aqueous solution of ammonium chloride
- EXAMPLE 7 In a method for preparing Hz-type photoconductive powder of CdS.
- n-type pure CdS powder was added several percent in weight of copper sulfide.
- the mixture was ground completely in a ball mill. and then sintered for 2 hours at a temperature within the range of about 700 to 900C in nitrogen ambient atmosphere to obtain p-type powder.
- the sintered product was first broken into pieces in a mortar and then ground for 24 hours in a ball mill. screened into classes, both the coarse powder and extremely fine powder were removed, and granules within the range of 1 to 20p. were obtained. These granules were sintered for minutes in a vacuum at 600 to 800C. An n-type layer was formed on the surface of p-type granules having sulfur vacancies.
- the powder was mixed with pure water and filtered. and moistened with a small amount of aqueous solution containing only a halide fusing agent or salts of indium, potassium. etc.. again filtered and dried completely, and sintered for about 2 hours at a temperature higher than its melting point in inactive ambient atmosphere. Then a more firm n-type layer was formed.
- EXAMPLE 8 In a method for preparing p-n-p-type photoconductive powder, copper or silver precipitate was adhered to the surface of the p-n-type powder obtained in the Example 7 by means of the method described in the Example through 4 and by subjecting the powder to heat diffusion or substitution with Cd.
- EXAMPLE 9 In a method for preparing n-i-p-type photoconductive powder, Examples 1 and 2 are practiced, except that the amounts of silver and copper are reduced to about less than one-tenth, and the powder is obtained. To 10 g of the obtained powder is added a solution of 30 mg Cu CN, 45 mg of Na CN dissolved in 20 cc pure water to obtain a mixture, which is agitated in a bath of C about 20 minutes. After tilt filtering. it is dried to obtain a Cu S layer of p-type semiconductivity on the surface of the particles.
- EXAMPLE 10 In a method for preparing n-i-p-type photoconductive powder, instead of the solution including Cu CN and NaCN in Example 9, a solution of 30 mg AgNO and 0.l cc concentrated nitric acid is used, by which a ptype layer of Ag- S is formed on the surface of the particles to obtain n-i-p type powder.
- This mixture was transferred on to a smooth aluminum leaf installed on a plane plate and leveled rapidly to a thickness of about microns.
- a Mylar insulation film about 25 microns in thickness was placed on the above-mentioned mixture, using a thin metal sheet frame as the spacer. Then using a metal rod having a wedge-like cross section, the mixture was squeezed through the Mylar insulation film, by utilizing the edge of the wedge.
- the entire body was placed in the thermostatic oven. left here for 3 hours at 70C, to harden the resin.
- the sensitivity of the three layered photosensitive plate of this invention mentioned above was compared with that of a photosensitive plate of the same composition but prepared by using photoconductive cadmium sulfide of the conventional method and by employing the same method as mentioned above.
- the photosensitive plate is positively charged to a surface potential of+l ,500V by corona discharge in an illuminated or dark place according to the electrophotographic process mentioned previously. Then, while projecting an optical image onto the photosensitive plate to form an electrostatic latent image, a corona discharge of about the same magnitude and opposite in polarity is applied to the plate to charge it negatively. or an AC corona is applied to remove the electric charge, and then the entire photosensitive plate is exposed to light.
- the sensitivity of the photosensitive plate wasjudged on the minimum amount of exposure required to obtain a latent image having sufficiently good contrast.
- the result obtained was i Lax.- sec for the electrophotographic plate of this invention, while the result for the conventional plate was foundto be times as large, i.e. 5 Lux.sec. Therefore, this invention is very advantageous in improving speed in an electrophotographic copying machine, in compactizing the machine size due to simplification of the light source, and in cost reduction.
- FIG. 3 shows the results of the measurement of the thermal excitation current of the photoconductive substance powder of this invention (the one shown in Example 8) and conventional powder (made by adding 0.003g of cupric oxide to lOg of CdS by sintering, using a fusing agent, and by treating the sintered product in sulfur vapor).
- the above-mentioned two kinds of photoconductive powder were mixed in weight ratio of 100 14 and the mixture was bound by epoxy resin containing an adequate amount of hardening agent. This mixture was transferred onto the metal electrodes, evaporated onto a sheet of glass at an interval of 0.5 mm and a width of 5 mm, dried for 3 hours at 70C, and then hardened to form a photosensitive layer.
- the photosensitive layer first received sufficient light irradiation from the glass plate side through the interelectrode gaps. The light was then interrupted and the specimen was kept in the dark. A voltage of 100V was applied across the electrodes and the temperature was decreased gradually from the nitrogen temperature at a constant rate, and the current that flowed through the specimen was measured at each temperature. The peak of the curve shows the trap level of the photoconductive substance. As clearly shown in the curve a, the photoconductive substance of this invention has a newly formed trap level compared with the conventional one (curve b). This is considered one of the causes of the excellent effect the photoconductive substance displayed when used as an electrophotographic photosensitive plate.
- This invention utilizes the H1 reversal phenomenon of granule surfaces, which occurs as a matter of course in manufacturing electrophotographic photoconductive substances in accordance with the invention.
- the idea of this invention contains various kinds of variations and is also applicable to plates that have no insulating layer on the surface.
- This invention is applicable to such materials as semiconductors other than the above-mentioned CdS and CdSe, such as ZnO. CdTe, ZnS, ZnSe, Su- O. GeS, Ge, Se. Bi S GaAs, and PbS which are known. to the use of components for the p-region and n-region which differ from each other, and to substances which are within the technical range of this invention.
- a photoconductive powder comprising a photoconductive core and a first photoconductive coating, said core exhibiting n-type semiconductivity. said first coating covering said core and exhibiting p-type semiconductivity.
- a photosensitive'member comprising the photoconductive powder claimed in claim 1 and a binder therefor.
- the photosensitive member claimed in claim 2 in which the photosensitive member is a photoconductive layer and including further an overlying insulative layer.
- Inorganic photoconductive powder comprising a photoconductive core, a first photoconductive coating covering the core and a second photoconductive coating covering the first coating, the core and the second coating each exhibiting the same type of conductivity selected from the group consisting of n-type semiconductivity and p-type semiconductivity and the first coating exhibiting a type of conductivity different from that of the core and the second coating and selected from the group consisting of n-type semiconductivity and p-type semiconductivity.
- a photosensitive member comprising the photoconductive powder claimed in claim 5 and a binder therefor.
- a photosensitive member comprising the photoconductive powder claimed in claim 6 and a binder therefor.
- the photosensitive member claimed in claim 7 in which the photosensitive member is a photoconductive layer and including further an overlying insulative layer.
- the photosensitive member claimed in claim 8 in which the photosensitive member is a photoconductive layer and including further an overlying insulative layer.
- Inorganic photoconductive powder comprising a photoconductive core, a first photoconductive coating covering the core and a second photoconductive coating covering the first coating.
- the first coating exhibiting positively introduced i-type semi-insulation and the core and the second coating each exhibiting a different type of conductivity selected from the group consisting of n-type semiconductivity and p-type semiconductivity.
- the core comprises CdS.
- the first coating comprises CdS and the second coating comprises Cu S. the second coating being formed on the first coating by chemical substitution reaction.
- a photosensitive member comprising the photo conductive powder claimed in claim 11 and a binder therefor.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Photoreceptors In Electrophotography (AREA)
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Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP43015287A JPS4910709B1 (de) | 1968-03-08 | 1968-03-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3904409A true US3904409A (en) | 1975-09-09 |
Family
ID=11884619
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US804142A Expired - Lifetime US3904409A (en) | 1968-03-08 | 1969-03-04 | Photoconductive body for electrophotography and the method of manufacturing the same |
Country Status (4)
Country | Link |
---|---|
US (1) | US3904409A (de) |
JP (1) | JPS4910709B1 (de) |
DE (1) | DE1911334B2 (de) |
NL (1) | NL6903538A (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4043813A (en) * | 1973-06-06 | 1977-08-23 | Bell & Howell Company | Photoconductive particles of zinc oxide |
US4093777A (en) * | 1974-10-10 | 1978-06-06 | Bayer Aktiengesellschaft | Coated stabilized cadmium chalcogenide pigments |
US4098609A (en) * | 1975-07-07 | 1978-07-04 | Bell & Howell Company | Method of making improved photoconductive particles |
US5128064A (en) * | 1989-04-18 | 1992-07-07 | Wisconsin Alumni Research Foundation | Cadmium sulfide membranes |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5646242A (en) * | 1979-09-19 | 1981-04-27 | Canon Inc | Electrophotographic photoconductive material |
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US2844640A (en) * | 1956-05-11 | 1958-07-22 | Donald C Reynolds | Cadmium sulfide barrier layer cell |
US2876202A (en) * | 1954-12-01 | 1959-03-03 | Rca Corp | Photoconducting powders and method of preparation |
US2908588A (en) * | 1957-03-15 | 1959-10-13 | Rca Corp | Zinc sulfide-coated phosphor particles, phosphor screen, and method of making screen |
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US3374108A (en) * | 1964-06-18 | 1968-03-19 | Kewanee Oil Co | Formation of barrier layers in cadmium sulfide solar cells |
US3379527A (en) * | 1963-09-18 | 1968-04-23 | Xerox Corp | Photoconductive insulators comprising activated sulfides, selenides, and sulfoselenides of cadmium |
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- 1968-03-08 JP JP43015287A patent/JPS4910709B1/ja active Pending
-
1969
- 1969-03-04 US US804142A patent/US3904409A/en not_active Expired - Lifetime
- 1969-03-06 DE DE19691911334 patent/DE1911334B2/de active Granted
- 1969-03-07 NL NL6903538A patent/NL6903538A/xx unknown
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US2876202A (en) * | 1954-12-01 | 1959-03-03 | Rca Corp | Photoconducting powders and method of preparation |
US2844640A (en) * | 1956-05-11 | 1958-07-22 | Donald C Reynolds | Cadmium sulfide barrier layer cell |
US2908588A (en) * | 1957-03-15 | 1959-10-13 | Rca Corp | Zinc sulfide-coated phosphor particles, phosphor screen, and method of making screen |
US3041166A (en) * | 1958-02-12 | 1962-06-26 | Xerox Corp | Xerographic plate and method |
US3060134A (en) * | 1959-03-03 | 1962-10-23 | New Jersey Zinc Co | Photoconductive zinc oxide pigment |
US3251714A (en) * | 1961-07-13 | 1966-05-17 | Philips Corp | Method of preparing a cadmium oxide photoconductor |
US3162526A (en) * | 1961-10-26 | 1964-12-22 | Grace W R & Co | Method of doping semiconductor materials |
US3351516A (en) * | 1962-10-13 | 1967-11-07 | Bayer Ag | Photoconductive structural element and process of manufacturing same |
US3307983A (en) * | 1963-03-12 | 1967-03-07 | Philips Corp | Method of manufacturing a photosensitive device |
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US3374108A (en) * | 1964-06-18 | 1968-03-19 | Kewanee Oil Co | Formation of barrier layers in cadmium sulfide solar cells |
US3312547A (en) * | 1964-07-02 | 1967-04-04 | Xerox Corp | Xerographic plate and processes of making and using same |
US3568306A (en) * | 1965-09-25 | 1971-03-09 | Matsushita Electric Ind Co Ltd | Method of making photovoltaic device by electroplating |
US3541028A (en) * | 1965-09-29 | 1970-11-17 | Fuji Photo Film Co Ltd | Photoconductive insulating materials |
US3449148A (en) * | 1966-06-30 | 1969-06-10 | Texas Instruments Inc | Formation of electron barriers on phosphor particles |
US3560398A (en) * | 1966-12-02 | 1971-02-02 | Texas Instruments Inc | Phosphors for color display systems |
US3519480A (en) * | 1967-01-13 | 1970-07-07 | Eastman Kodak Co | Process for treating photoconductive cadmium sulfide layers |
US3595646A (en) * | 1967-08-22 | 1971-07-27 | Katsuragawa Denki Kk | Method of treating photoconductors of the cadmium series to form electrophotosensitive material manifesting persistent internal polarization |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4043813A (en) * | 1973-06-06 | 1977-08-23 | Bell & Howell Company | Photoconductive particles of zinc oxide |
US4093777A (en) * | 1974-10-10 | 1978-06-06 | Bayer Aktiengesellschaft | Coated stabilized cadmium chalcogenide pigments |
US4098609A (en) * | 1975-07-07 | 1978-07-04 | Bell & Howell Company | Method of making improved photoconductive particles |
US5128064A (en) * | 1989-04-18 | 1992-07-07 | Wisconsin Alumni Research Foundation | Cadmium sulfide membranes |
Also Published As
Publication number | Publication date |
---|---|
NL6903538A (de) | 1969-09-10 |
JPS4910709B1 (de) | 1974-03-12 |
DE1911334A1 (de) | 1969-10-02 |
DE1911334B2 (de) | 1977-02-24 |
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