Patent GB-987866-A (GB)
Title: Modified film of a zinc-sulphite-type compound and method of making it
IPC: H01L33/00
Filed: 1961-04-13
Abstract: <PICT:0987866/C4-C5/1> <PICT:0987866/C4-C5/2> <PICT:0987866/C4-C5/3> The surface of a crystalline layer of a zinc-sulphide type compound consisting of one or both of zinc and cadmium with one or more of oxygen, sulphur, selenium, and tellurium has a layer formed on its surface in which the cation is partly replaced by another metallic ion.  As described, the metallic ion is replaced by a Group IB metal so that the adjacent layers have the same anion.  The original compound may contain suitable activators to produce luminiscence and may be deposited on substrates or heat resisting glass or a polyethylene terephthalate tape.  The zinc sulphide type layer may be produced as shown in Fig. 1 by vapour deposition of a zinc or cadmium coating from a crucible 4 heated by an electric current on to glass plate 8 which is heated by a resistance winding 11.  The jar is evacuated through an outlet 3. alternatively, if a vapour reaction technique is to be used, substrate 8 is heated by a coil 11 and a suitable compound such as zinc chloride is evaporated while hydrogen sulphide is admitted through inlet tube 13 to react with the zinc chloride and deposit zinc sulphide on the plate.  If manganese chloride is included in the crucible, the zinc sulphide layer is manganese and chloride activated.  In further examples, the crucible contains zinc chloride and the gas admitted is hydrogen selenide or hydrogen telluride.  In a still further example, elemental zinc, cadmium, and zinc chloride are evaporated in an atmosphere of hydrogen sulphide.  After the deposition of the zinc sulphide type compound, the coated substrate is immersed in a solution which exchanges the cation in the compound for <PICT:0987866/C4-C5/4> copper, silver or gold.  Suitable compounds are copper acetate, sulphate, chloride, bromide, nitrate, and carbonate, copper acetyl, acetonal and the corresponding gold and silver compounds. The salts used are generally divalent but a monovalent stable salt is suitable. Their solutes may be present with reducing agents such as hydrazine sulphate and sodium hypophosphite which cause the metallic ion to exist in a monovalent state.  The solvent may be water or an organic polar liquid such as ethyl or methyl alcohol or ethylene glycol.  A complexing agent may be added since monovalent compounds are not readily soluble.  Pyridine, ammonia, aniline quinoline and thiourea are suggested. The monovalent ions in solution are said to replace the zinc or cadmium in the crystal lattice resulting in a film or skin of a copper, silver or gold compound of sulphur, selenium, or tellerium.  Cathode ray tube coating (Fig. 3).-The face plate of a cathode ray tube has on it a phosphor layer 12 in which the zinc or cadmium of the zinc sulphide type compound is replaced as described above to form a conducting coating 15.  Heated windshield.-The zinc sulphide type compound may be deposited on a plastic or glass windshield to act as a heater to prevent ice formation.  Such a layer may also be used as a radiant heater.  Thermo-plastic recording system.-A roll of polyethylene terephthalate tape may be coated in the apparatus shown in Fig. 5 in which the tape is driven from roller 27 to roller 28 while vapour deposition of the zinc sulphide type layer takes place. Treatment of the tape as described produces a conducting layer on the surface and the tape is then recoated with a thermoplastic player of spraying and passing over a doctor roller. Electroluminescent device.-Fig. 6 shows a collision excitation electroluminescent device including an N-type region of any of the zinc and cadmium sulpho-selenide family of phosphors including zinc selenide, zinc sulphide, cadmium sulphide, cadmium selenide, zinc cadmium sulphide, zinc cadmium selenide, zinc cadmium sulpho-selenide, zinc sulpho-selenide, cadmium sulpho-selenide, zinc oxide and mixtures thereof.  A P-type region 43 is contiguous with the N region and is a compound having a cation selected from Group IB of the Periodic Table and has the same anion as the N-type region. Electrodes 45, 46 of indium, silver or tin ether oxide or reduced are in contact with the P and N layers and the whole is supported on a glass plate 47.  The lower electrode may be light reflecting.  The P region is 30<\>rA in thickness and the N region 10 microns.  The phosphor may be activated with any of copper, silver, chlorine, bromine, indium, gallium and aluminium while manganese, arsenic and antimony with a co-activator of chlorine are suggested for D.C. operation.  In a further device (Fig. 7, not shown) a recombination electroluminescent device has an N layer of 5 microns thickness and a P layer 122 greater than one minority carrier diffusion length thick, say 1/2 to 1 micron. Each layer should also have sufficient impurities to serve as recombination centres.  The device is connected with the junction biased in the forward direction.ALSO:<PICT:0987866/C6-C7/1> <PICT:0987866/C6-C7/2> <PICT:0987866/C6-C7/3> <PICT:0987866/C6-C7/4> The surface of a crystalline layer of a zinc-sulphide type compound consisting of one or both of zinc and cadmium with one or more of oxygen, sulphur, selenium, and tellurium, has a layer formed on its surface in which the cation is partly replaced by another metallic ion. As described, the metallic ion is replaced by a Group Ib metal so that the adjacent layers have the same anion.  The original compound may contain suitable activators to produce luminescence and may be deposited on substrates of heat-resisting glass or a polyethylene terephthalate tape. The zinc-sulphide type layer may be produced as shown in Fig. 1 by vapour deposition of a zinc or cadmium coating from a crucible 4 heated by an electric current on to a glass plate 8 which is heated by a resistance winding 11. The jar is evacuated through an outlet 3. Alternatively, if a vapour reaction technique is to be used, substrate 8 is heated by a coil 11 and suitable compound such as zinc chloride is evaporated while hydrogen sulphide is admitted through inlet tube 13 to react with the zinc chloride and deposit zinc sulphide on the plate. If manganese chloride is included in the crucible the zinc-sulphide layer is manganese and chlorine activated. In further examples, the crucible contains zinc chloride and the gas admitted is hydrogen selenide or hydrogen telluride. In a still further example, elemental zinc cadmium and zinc chloride are evaporated in an atmosphere of hydrogen sulphide.  After the deposition of the zinc-sulphide type compound, the coated substrate is immersed in a solution which exchanges the cation in the compound for copper, silver or gold. Suitable compounds are copper acetate, sulphate, chloride, bromide, nitrate, and carbonate, copper acetyl, acetonal and the corresponding gold and silver compounds.  The salts used are generally divalent but a monovalent stable salt is suitable. Their solutes may be present with reducing agents such as hydrazine sulphate and sodium hypophosphite which cause the metallic ion to exist in a monovalent state.  The solvent may be water or an organic polar liquid such as ethyl or methyl alcohol or ethylene glycol.  A complexing agent may be added since monovalent compounds are not readily soluble.  Pyridine, ammonia, aniline quinoline and thiorea are suggested. The monovalent ions in solution are said to replace the zinc or cadmium in the crystal lattice resulting in a film or skin of a copper, silver or gold compound of sulphur, selenium, or tellurium.  Cathode ray tube coating (Fig. 3).  The face plate of a cathode ray tube has on it a phosphor layer 12 in which the zinc or cadmium of the zinc-sulphide type compound is replaced as described above to form a conducting coating 15.  Heated windshield.  The zinc-sulphide type compound may be deposited on a plastic or glass windshield to act as a heater to prevent ice formation.  The modified conductivity of the surface provides the connection to the layer. Such a modified layer may also act as a radiant heater. Thermoplastic recording system.  A roll of polyethylene terephthalate tape may be coated in the apparatus shown in Fig. 5 in which the tape is driven from roller 27 to roller 28 while vapour deposition of the zinc-sulphide type layer takes place. Treatment of the tape as described produces a conducting layer on the surface and the tape is then recoated with a thermoplastic layer by spraying and passing over a doctor roller.  Electroluminescent device.  Fig. 6 shows a collision excitation electroluminescent device including an N type region of any of the zinc and cadmium sulpho-selenide family of phosphors including zinc selenide, zinc sulphide, cadmium sulphide, cadmium selenide, zinc cadmium sulphide, zinc cadmium selenide, zinc cadmium sulpho-selenide, zinc sulpho-selenide, cadmium sulpho-selenide, zinc oxide and mixtures thereof.  A P type region 43 is contiguous with the N region and is a compound having a cation selected from Group Ib of the Periodic Table and has the same anion as the N type region.  Electrodes 45, 46, of indium, silver or tin, either oxide or reduced are in contact with the P and N layers and the whole is supported on a glass plate 47.  The lower electrode may be light reflecting.  The P region is 30 <\>rA in thickness and the N region 10 microns.  The phosphor may be activated with any of copper, silver, chlorine, bromine, indium, gallium and aluminium while manganese, arsenic and antimony with a coactivator or chlorine are suggested for D.C. operation.. In a further device, Fig. 7 (not shown), a recombination electroluminescent device has an N layer of 5 microns thickness and a P layer 122 greater than one minority carrier diffusion length thick, say 1/2 -1 micron.  Each layer should also have sufficient impurities to serve as recombination centres. The device is connected with the junction biased in the forward direction.