US2876202A - Photoconducting powders and method of preparation - Google Patents

Photoconducting powders and method of preparation Download PDF

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US2876202A
US2876202A US472354A US47235454A US2876202A US 2876202 A US2876202 A US 2876202A US 472354 A US472354 A US 472354A US 47235454 A US47235454 A US 47235454A US 2876202 A US2876202 A US 2876202A
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powder
photoconducting
cadmium
firing
powders
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Charles J Busanovich
Soren M Thomsen
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RCA Corp
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RCA Corp
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Priority to GB26240/55A priority patent/GB815365A/en
Priority to DER17490A priority patent/DE1043536B/de
Priority to BE541623A priority patent/BE541623A/fr
Priority to JP2566155A priority patent/JPS324768B1/ja
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    • 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
    • H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
    • 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
    • G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
    • H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
    • H01L21/479—Application of electric currents or fields, e.g. for electroforming
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/22—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds
    • H01L29/227—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds further characterised by the doping material
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof

Definitions

  • This invention relates to improved photoconducting powders which are particularly useful in gap type and area type photocells and in other devices having bodies including photoconductive powders incorporated therein.
  • the invention includes improved methods for preparing hotoconducting powders and improved devices utilizing the photoconducting powders of the invention.
  • a photoconductive device is one which displays a reduced resistance to electric current flow when irradiated, as, for example, with light.
  • a photo conductive device comprises a body of photoconductive material and a pair of electrodes attached thereto. With a voltage applied to the electrodes, the device passes an increased amount of electric current when there is an increase in the intensity of light irradiating the device.
  • a photoconductive device is a perfect insulator when light to which it is sensitive is absent, and is a per feet conductor when a maximum intensity of light to which it is sensitive is present.
  • a photoconduo tive device behaves as a high resistance conductor when light to which it is sensitive is absent, and behaves as a lower resistance conductor when irradiated with light to which the device is sensitive.
  • the change in conduction produced by a unit variation of light intensity is referred to as the photosensitivity of the device.
  • the measure of photosensitivity is in terms of photocurrent under standard conditions.
  • the current passed by the device in darkness is referred to as the dark current; the current passed when the device is irradiated is referred to as the light current; and the diflference between the light-current and the dark current is referred to as the-photocurrent.
  • One type of photoconductve device comprises a single crystal of a photoconductive material and electrodes attached to the crystal.
  • Such single crystal photocells exhibit large photocurrents and high ratios of light current to dark current. and consequently the total current passed by a single crystal is small.
  • the crystal heats up and the photosensitivity of the crystal is reduced, either temporarily or permanently.
  • photoconductive crystals are difiicult to grow and are fragile. Thus, the expense of manufacture and maintenance often prohibits the use of single crystal photocells.
  • Another type of photoconductive device comprises a body including finely-divided photoconducting powder particles and electrodes attached to said body.
  • the body may include, for example, an unbonded powder or a powder mixed with a binder such as a synthetic resin.
  • Such powder photocells often exhibit a broader band of spectral response than single crystal photocells.
  • powder photocells may be made in any desired size, shape or current carrying capacity.
  • powder photocells have had the disadvantage of relatively low photosensitivity when the device is irradiated-with light to which his sensitive.
  • the low photosensitivity and high resistance of powder cells is generally attributed to the large number of electrical barriers existing between the electrodes.
  • the elec. tric current passing between the electrodes must travel through a chain of powder particles.
  • the resistance due .to poor electric contact between adjacent particles is multiplied by the number of particles in the chain, partly or completely masking the photosensitivity of the volume of each particle by limiting the maximum amount of current that can be passed by each chain of particles and by heating the particles during the flow of electric current.
  • i Powders which have been prepared as phosphors and which exhibit photoconductivity include cadmium sulphide and cadmium selenide with activator proportions of copper or silver and prepared with or without a halide.
  • Bodies of these phosphor powders exhibit very low photo sensitivity and therefore have been of little commercial value as photoconductive materials.
  • large single crystals of cadmium sulphide and cadmium selenide which exhibit high photosensitivity have been crushed to a powder. Bodies of these crushed powders exhibit practically no photosensitivity.
  • An object of the invention is to provide improved photoconducting powders.
  • Another object is to improve the photosensitivity of photoconducting powders, and bodies including photoconducting powders.
  • Another object is to provide photoconducting powder particles, the surfaces of said particles providing low resistance contact to one another in the presence of incident radiation in-the range between 4000 A. and 9000 A.
  • a further object is to provide improved photoconducting powders and bodies including Photoconducting powders comprising particles in the size range between 0.1 and 1.7 mils and having a dark resistivity above 10.0 ohm cm. and a light resistivity below 10 ohm cm. in the presence of about 5 foot candles of light from an incandescent source.
  • Another object is to provide improved photoconductive devices comprising the improved powders and bodies of the invention.
  • a further object is to provide improved methods for preparing photoconducting powders.
  • Photoconducting powders according to the invention comprise particles of a host crystal selected from the group consisting of selenides, sulphides,- and sulpho-selenides of cadmium having incorporated therein activator proportions of a halide and activator proportions of a metal selected from the group consisting of copper and silver, said particles being adapted to make low resistance contact to one another in the presence of incident radiation in the range between 4000 A. and 9000 A.
  • a photoconductive body according to the invention comprises a mass of the photoconducting powder of the invention with or without a binder.
  • the devices according to the invention comprise a body of the photoconducting powder according to the invention and electrodes attached thereto.
  • the improved method for producing a photoconducting powder comprises recrystallizing a material selected from the group consisting of sulphides, selenides and sulpho-selenides of cadmium to a desired range of particle size, incorporating into said recrystallized material activator proportions of a halide and activator proportions of ametal selected from the group consisting of copper and silver.
  • a material selected from the group consisting of sulphides, selenides and sulpho-selenides of cadmium to a desired range of particle size
  • activator proportions of a halide and activator proportions of ametal selected from the group consisting of copper and silver.
  • Figure l is a sectional. view of an apparatus for preparing the photocon-ducting powder according to one method of the invention
  • Figure 2 is a series of curves illustrating the spectral sensitivities of some typical photoconducting powders of the invention
  • Figure 3 is a perspective view of a photocell according to the invention.
  • Figure 4 is a linear scale curve illustrating the current-voltage characteristic of a typical photoconducting powder of the invention
  • Figure 5 is the curve of Figure 4 with the current ordinate plotted on a logarithmic scale
  • Figure 6 isa sectional view of an apparatus for preparing the photoconducting powder according to another method of the invention.
  • Example 1 A preferred method for preparing the photoconducting powder according to the invention follows.
  • An intimate mixture of 100 grams of cadmium sulphide, 10 grams of cadmium chloride, 1 gram of ammonium chloride, 1.7 milliliters of 0.1 M copper chloride, and 250 milliliters of water is prepared. This mixture may be prepared in a blender such as is used for mixing powders with water. The yellow, viscous liquid is dried at about 150 C. for about hours.
  • the dried cake is then broken up into pea-size lumps and packed. into a 12 inch test tube 21 to a depth of about seven inches.
  • the tube 21 is provided with a stopper 23 having an inlet tube 25 therethrough for the purpose of maintaining a. substantially stagnant atmosphere in the test tube 21 while maintaining atmospheric pressure through the subsequent firing steps.
  • the test tube 21 filled with the dried mixture 27, is fired at about 600 C. for about minutes and the fired product is then removed from the test tube 21 and allowed to soak in water until it disintegrates. This ordinarily takes about 20 minutes.
  • the product is washed on a fine, sintered, glass filter, dispersing the cake once or twice in water until thewashings contain less than 0.01 M cadmium chloride.
  • the product of the first firing is brown in color a relatively fine particle size.
  • cadmium chloride which is a solvent flux for cadmium sulphide.
  • the washed product of the first firing is moistened with a solution containing equal parts of 0.1 M aqueous cadmium chloride and 1.0 M ammonium chloride. The excess solution is removed by suction. After drying, the powder is passed through a 325 mesh sieve and the tailingsv discarded.
  • the dry powder 27 is placed in a test tube 21 to a depth not greater than 4.5 inches and fired for about 20 minutes at 600 C. in a stagnant atmosphere.
  • the fired mass 27 is removed from the furnace and permitted to cool.
  • the powder sint'ers to a stick, which is'then grated through a 50 mesh sieve.
  • the gently sintered stick is easily broken up into a powder which exhibits a low dark resistivity and high dark current.
  • the sulphur vaporizes and passes through the mass of brown powder.
  • the product of the third firing exhibits a high dark resistivity, low dark current and extremely high photosensitivity. Typical measurements indicate the ratio of light current to dark current of about 10 and a high speed of response.
  • the cadmium sulphide photoconducting powder which is the product of the third firing is brown to nearly black in color, the color darkening with increases in, either the proportions of copper or increases of the first firing temperature.
  • the average particle size varies according to the first firing temperature, being of the order of 0.3 mil for 600 C. and of the order of 0.7 mil for 650 C. Referring to Figure 2 the powders. exhibit a panchromatic absorption, although the spectral response is peaked in red and is practically nil in the blue region of the spectrum as indicated by cur /e31.
  • the powder is non-luminescent, has a substantially uniform particle size and is free-flowing.
  • Example 1 may be varied for example, cadmium selenides and cadmium. sulphoselenides may be substituted for cadmium sulphide. Cadmium sulphide is soluble in molten cadmium chloride at least to the extent of 30%. The presence of about 10% cadmium chloride in the mix during the first firing permits the growth of discrete uniformly sized crystals bonded by the .waterv soluble cadmium chloride. The
  • cadmium chloride is not critical, its purpose being principally to provide a crystallizing medium for the cadmium'sulphide host crystal.
  • cadmium chloride is preferred, any crystallizing medium for the host crystal which does not otherwise adversely effeet the product, may be used in place of cadmium chloride. Similar crystallizing media are used for other host crystals.
  • Ammonium chloride is introduced into the mix to (1). convert to cadmium chloride any cadmium oxide which may be present in the mix, and (2) to provide a firing atmosphere that prevents oxidation.
  • An activator proportion of chloride is incorporated into the host crystal during the first firing. This amount is extremely small and may come from either the cadmium chloride or the ammonium chloride.
  • Copper is introduced into the mix in a proportion equivalent to parts per million of copper with respect to cadmium sulphide.
  • the amount of copper is not critical; however, it is preferred to use between 50 and 300 parts per million of copper.
  • other monovalent cations may be incorporated into the cadmium sulphide host crystal. For example, 200 parts per million of silver in place of copperp'roduces an orangecolored powder having an intermediate photosensitivity and a low rate of decay.
  • the firing temperature during the first firing is somewhat critical.
  • the firing temperature should be above the melting point of cadmium chloride which is about 550 C. Below this temperature practically no crystal growth occurs and the copper does not diffuse into the host crystal.
  • Higher temperatures during the first firing produces a powder which has a darker color, larger particle size, lower dark resistivity and higher dark current.
  • the preferred temperature is the lowest temperature that insures prompt melting of the solvent material, produces a small particle size and a high dark resistivity in the final product. A temperature of about 600 C. is preferred.
  • the second firing sinters the powder into a stick and increases the conductivity and photosensitivity of the material. Small particles are probably sintered onto the surface of the larger ones, thus, reducing the number of particle-to-particle contacts.
  • a firing temperature of the order of 600 C. is preferred as the lowest temperature which insures the prompt melting of cadmium chloride.
  • the sulphur vapor which passes through the mass of photoconducting powder, reduces the dark current of the powder, presumably by diminishing the chloride. in the-powder to a value substantially equivalent to the amount of copper present in the product.
  • the powder does not sinter and the photosensitivity of the powder is only slightly affected. At higher temperatures, the loss in photosensitivity is greater.
  • the powder from the first firing is put through a 325 mesh sieve to eliminate the few lumps which may have formed in earlier steps in the process and also to establish an upper limit (1.7 mils) to particle size.
  • the 50 mesh sieve is used to achieve a more uniform disintegration of the sintered stick and to avoid crushing.
  • the final product is passed through a 325 mesh to eliminate any aggregates over 1.7 mils. Less than 5% is lost at this stage. In passing material through a sieve no hard rubbing is used. a The electrical properties of the final product are influenced by the amount of chloride present during the second firing. With too much chloride, the final product has a high dark current; with too little chloride, the final product has a low sensitivity.
  • Another method, according to the invention is to crystallize the cadmium sulphide from a molten solvent containing a halide, and then to leach out the solvent after cooling. Copper is then added difiused into the cadmium sulphide particles during the second firing. Approximately the same proportion of copper produces the same results as described in Example 1.
  • a photocell according to the invention comprises a pair of spaced electrodes 52 attached to a photoconducting body 54 comprising the phot'oconducting powder of the invention.
  • a device used to test the photoconducting powders of the invention is prepared as follows.
  • a glassplate 50 is provided with a strip of conducting material 200 mils wide and having a 20 mil gap running across and at right angles to the strip providing two electrodes 52.
  • 'A mixture is prepared comprising a quantity of the photoconducting powder of the invention and an equal volume of a 1% solution of ethyl cellulose in amyl alcohol.
  • a drop 54 of this mixture is placed on the gap and allowed to dry. When the drop 54 is dry, the photocell is ready for use.
  • a voltage usually 300 volts, unless otherwise indicated, is applied to the electrodes. Tables I and II summarize the terminology notation and conditions of measurement.
  • test photocell utilizes a photoconducting body 54 comprising a resin-bonded powder
  • an unbonded powder may also be used.
  • Other resins may be'used as a binder, for example, a silicone resin.
  • Table III gives the data for some typical measurements of powders prepared andtested according to the invention.
  • Conducting CdS:Cl is the product of the first firing of a mixture without copper, as described above.
  • Figures 4 and 5 show the photocurrent as a function of voltage for a typical test photocell prepared with the photoconducting powders of the invention. A transition occurs at about volts. Above this, i is linear with voltage and below this log i is linear with voltage. This indicates the presence of barriers presumably at the points of contact between the particles, totaling about 150 volts for the series of barriers along 20 mil distance.
  • Table III The data of Table III indicates that, with the mixture of photoconducting powder of Example 1 and ethyl cellulose'applied across a 20 by 200 mil gap with 300 volts;applied, there is available about 4 volts per particle. About half of this, .or' 2 volts per. particle, is. a barrier due to the resistive; surface contact between particles. Assuming a single layer of powder across the gap, about 1,000 microamperes. current is, carried by 700 chains of particles. This is equivalent to about 1 microampere per chain :and per particle.
  • the powders of the invention have a dark resistivity above 10 ohm cm. and a light resistivity below 10 ohm cr'n. when, illuminated with about foot candles of light. Such a range provides the necessary properties for com flashal applications.
  • the voltage appliedto a photocell such as the one above described may be either alternating or direct current. If an alternating current is used, the i /i ratio decreases with increased frequency for two reasons: first, because the z decreases as a function of the time constant of the photoconductor, and second, because the i increases as a function of the capacitance, across the gap.
  • alternating current is used, the i /i ratio decreases with increased frequency for two reasons: first, because the z decreases as a function of the time constant of the photoconductor, and second, because the i increases as a function of the capacitance, across the gap.
  • the specific examples of operational characteristics given herein are in connection with direct current operation. Such examples are equally representative of low frequency alternating current operation.
  • Example 2 Another photoconducting powder of the invention is prepared by the method described in Example 1 except that cadmium selenide is substituted for cadmium sulphide in the starting mixture.
  • the starting mixture comprises 100 grams of cadmium selenide, grams of cadmium chloride, 1 gram of ammonium chloride, 1.7 milliliters of 0.1 M copper chloride, and 250 milliliters of water.
  • Example 3 50 grams of cadmium sulphide, 8- milliliters of 0.01 M copper nitrate solution and 0.006 grain of cadmium chloride is slurried inzwater, dried at about 250* C., placed in a test tube 43 and fired at' about .700 C. for minutes in an atmosphere offflowing' hydrogen. Upon cooling the powder is ready for use-
  • Example 3 utilizes about .100 parts per million of copper with respect to cadmium sulphide. Amounts between 10 and 10,000 parts per million may be used in this method.
  • any gas which is inert to cadmium sulphide, such as nitrogen, helium or hydrogen sulphide may be, used.
  • Firing times from 10 to 60 minutes at 900 C. may be used.
  • Firing temperatures from 500 C. to 1200 C. may be used with a suitable firing time.
  • Example 4 The same mixture as described in Ex: ample 3 is fired in an atmosphere of flowing nitrogen containing free bromine. by passing 50 milliliters per minute of nitrogen through bromine water. it is preferred to introduce the brominecontaining nitrogen into the powder mass so that it passes freely through the powder during firing.
  • the method of the invention includes steps for introducing free electrons. as charge compensators and steps for removing, the free electrons.
  • each Cu ion probably substitutes for a Cd+ ion and each (llion probably substitutes for. an 8- ion in the crystal. Since each Cu ion. makes. the crystal deficient in one electron, the excess electron brought into the lattice by the Clion compensates for this deficiency, thus preserving electroneutrality in the lattice.
  • copper is introduced into the. mix us. Go, it nevertheless enters the lattice as Ctr- Itis believed that'Cu+ is reduced during firing.
  • a balance of copper and a halide is attained, such that a maximum insulating value is obtained in the darkness and a maximum number of photo-excitable electrons are provided in the volume of the crystal.
  • the photosensitivity of the volume is usually masked due to the high sensitivity of the contact between the particles.
  • Treatment of the particles ac? cording to the invention adapts the surface of each particle to make a low resistance contact with other particles with which it is in physical contact when light is applied thereto.
  • the powders of the invention may be utilized to prepare photoconductive devices and elements that are useful in meters, relays, picture converters, picture intensifiers, pickup devices, switches and so forth.
  • the devices comprise a body including the photoconducting powder of the invention and an electrode attached to said body.
  • the body may be any shape; however, it is preferred to prepare the body as a layer of material.
  • a method of preparing a photoconducting powder comprising recrystallizing cadmium sulphide from molten cadmium chloride containing activator proportions of copper, as a copper salt, washing said recrystallized cadmium sulphide to remove water-soluble material including said cadmium chloride, coating said washed cadmium sulphide particles with a thin layer of a halide, firing said coated cadmium sulphide particles to diffuse said halide into said cadmium sulphide, retiring said fired cadmium sulphide particles in a sulphur-containing atmosphere until the dark conductivity of said fired CdS is reduced to a desired value.
  • a method for preparing a photoconducting powder comprising firing a mixture comprising parts byweight of cadmium sulphide, 10 parts by weight of cadmium chloride, 1 part by weight of ammonium chlo ride, and .0001 part by weight of copper as copper chloride to about 600 C. for about 20 minutes, washing said fired product to remove water soluble materials, refiring said washed product with a trace of cadmium chlorides at about 600 C. for about 20 minutes, and then refiring saidrefired. product in a sulphur containing atmosphere at about 500 C. for about 10 minutes.
  • A. method for preparing a photoconducting powder comprising firing a mixture comprising 100 parts byweight of cadmium selenide, 10. parts by weight. of cad:
  • a method for preparing a photoconducting powder comprising recrystallizing from a molten solvent a material selected from the group consisting of sulfides, selenides, and sulfo-selenides of cadmium, said molten solvent containing activator proportions of a cation selected from the group consisting of copper and silver, washing said recrystallized material to remove water-soluble constituents, diffusing a trace of halide into said washed material, and then firing said halide-diffused material in a sulfur-containing atmosphere.
  • a method for preparing a photoconducting powder comprising recrystallizing from a molten halide a material selected from the group consisting of sulfides, selenides, and sulfo-selenides of cadmium, said molten halide containing activator proportions of copper as a salt thereof, washing said recrystallized material to remove water-soluble constituents, firing said washed material with a trace of a halide to difiuse said halide into said material, and then refiring said fired material in a 1% sulfur-containing atmosphere until the dark conductivity oi said material is reduced to a desired value.
  • a method for preparing a photoconducting powder comprising recrystallizing cadmium sulfide from a molten halide, said molten halide containing activator proportions of copper as a salt thereof, washing said recrystallized cadmium sulfide to remove water-soluble constituents, firing said washed material with a trace of a halide to diffuse said halide into said material, and then refiring said fired material in a sulfur-containing atmosphere until the dark conductivity of said material is reduced to a desired value.
  • a method for preparing a photoconducting powder comprising recrystallizing cadmium selenide from a molten halide, said molten halide containing activator proportions of copper as a salt thereof, washing said recrystallized cadmium selenide to remove water-soluble constituents, firing said washed material with a trace of a halide to diffuse said halide into said material, and then refiring said fired material in a sulfur-containing atmosphere until the dark conductivity of said material is reduced to a desired value.

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US472354A 1954-09-27 1954-12-01 Photoconducting powders and method of preparation Expired - Lifetime US2876202A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US287620D USB287620I5 (fr) 1954-12-01
US472354A US2876202A (en) 1954-12-01 1954-12-01 Photoconducting powders and method of preparation
GB26240/55A GB815365A (en) 1954-09-27 1955-09-13 Improvements relating to photoconductive materials and devices
DER17490A DE1043536B (de) 1954-09-27 1955-09-26 Verfahren zur Herstellung von photoleitfaehigem Material, bestehend aus einer Mischung von Kadmiumsulfid, -selenid oder -sulfidselenid
BE541623A BE541623A (fr) 1954-09-27 1955-09-27 Matieres et appareils photoconducteurs.
JP2566155A JPS324768B1 (fr) 1954-09-27 1955-09-27

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US472354A US2876202A (en) 1954-12-01 1954-12-01 Photoconducting powders and method of preparation

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2937353A (en) * 1959-02-27 1960-05-17 Sylvania Electric Prod Photoconductive devices
US2995474A (en) * 1959-10-02 1961-08-08 Eastman Kodak Co Photoconductive cadmium sulfide and method of preparation thereof
US3037941A (en) * 1959-07-15 1962-06-05 Thorn Electrical Ind Ltd Photoconductive materials
US3133888A (en) * 1960-05-11 1964-05-19 Hitachi Ltd Production of semiconductor materials
US3238150A (en) * 1962-09-12 1966-03-01 Xerox Corp Photoconductive cadmium sulfide powder and method for the preparation thereof
US3379527A (en) * 1963-09-18 1968-04-23 Xerox Corp Photoconductive insulators comprising activated sulfides, selenides, and sulfoselenides of cadmium
US3492718A (en) * 1966-08-15 1970-02-03 Matsushita Electric Ind Co Ltd Method for preparing infrared quenching photoconductive material
US3647430A (en) * 1967-06-08 1972-03-07 Canon Camera Co METHOD OF THE PREPARATION OF CdS OR CdSe POWDER FOR ELECTROPHOTOGRAPHY AND METHOD OF MAKING AN ELECTROPHOTOGRAPHIC PHOTOSENSITIVE PLATE BY USING THE POWDER
US3691104A (en) * 1969-05-15 1972-09-12 Canon Kk Process for preparing photoconductive powders
US3895943A (en) * 1967-06-08 1975-07-22 Canon Camera Co Method for the preparation of CdS or CdSe powder for electrophotography
US3904409A (en) * 1968-03-08 1975-09-09 Canon Kk Photoconductive body for electrophotography and the method of manufacturing the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2651700A (en) * 1951-11-24 1953-09-08 Francois F Gans Manufacturing process of cadmium sulfide, selenide, telluride photoconducting cells
US2765385A (en) * 1954-12-03 1956-10-02 Rca Corp Sintered photoconducting layers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2651700A (en) * 1951-11-24 1953-09-08 Francois F Gans Manufacturing process of cadmium sulfide, selenide, telluride photoconducting cells
US2765385A (en) * 1954-12-03 1956-10-02 Rca Corp Sintered photoconducting layers

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2937353A (en) * 1959-02-27 1960-05-17 Sylvania Electric Prod Photoconductive devices
US3037941A (en) * 1959-07-15 1962-06-05 Thorn Electrical Ind Ltd Photoconductive materials
US2995474A (en) * 1959-10-02 1961-08-08 Eastman Kodak Co Photoconductive cadmium sulfide and method of preparation thereof
US3133888A (en) * 1960-05-11 1964-05-19 Hitachi Ltd Production of semiconductor materials
US3238150A (en) * 1962-09-12 1966-03-01 Xerox Corp Photoconductive cadmium sulfide powder and method for the preparation thereof
US3379527A (en) * 1963-09-18 1968-04-23 Xerox Corp Photoconductive insulators comprising activated sulfides, selenides, and sulfoselenides of cadmium
US3492718A (en) * 1966-08-15 1970-02-03 Matsushita Electric Ind Co Ltd Method for preparing infrared quenching photoconductive material
US3647430A (en) * 1967-06-08 1972-03-07 Canon Camera Co METHOD OF THE PREPARATION OF CdS OR CdSe POWDER FOR ELECTROPHOTOGRAPHY AND METHOD OF MAKING AN ELECTROPHOTOGRAPHIC PHOTOSENSITIVE PLATE BY USING THE POWDER
US3895943A (en) * 1967-06-08 1975-07-22 Canon Camera Co Method for the preparation of CdS or CdSe powder for electrophotography
US3904409A (en) * 1968-03-08 1975-09-09 Canon Kk Photoconductive body for electrophotography and the method of manufacturing the same
US3691104A (en) * 1969-05-15 1972-09-12 Canon Kk Process for preparing photoconductive powders

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