US20020125129A1 - Sputtering targets and method for the preparation thereof - Google Patents
Sputtering targets and method for the preparation thereof Download PDFInfo
- Publication number
- US20020125129A1 US20020125129A1 US10/008,949 US894901A US2002125129A1 US 20020125129 A1 US20020125129 A1 US 20020125129A1 US 894901 A US894901 A US 894901A US 2002125129 A1 US2002125129 A1 US 2002125129A1
- Authority
- US
- United States
- Prior art keywords
- titanium dioxide
- plasma
- target
- sub
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2456—Coating containing TiO2
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
Definitions
- the present invention relates to a process for the preparation of improved high rate sputtering targets and, in particular, to a process for the preparation of sputtering targets comprising sub-stoichiometric titanium dioxide with high electrical conductivity to be used in D.C. sputtering at high power levels.
- Sputtered coatings of various oxides e.g. silica
- nitrides e.g. silicon nitride
- These coatings are usually made of stacks of several different layers with different refractive indices, preferably a combination of low and high refractive index, to produce optical filters.
- antireflective coatings it is preferred to combine two materials showing the highest and the lowest possible refractive indices. Such materials are titania and silica. Another advantage of these materials is their durability.
- For low emissivity films on window glasses it is preferred to combine a silver layer with a high refractive index material to dereflect the silver which improves light transmission.
- Titanium dioxide coatings have a high refractive index and can thus be used to provide coatings of a high refractive index or to provide the high refractive index coatings in optical stacks.
- the existing process for producing titanium dioxide coatings comprises using titanium metal as the sputtering target and using oxygen as a component of the plasma gas. The titanium is thus converted to titanium dioxide during the sputtering process. Although satisfactory coatings of titanium dioxide can be produced, the rate of deposition is very slow and much slower than coating with zinc oxide and/or tin oxide.
- niobium oxide As a substitute for titanium dioxide it has been suggested to use alternative materials such as niobium oxide. Whilst it is possible to coat a substrate with niobium oxide using a niobium metal target at slightly higher speeds than the equivalent process using titanium, niobium is very expensive.
- JP-A-07-233469 describes the preparation of a sputtering target by hot-pressing titanium dioxide powder in a nonoxidizing atmosphere and sintering the compact.
- the sintered compact comprises TiO x where 1 ⁇ x ⁇ 2 with a resistivity of 10 ohm.cm which is too high for D.C. sputtering at high power levels.
- the stability of the sputtering process and the arc rate are both very dependent upon the conductivity of the target, particularly at high power levels.
- JP-A-62-161945 describes a method of manufacturing a ceramic sputtering target in which a ceramic material consisting mainly of ZrO 2 , TiO 2 , SiO 2 , Ta 2 O 3 , Al 2 O 3 , Fe 2 O 3 or a compound of these materials is sprayed using a water plasma spray to produce a formed body which may be used as a sputtering target.
- the sputtering target is used for high frequency sputtering of non-conductive target materials.
- titanium dioxide can be D.C. sputtered at high power levels from a target comprising sub-stoichiometric titanium dioxide to provide Oa coating on a substrate of sub-stoichiometric or stoichiometric titanium dioxide.
- the present invention provides a process for the preparation of a sputtering target which comprises sub-stoichiometric titanium dioxide, TiO x , where x is below 2 having an electrical resistivity of less than 0.5 ohm.cm, optionally together with niobium oxide, which process comprises plasma spraying titanium dioxide, TiO 2 optionally together with niobium oxide, onto a target base in an atmosphere which is oxygen deficient and which does not contain oxygen-containing compounds, the target base being coated with TiO x which is solidified by cooling under conditions which prevent the sub-stoichiometric titanium dioxide from combining with oxygen.
- Sub-stoichiometric titanium dioxide, TiO x , where x is below 2 and generally is in the range of from 1.55 to 1.95 is known in the art.
- the electrical conductivity will vary, depending upon the stoichiometry, the most preferred form having an electrical resistivity of 0.02 ohm.cm.
- TiO 2 is plasma sprayed onto a target base, such as a backing tube or plate, for example a target base of an electrically conductive material, for example stainless steel or titanium metal, aluminium or copper.
- a target base such as a backing tube or plate
- the target may be of any type known in the art, for example a rotatable target or a flat magnetron target.
- the action of the plasma flame on the titanium dioxide causes the titanium dioxide to lose some oxygen atoms from its lattice, preferably from the surface of the particles.
- the titanium dioxide is converted into the sub-stoichiometric form, i.e. non-stoichiometric oxygen deficient titania.
- the primary plasma gas used for the plasma spraying is preferably argon, with hydrogen as the secondary plasma gas in order to obtain the highest temperatures of the particles.
- the titanium dioxide which is subjected to plasma spraying preferably has a particle size in the range of from 1 to 60 micrometers, preferably in the range of from 1 to 20 micrometers.
- the sub-stoichiometric titanium dioxide which is coated on the target base is solidified under conditions which prevent it from regaining oxygen and reconverting to TiO 2 .
- the target base is water cooled during the plasma spraying in order to quench the titanium dioxide in the sub-stoichiometric form and to improve the conductivity thereof. It is also important to use a certain amount of hydrogen or nitrogen in the plasma gas in order to produce a high temperature plasma and to assist in the reduction. Hydrogen is preferred because of its reducing powers.
- particle temperatures of above 2000° C. are used, more preferably above 2500° C.
- the titanium dioxide may be plasma sprayed together with niobium oxide.
- the present invention also provides a process for the preparation of sub-stoichiometric titanium dioxide, TiO x , where x is below 2 having an electrical resistivity of less than 0.1 ohm.cm, which process comprises subjecting titanium dioxide to a plasma treatment in an atmosphere which is oxygen deficient and which does not contain oxygen-containing compounds.
- the titanium dioxide is preferably sprayed through a plasma flame, for example a plasma flame using a mixture of argon and hydrogen as the plasma gas.
- the plasma flame will operate at a high temperature to raise the temperature of the particles to above 2000° C.
- the sputtering targets which are produced according to the process of the invention have a high electrical conductivity and thus are able to run at high power levels using conventional D.C. power supplies, without the need for expensive arc diverter systems, or D.C. switching power supplies, or the Twin-Mag System where two targets are sequentially used as anode and cathode with a mid-frequency power supply, or any special requirements of a gas control system.
- D.C. sputtering can be carried out at power levels of up to 100Kw.
- large target bases e.g. rotatable 3.5 meters long and 150 mm in diameter can be coated up to a typical coating thickness of 6 mm.
- the targets produced by the process of the present invention do not suffer from significant arcing problems because titanium dioxide has a higher melting point than titanium metal for which so called “vapour arcing” is a problem due to the lower melting point of the metal. Even if some arcing does occur for titanium dioxide there is little accompanying damage to the target.
- a rotatable target, water cooled on the inside to 35° C., comprising a tube of stainless steel of diameter 133 mm and length 800 mm was coated to a thickness of from 4 to 10 mm with sub-stoichiometric titanium dioxide, TiO x , where x is below 2 as hereinbefore described by plasma spraying titanium dioxide (rutile) having a particle size of from 10 to 40 ⁇ m onto the target using argon as the primary plasma gas and hydrogen as the secondary plasma gas. 72 liters (60% argon, 40% hydrogen) were used. The power level was 45kW (455A, 96V).
- a commercial white pigment consisting of titanium dioxide in the anatase crystal form was used. This powder is stoichiometric and electrically insulating. The powder was mechanically agglomerated and compacted into flakes, ground, sieved (70-100 ⁇ m) and sintered at 1300° C. in air. The sintered body was then ground and sieved to a particle size of 10-40 ⁇ m. The particles were yellow stoichiometric, non-conductive, titanium dioxide with a rutile crystalline structure.
- a rotatable target comprising a backing tube of aluminium (2.50 m long and 133 mm 5 diameter) was prepared by plasma spraying of the above rutile powder using argon as the primary gas and hydrogen as the secondary gas. 75 liters (40% argon, 60% hydrogen) were used. The power level was 50kW (110V, 455A). The plasma spraying was carried out under a nitrogen atmosphere.
- the target was rotated at 100 rpm and the torch translation was 2.5 m/min until a coating 4 mm thick was obtained.
- the inside of the aluminium tube was water cooled to a temperature of 35° C.
- the coated target had a resistivity of 0.07 ohm.cm.
- the target was subsequently tested at power levels of up to 100kW and worked well in the sputtering equipment without significant arcing.
- the deposition of titanium dioxide was six times higher than the rate from a titanium metal target in reactive sputtering.
- Example 2 was repeated with a low pressure vacuum plasma operating at 200 mBar using titanium dioxide in the anatase form having a particle size in the range of from 1 to 10 ⁇ m. Using the low pressure plasma, powders with a smaller particle size can be used.
- Example 2 On spraying onto a target base under the conditions of Example 2 the anatase was converted into a sub-stoichiometric rutile form of titanium dioxide.
- the coated target had a resistivity of 0.02 ohm.cm.
- a mixture of niobium oxide (25 parts by weight) and titanium dioxide (75 parts by weight) having a particle size of from 0.1 to 2 ⁇ m was agglomerated and compacted, dried and sintered at 1300° C. in air. The sintered body was then ground to a particle size of 10 to 40 ⁇ m.
- the powder mixture was then plasma sprayed under the conditions given in Example 2 onto an aluminium backing tube to a coating thickness of 4 mm.
- the coated target had an electrical resistivity of 0.5 ohm.cm and thus could be used as a D.C. sputtering target.
Abstract
Sputtering targets comprising sub-stoichiometric titanium dioxide, TiOx, where x is below 2, are provided. The targets are preferably formed by plasma spraying so as to have an electrical resistivity of less than 0.5 ohm.cm.
Description
- The present application is a divisional of U.S. patent application filed Feb. 17, 1998 and assigned Ser. No.09/024,240, the entire disclosure of which is incorporated herein by reference.
- The present invention relates to a process for the preparation of improved high rate sputtering targets and, in particular, to a process for the preparation of sputtering targets comprising sub-stoichiometric titanium dioxide with high electrical conductivity to be used in D.C. sputtering at high power levels.
- Sputtered coatings of various oxides (e.g. silica) and nitrides (e.g. silicon nitride) are used to form optical coatings showing interesting properties on a number of substrates. Known applications include low emissivity films on window glasses, cold mirrors on reflectors, enhanced mirrors for photocopiers and antireflective coatings on picture glass or TV screens. These coatings are usually made of stacks of several different layers with different refractive indices, preferably a combination of low and high refractive index, to produce optical filters. For antireflective coatings it is preferred to combine two materials showing the highest and the lowest possible refractive indices. Such materials are titania and silica. Another advantage of these materials is their durability. For low emissivity films on window glasses it is preferred to combine a silver layer with a high refractive index material to dereflect the silver which improves light transmission.
- Titanium dioxide coatings have a high refractive index and can thus be used to provide coatings of a high refractive index or to provide the high refractive index coatings in optical stacks. The existing process for producing titanium dioxide coatings comprises using titanium metal as the sputtering target and using oxygen as a component of the plasma gas. The titanium is thus converted to titanium dioxide during the sputtering process. Although satisfactory coatings of titanium dioxide can be produced, the rate of deposition is very slow and much slower than coating with zinc oxide and/or tin oxide.
- As a substitute for titanium dioxide it has been suggested to use alternative materials such as niobium oxide. Whilst it is possible to coat a substrate with niobium oxide using a niobium metal target at slightly higher speeds than the equivalent process using titanium, niobium is very expensive.
- JP-A-07-233469 describes the preparation of a sputtering target by hot-pressing titanium dioxide powder in a nonoxidizing atmosphere and sintering the compact. The sintered compact comprises TiOx where 1<x<2 with a resistivity of 10 ohm.cm which is too high for D.C. sputtering at high power levels. The stability of the sputtering process and the arc rate are both very dependent upon the conductivity of the target, particularly at high power levels.
- JP-A-62-161945 describes a method of manufacturing a ceramic sputtering target in which a ceramic material consisting mainly of ZrO2, TiO2, SiO2, Ta2O3, Al2O3, Fe2O3 or a compound of these materials is sprayed using a water plasma spray to produce a formed body which may be used as a sputtering target. The sputtering target is used for high frequency sputtering of non-conductive target materials.
- Accordingly, there is a need for an improved process for the production of sputtering targets comprising sub-stoichiometric TiO2 which does not involve the hot-pressing and sintering route of JP-A-07-233469 and which can be used to produce such targets which have a high enough electrical conductivity to be used as large size targets with complex shapes at high power levels.
- We have now surprisingly discovered that titanium dioxide can be D.C. sputtered at high power levels from a target comprising sub-stoichiometric titanium dioxide to provide Oa coating on a substrate of sub-stoichiometric or stoichiometric titanium dioxide.
- Accordingly, the present invention provides a process for the preparation of a sputtering target which comprises sub-stoichiometric titanium dioxide, TiOx, where x is below 2 having an electrical resistivity of less than 0.5 ohm.cm, optionally together with niobium oxide, which process comprises plasma spraying titanium dioxide, TiO2 optionally together with niobium oxide, onto a target base in an atmosphere which is oxygen deficient and which does not contain oxygen-containing compounds, the target base being coated with TiOx which is solidified by cooling under conditions which prevent the sub-stoichiometric titanium dioxide from combining with oxygen.
- Sub-stoichiometric titanium dioxide, TiOx, where x is below 2 and generally is in the range of from 1.55 to 1.95 is known in the art. When produced according to the process of the present invention the electrical conductivity will vary, depending upon the stoichiometry, the most preferred form having an electrical resistivity of 0.02 ohm.cm.
- In carrying out the process of the present invention titanium dioxide, TiO2 is plasma sprayed onto a target base, such as a backing tube or plate, for example a target base of an electrically conductive material, for example stainless steel or titanium metal, aluminium or copper. The target may be of any type known in the art, for example a rotatable target or a flat magnetron target.
- During the plasma spraying process, the action of the plasma flame on the titanium dioxide causes the titanium dioxide to lose some oxygen atoms from its lattice, preferably from the surface of the particles. The titanium dioxide is converted into the sub-stoichiometric form, i.e. non-stoichiometric oxygen deficient titania. The primary plasma gas used for the plasma spraying is preferably argon, with hydrogen as the secondary plasma gas in order to obtain the highest temperatures of the particles. The titanium dioxide which is subjected to plasma spraying preferably has a particle size in the range of from 1 to 60 micrometers, preferably in the range of from 1 to 20 micrometers. The sub-stoichiometric titanium dioxide which is coated on the target base is solidified under conditions which prevent it from regaining oxygen and reconverting to TiO2. Preferably the target base is water cooled during the plasma spraying in order to quench the titanium dioxide in the sub-stoichiometric form and to improve the conductivity thereof. It is also important to use a certain amount of hydrogen or nitrogen in the plasma gas in order to produce a high temperature plasma and to assist in the reduction. Hydrogen is preferred because of its reducing powers. Preferably particle temperatures of above 2000° C. are used, more preferably above 2500° C.
- In a particular embodiment of the present invention, the titanium dioxide may be plasma sprayed together with niobium oxide.
- In a further aspect the present invention also provides a process for the preparation of sub-stoichiometric titanium dioxide, TiOx, where x is below 2 having an electrical resistivity of less than 0.1 ohm.cm, which process comprises subjecting titanium dioxide to a plasma treatment in an atmosphere which is oxygen deficient and which does not contain oxygen-containing compounds. In carrying out this process the titanium dioxide is preferably sprayed through a plasma flame, for example a plasma flame using a mixture of argon and hydrogen as the plasma gas. Preferably the plasma flame will operate at a high temperature to raise the temperature of the particles to above 2000° C.
- The sputtering targets which are produced according to the process of the invention have a high electrical conductivity and thus are able to run at high power levels using conventional D.C. power supplies, without the need for expensive arc diverter systems, or D.C. switching power supplies, or the Twin-Mag System where two targets are sequentially used as anode and cathode with a mid-frequency power supply, or any special requirements of a gas control system. Using the targets produced according to the present invention, D.C. sputtering can be carried out at power levels of up to 100Kw. The main consequence is that large target bases, e.g. rotatable 3.5 meters long and 150 mm in diameter can be coated up to a typical coating thickness of 6 mm.
- The targets produced by the process of the present invention do not suffer from significant arcing problems because titanium dioxide has a higher melting point than titanium metal for which so called “vapour arcing” is a problem due to the lower melting point of the metal. Even if some arcing does occur for titanium dioxide there is little accompanying damage to the target.
- The present invention will be further described with reference to the following Examples.
- A rotatable target, water cooled on the inside to 35° C., comprising a tube of stainless steel of diameter 133 mm and length 800 mm was coated to a thickness of from 4 to 10 mm with sub-stoichiometric titanium dioxide, TiOx, where x is below 2 as hereinbefore described by plasma spraying titanium dioxide (rutile) having a particle size of from 10 to 40 μm onto the target using argon as the primary plasma gas and hydrogen as the secondary plasma gas. 72 liters (60% argon, 40% hydrogen) were used. The power level was 45kW (455A, 96V).
- A commercial white pigment consisting of titanium dioxide in the anatase crystal form was used. This powder is stoichiometric and electrically insulating. The powder was mechanically agglomerated and compacted into flakes, ground, sieved (70-100 μm) and sintered at 1300° C. in air. The sintered body was then ground and sieved to a particle size of 10-40 μm. The particles were yellow stoichiometric, non-conductive, titanium dioxide with a rutile crystalline structure.
- A rotatable target comprising a backing tube of aluminium (2.50 m long and 133 mm 5 diameter) was prepared by plasma spraying of the above rutile powder using argon as the primary gas and hydrogen as the secondary gas. 75 liters (40% argon, 60% hydrogen) were used. The power level was 50kW (110V, 455A). The plasma spraying was carried out under a nitrogen atmosphere.
- The target was rotated at 100 rpm and the torch translation was 2.5 m/min until a coating 4 mm thick was obtained. The inside of the aluminium tube was water cooled to a temperature of 35° C. The coated target had a resistivity of 0.07 ohm.cm. The target was subsequently tested at power levels of up to 100kW and worked well in the sputtering equipment without significant arcing. The deposition of titanium dioxide was six times higher than the rate from a titanium metal target in reactive sputtering.
- Example 2 was repeated with a low pressure vacuum plasma operating at 200 mBar using titanium dioxide in the anatase form having a particle size in the range of from 1 to 10 μm. Using the low pressure plasma, powders with a smaller particle size can be used.
- On spraying onto a target base under the conditions of Example 2 the anatase was converted into a sub-stoichiometric rutile form of titanium dioxide. The coated target had a resistivity of 0.02 ohm.cm.
- A mixture of niobium oxide (25 parts by weight) and titanium dioxide (75 parts by weight) having a particle size of from 0.1 to 2 μm was agglomerated and compacted, dried and sintered at 1300° C. in air. The sintered body was then ground to a particle size of 10 to 40 μm.
- The powder mixture was then plasma sprayed under the conditions given in Example 2 onto an aluminium backing tube to a coating thickness of 4 mm. The coated target had an electrical resistivity of 0.5 ohm.cm and thus could be used as a D.C. sputtering target.
Claims (14)
1. A process for the preparation of a sputtering target which comprises sub-stoichiometric titanium dioxide, TiOx, where x is below 2 having an electrical resistivity of less than 0.5 ohm.cm, optionally together with niobium oxide, which process comprises plasma spraying titanium dioxide, TiO2, optionally together with niobium oxide, onto a target base in an atmosphere which is oxygen deficient and which does not contain oxygen-containing compounds, the target base being coated with TiOx which is solidified by cooling under conditions which prevent the sub-stoichiometric titanium dioxide from combining with oxygen.
2. A process as claimed in claim 1 wherein the target base is water cooled during the plasma spraying.
3. A process as claimed in claim 1 or claim 2 wherein the plasma spraying is carried out using argon as the plasma gas and hydrogen as the secondary plasma gas.
4. A process as claimed in any one of the preceding claims wherein the target base is titanium, stainless steel, aluminium or copper.
5. A process as claimed in claim 4 wherein the target base is a rotatable target or a flat magnetron target.
6. A process as claimed in any one of the preceding claims wherein the titanium dioxide which is plasma sprayed has particle size in the range of from 1 to 60 micrometers.
7. A process as claimed in any one of the preceding claims wherein the titanium dioxide is plasma sprayed together with Nb2O3.
8. A process as claimed in any one of the preceding claims wherein the sub-stoichiometric titanium dioxide, TiOx, has a value of x in the range of from 1.55 to 1.95.
9. A process as claimed in any one of the preceding claims wherein the sputtering target has an electrical resistivity of about 0.02 ohm.cm.
10. A sputtering target comprising sub-stoichiometric titanium dioxide whenever prepared by a process as claimed in any one of the preceding claims.
11. A sputtering target as claimed in claim 10 which has an electrical resistivity of about 0.02 ohm.cm.
12. A process for the preparation of sub-stoichiometric titanium dioxide, TiOx, where x is below 2 having an electrical resistivity of less than 0.1 ohm.cm which process comprises subjecting titanium dioxide to a plasma treatment in an atmosphere which is oxygen deficient and which does not contain any oxygen-containing compounds.
13. A process as claimed in claim 12 wherein the titanium dioxide is sprayed through a plasma flame having a temperature of above 2000° C.
14. A process as claimed in claim 13 wherein the plasma flame uses a mixture of hydrogen and argon as the plasma gas.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/008,949 US20020125129A1 (en) | 1996-01-05 | 2001-12-07 | Sputtering targets and method for the preparation thereof |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9600210.0 | 1996-01-05 | ||
GBGB9600210.0A GB9600210D0 (en) | 1996-01-05 | 1996-01-05 | Improved sputtering targets and method for the preparation thereof |
US2424098A | 1998-02-17 | 1998-02-17 | |
US09/759,661 US20010019738A1 (en) | 1996-01-05 | 2001-01-12 | Sputtering targets and method for the preparation thereof |
US10/008,949 US20020125129A1 (en) | 1996-01-05 | 2001-12-07 | Sputtering targets and method for the preparation thereof |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/759,661 Continuation US20010019738A1 (en) | 1996-01-05 | 2001-01-12 | Sputtering targets and method for the preparation thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
US20020125129A1 true US20020125129A1 (en) | 2002-09-12 |
Family
ID=10786662
Family Applications (11)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/101,405 Expired - Lifetime US6461686B1 (en) | 1996-01-05 | 1997-01-03 | Sputtering targets and method for the preparation thereof |
US09/589,098 Expired - Fee Related US6468402B1 (en) | 1996-01-05 | 2000-06-08 | Process for coating a substrate with titanium dioxide |
US09/759,661 Abandoned US20010019738A1 (en) | 1996-01-05 | 2001-01-12 | Sputtering targets and method for the preparation thereof |
US09/780,537 Abandoned US20010010288A1 (en) | 1996-01-05 | 2001-02-12 | Sputtering targets and method for the preparation thereof |
US09/899,581 Abandoned US20020071971A1 (en) | 1996-01-05 | 2001-07-05 | Process for coating a substrate with titanium dioxide |
US09/966,636 Abandoned US20020081465A1 (en) | 1996-01-05 | 2001-09-28 | Sputtering targets and method for the preparation thereof |
US10/032,901 Abandoned US20020127349A1 (en) | 1996-01-05 | 2001-10-19 | Sputtering targets and method for the preparation thereof |
US10/001,964 Expired - Fee Related US6511587B2 (en) | 1996-01-05 | 2001-12-05 | Sputtering targets and method for the preparation thereof |
US10/008,949 Abandoned US20020125129A1 (en) | 1996-01-05 | 2001-12-07 | Sputtering targets and method for the preparation thereof |
US10/417,413 Abandoned US20040069623A1 (en) | 1996-01-05 | 2003-04-17 | Sputtering targets and method for the preparation thereof |
US11/346,372 Abandoned US20060249373A1 (en) | 1996-01-05 | 2006-02-03 | Sputtering targets and method for the preparation thereof |
Family Applications Before (8)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/101,405 Expired - Lifetime US6461686B1 (en) | 1996-01-05 | 1997-01-03 | Sputtering targets and method for the preparation thereof |
US09/589,098 Expired - Fee Related US6468402B1 (en) | 1996-01-05 | 2000-06-08 | Process for coating a substrate with titanium dioxide |
US09/759,661 Abandoned US20010019738A1 (en) | 1996-01-05 | 2001-01-12 | Sputtering targets and method for the preparation thereof |
US09/780,537 Abandoned US20010010288A1 (en) | 1996-01-05 | 2001-02-12 | Sputtering targets and method for the preparation thereof |
US09/899,581 Abandoned US20020071971A1 (en) | 1996-01-05 | 2001-07-05 | Process for coating a substrate with titanium dioxide |
US09/966,636 Abandoned US20020081465A1 (en) | 1996-01-05 | 2001-09-28 | Sputtering targets and method for the preparation thereof |
US10/032,901 Abandoned US20020127349A1 (en) | 1996-01-05 | 2001-10-19 | Sputtering targets and method for the preparation thereof |
US10/001,964 Expired - Fee Related US6511587B2 (en) | 1996-01-05 | 2001-12-05 | Sputtering targets and method for the preparation thereof |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/417,413 Abandoned US20040069623A1 (en) | 1996-01-05 | 2003-04-17 | Sputtering targets and method for the preparation thereof |
US11/346,372 Abandoned US20060249373A1 (en) | 1996-01-05 | 2006-02-03 | Sputtering targets and method for the preparation thereof |
Country Status (12)
Country | Link |
---|---|
US (11) | US6461686B1 (en) |
EP (2) | EP0871794B1 (en) |
JP (3) | JP3980643B2 (en) |
KR (1) | KR100510609B1 (en) |
CN (2) | CN1727514A (en) |
AU (2) | AU716603B2 (en) |
BR (1) | BR9706954A (en) |
CA (1) | CA2241878C (en) |
DE (2) | DE69715592T2 (en) |
GB (1) | GB9600210D0 (en) |
IL (1) | IL125103A0 (en) |
WO (2) | WO1997025450A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040115362A1 (en) * | 2002-01-14 | 2004-06-17 | Klause Hartig | Photocatalytic sputtering targets and methods for the production and use thereof |
US20080280078A1 (en) * | 2006-06-30 | 2008-11-13 | Krisko Annette J | Carbon nanotube glazing technology |
Families Citing this family (76)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1452622A3 (en) | 1995-08-23 | 2004-09-29 | Asahi Glass Ceramics Co., Ltd. | Target and process for its production, and method for forming a film having a high refractive index |
GB9600210D0 (en) * | 1996-01-05 | 1996-03-06 | Vanderstraeten E Bvba | Improved sputtering targets and method for the preparation thereof |
US6262850B1 (en) | 1998-11-03 | 2001-07-17 | Cardinal Glass Industries, Inc. | Heat-treatable dichroic mirrors |
US6292302B1 (en) * | 1998-11-03 | 2001-09-18 | Cardinal Glass Industries, Inc. | Heat-treatable dichroic mirrors |
WO2000037377A1 (en) † | 1998-12-21 | 2000-06-29 | Cardinal Ig Company | Soil-resistant coating for glass surfaces |
DE19958424C2 (en) * | 1999-12-03 | 2002-05-29 | Zentrum Fuer Material Und Umwe | Atomization target for thin coating of large-area substrates and process for its production |
CN1158403C (en) * | 1999-12-23 | 2004-07-21 | 西南交通大学 | Process for modifying surface of artificial organ |
AU2001241144A1 (en) | 2000-03-22 | 2001-10-03 | Nippon Sheet Glass Co. Ltd. | Substrate with photocatalytic film and method for producing the same |
JP3708429B2 (en) * | 2000-11-30 | 2005-10-19 | Hoya株式会社 | Method for manufacturing vapor deposition composition, method for manufacturing optical component having vapor deposition composition and antireflection film |
WO2002057508A2 (en) * | 2001-01-17 | 2002-07-25 | N.V. Bekaert S.A. | Method for the production of sputtering targets |
DE10140514A1 (en) | 2001-08-17 | 2003-02-27 | Heraeus Gmbh W C | Sputtering target based on titanium dioxide |
US20040240093A1 (en) * | 2001-10-18 | 2004-12-02 | Masato Yoshikawa | Optical element and production method therefor, and band pass filter, near infrared cut filter and anti-reflection film |
US7067195B2 (en) | 2002-04-29 | 2006-06-27 | Cardinal Cg Company | Coatings having low emissivity and low solar reflectance |
KR20020077852A (en) * | 2002-08-30 | 2002-10-14 | 주식회사 새롬원 | Glass board members for anti-contamination |
AU2003301622A1 (en) * | 2002-10-24 | 2004-05-13 | Honeywell International Inc | Target designs and related methods for enhanced cooling and reduced deflection and deformation |
US20040149307A1 (en) * | 2002-12-18 | 2004-08-05 | Klaus Hartig | Reversible self-cleaning window assemblies and methods of use thereof |
DE10320472A1 (en) * | 2003-05-08 | 2004-12-02 | Kolektor D.O.O. | Plasma treatment for cleaning copper or nickel |
US6915095B2 (en) * | 2003-06-16 | 2005-07-05 | Xerox Corporation | Charging member having titanium oxide outer coating on grit blasted substrate |
US20050092599A1 (en) * | 2003-10-07 | 2005-05-05 | Norm Boling | Apparatus and process for high rate deposition of rutile titanium dioxide |
DE10359508B4 (en) * | 2003-12-18 | 2007-07-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method and apparatus for magnetron sputtering |
CA2550331A1 (en) * | 2003-12-22 | 2005-07-14 | Cardinal Cg Compagny | Graded photocatalytic coatings |
WO2005082610A1 (en) | 2004-02-25 | 2005-09-09 | Afg Industries, Inc. | Heat stabilized sub-stoichiometric dielectrics |
JPWO2005100013A1 (en) * | 2004-04-06 | 2008-03-06 | 帝人デュポンフィルム株式会社 | Antireflection film |
EP1780299A4 (en) * | 2004-06-29 | 2008-03-12 | Pioneer Corp | Sputtering target for thin film formation, dielectric thin film, optical disk, and process for producing the same |
DE102004032635A1 (en) * | 2004-07-06 | 2006-02-09 | Gfe Metalle Und Materialien Gmbh | Process for producing a titanium-suboxide-based coating material, correspondingly produced coating material and sputtering target provided therewith |
US7713632B2 (en) | 2004-07-12 | 2010-05-11 | Cardinal Cg Company | Low-maintenance coatings |
CA2575586A1 (en) * | 2004-08-10 | 2006-02-23 | Cardinal Cg Company | Lcd mirror system and method |
EP1797017B1 (en) * | 2004-10-04 | 2010-11-24 | Cardinal CG Company | Thin film coating and temporary protection technology, insulating glazing units, and associated methods |
US7923114B2 (en) | 2004-12-03 | 2011-04-12 | Cardinal Cg Company | Hydrophilic coatings, methods for depositing hydrophilic coatings, and improved deposition technology for thin films |
US8092660B2 (en) | 2004-12-03 | 2012-01-10 | Cardinal Cg Company | Methods and equipment for depositing hydrophilic coatings, and deposition technologies for thin films |
US7968216B2 (en) * | 2005-01-08 | 2011-06-28 | Toyoda Gosei Co., Ltd. | Internal gear pump |
US7442933B2 (en) * | 2005-02-03 | 2008-10-28 | Lin Alice L | Bolometer having an amorphous titanium oxide layer with high resistance stability |
FR2881757B1 (en) * | 2005-02-08 | 2007-03-30 | Saint Gobain | THERMAL PROJECTION DEVELOPING METHOD OF TARGET BASED ON SILICON AND ZIRCONIUM |
US8053048B2 (en) * | 2005-04-25 | 2011-11-08 | Baxter International Inc. | Overpouch film and container and method of making same |
DE102005029952B3 (en) * | 2005-06-28 | 2007-01-11 | Lanxess Deutschland Gmbh | Leveling bracket |
US7342716B2 (en) | 2005-10-11 | 2008-03-11 | Cardinal Cg Company | Multiple cavity low-emissivity coatings |
CA2626073A1 (en) * | 2005-11-01 | 2007-05-10 | Cardinal Cg Company | Reactive sputter deposition processes and equipment |
US20070134500A1 (en) * | 2005-12-14 | 2007-06-14 | Klaus Hartig | Sputtering targets and methods for depositing film containing tin and niobium |
CN101466649B (en) | 2006-04-11 | 2013-12-11 | 卡迪奈尔镀膜玻璃公司 | Photocatalytic coatings having improved low-maintenance properties |
JP2009534563A (en) | 2006-04-19 | 2009-09-24 | 日本板硝子株式会社 | Opposing functional coating with equivalent single surface reflectivity |
DE102006027029B4 (en) * | 2006-06-09 | 2010-09-30 | W.C. Heraeus Gmbh | Sputtering target with a sputtering material based on TiO2 and manufacturing process |
US20070289869A1 (en) * | 2006-06-15 | 2007-12-20 | Zhifei Ye | Large Area Sputtering Target |
US20080011599A1 (en) | 2006-07-12 | 2008-01-17 | Brabender Dennis M | Sputtering apparatus including novel target mounting and/or control |
EP2408268A1 (en) * | 2006-11-17 | 2012-01-18 | Saint-Gobain Glass France | Electrode for an organic light-emitting device, acid etching thereof, and organic light-emitting device incorporating it |
US7807248B2 (en) * | 2007-08-14 | 2010-10-05 | Cardinal Cg Company | Solar control low-emissivity coatings |
US7622717B2 (en) * | 2007-08-22 | 2009-11-24 | Drs Sensors & Targeting Systems, Inc. | Pixel structure having an umbrella type absorber with one or more recesses or channels sized to increase radiation absorption |
KR101563197B1 (en) | 2007-09-14 | 2015-10-26 | 카디날 씨지 컴퍼니 | Low-maintenance coatings and methods for producing low-maintenance coatings |
US7655274B2 (en) † | 2007-11-05 | 2010-02-02 | Guardian Industries Corp. | Combustion deposition using aqueous precursor solutions to deposit titanium dioxide coatings |
JP4993745B2 (en) * | 2007-12-28 | 2012-08-08 | 株式会社アルバック | Deposition equipment |
US20130026535A1 (en) * | 2011-07-26 | 2013-01-31 | Battelle Energy Alliance, Llc | Formation of integral composite photon absorber layer useful for photoactive devices and sensors |
US9371226B2 (en) | 2011-02-02 | 2016-06-21 | Battelle Energy Alliance, Llc | Methods for forming particles |
US8951446B2 (en) | 2008-03-13 | 2015-02-10 | Battelle Energy Alliance, Llc | Hybrid particles and associated methods |
US8003070B2 (en) * | 2008-03-13 | 2011-08-23 | Battelle Energy Alliance, Llc | Methods for forming particles from single source precursors |
US8324414B2 (en) | 2009-12-23 | 2012-12-04 | Battelle Energy Alliance, Llc | Methods of forming single source precursors, methods of forming polymeric single source precursors, and single source precursors and intermediate products formed by such methods |
EP2116631A1 (en) * | 2008-04-30 | 2009-11-11 | Applied Materials, Inc. | Sputter target |
US20090272641A1 (en) * | 2008-04-30 | 2009-11-05 | Applied Materials, Inc. | Sputter target, method for manufacturing a layer, particularly a tco (transparent conductive oxide) layer, and method for manufacturing a thin layer solar cell |
JP5624712B2 (en) * | 2008-09-01 | 2014-11-12 | 豊田合成株式会社 | Manufacturing method of conductive transparent layer made of TiO2 and manufacturing method of semiconductor light emitting device using manufacturing method of said conductive transparent layer |
JP2010231172A (en) * | 2009-03-04 | 2010-10-14 | Seiko Epson Corp | Optical article and method for producing the same |
FR2944293B1 (en) * | 2009-04-10 | 2012-05-18 | Saint Gobain Coating Solutions | THERMAL PROJECTION DEVELOPING METHOD OF A TARGET |
JP5588135B2 (en) * | 2009-08-10 | 2014-09-10 | ホーヤ レンズ マニュファクチャリング フィリピン インク | Method for manufacturing optical article |
JP2012032690A (en) | 2010-08-02 | 2012-02-16 | Seiko Epson Corp | Optical article and manufacturing method thereof |
DE102010048089B4 (en) * | 2010-10-01 | 2016-09-01 | Carl Zeiss Vision International Gmbh | A method of producing a multilayer antistatic coating for a lens element |
CN103814151B (en) | 2011-06-27 | 2016-01-20 | 梭莱有限公司 | PVD target and castmethod thereof |
CN102286717B (en) * | 2011-09-01 | 2013-07-03 | 基迈克材料科技(苏州)有限公司 | Cylindrical large-area film coating target prepared through plasma spray coating and method |
DE102011116062A1 (en) * | 2011-10-18 | 2013-04-18 | Sintertechnik Gmbh | Ceramic product for use as a target |
EP2613358A2 (en) * | 2012-01-04 | 2013-07-10 | OC Oerlikon Balzers AG | Double layer antireflection coating for silicon based solar cell modules |
DE102012112739A1 (en) * | 2012-10-23 | 2014-04-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Light-absorbing layer system and its production as well as a suitable sputtering target |
DE102012022237A1 (en) * | 2012-11-14 | 2014-05-15 | Heraeus Materials Technology Gmbh & Co. Kg | Sputtering target with optimized usage properties |
WO2014122120A1 (en) * | 2013-02-05 | 2014-08-14 | Soleras Advanced Coatings Bvba | (ga) zn sn oxide sputtering target |
RU2013158730A (en) * | 2013-12-27 | 2015-07-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Самарский государственный аэрокосмический университет имени академика С.П. Королева" (национальный исследовательский университет)" (СГАУ) | METHOD FOR PRODUCING A CATHODE TARGET FOR SPRAYING CERAMIC MATERIALS |
JP5784849B2 (en) * | 2015-01-21 | 2015-09-24 | 三井金属鉱業株式会社 | Ceramic cylindrical sputtering target material and manufacturing method thereof |
US10604442B2 (en) | 2016-11-17 | 2020-03-31 | Cardinal Cg Company | Static-dissipative coating technology |
PL3375904T3 (en) * | 2017-03-14 | 2022-10-10 | Materion Advanced Materials Germany Gmbh | Cylindrical titanium oxide sputtering target and process for manufacturing the same |
DE102017118172A1 (en) * | 2017-08-09 | 2019-02-14 | Forplan AG | Coating method, coating device for carrying out this method and coating system with such a coating device |
CN110257790B (en) * | 2019-07-29 | 2020-07-03 | 福建阿石创新材料股份有限公司 | Aluminum oxide-TiOxTarget material and preparation method and application thereof |
WO2023097583A1 (en) * | 2021-12-01 | 2023-06-08 | 宁德时代新能源科技股份有限公司 | Doped nickel oxide target material, and preparation method therefor and use thereof |
Family Cites Families (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US232680A (en) | 1880-09-28 | Peters | ||
US1231280A (en) | 1916-11-16 | 1917-06-26 | John F Metten | Safety-valve. |
US1438462A (en) | 1919-04-17 | 1922-12-12 | Skf Svenska Kullagerfab Ab | Shock indicator |
US1595061A (en) | 1922-10-17 | 1926-08-03 | Valerius Johann | Electric cut-out |
GB232680A (en) | 1924-01-23 | 1925-04-23 | Metal & Thermit Corp | Improvements in the production of a form of titanium oxide |
US3616445A (en) | 1967-12-14 | 1971-10-26 | Electronor Corp | Titanium or tantalum base electrodes with applied titanium or tantalum oxide face activated with noble metals or noble metal oxides |
DE2300422C3 (en) * | 1973-01-05 | 1981-10-15 | Hoechst Ag, 6000 Frankfurt | Method of making an electrode |
DE2405010C3 (en) | 1974-02-02 | 1982-08-05 | Sigri Elektrographit Gmbh, 8901 Meitingen | Sintered electrode for electrochemical processes and methods of manufacturing the electrode |
GB1595061A (en) * | 1976-11-22 | 1981-08-05 | Atomic Energy Authority Uk | Electrically conductive layers produced by plasma spraying |
DE2752875C2 (en) | 1977-11-26 | 1986-05-15 | Sigri GmbH, 8901 Meitingen | Electrode for electrochemical processes and processes for their production |
GB2028376B (en) | 1978-08-23 | 1982-11-03 | Ppg Industries Inc | Electrically conductive coatings |
US4216259A (en) | 1979-01-02 | 1980-08-05 | Bfg Glassgroup | Heat reflecting pane and a method of producing it |
US4422917A (en) * | 1980-09-10 | 1983-12-27 | Imi Marston Limited | Electrode material, electrode and electrochemical cell |
DE3039821A1 (en) * | 1980-10-22 | 1982-06-03 | Robert Bosch Gmbh, 7000 Stuttgart | MULTI-LAYER SYSTEM FOR HEAT PROTECTION APPLICATION |
US4336119A (en) | 1981-01-29 | 1982-06-22 | Ppg Industries, Inc. | Method of and apparatus for control of reactive sputtering deposition |
US4422916A (en) * | 1981-02-12 | 1983-12-27 | Shatterproof Glass Corporation | Magnetron cathode sputtering apparatus |
US5126218A (en) | 1985-04-23 | 1992-06-30 | Clarke Robert L | Conductive ceramic substrate for batteries |
JPS62161945A (en) * | 1985-08-20 | 1987-07-17 | Toyo Soda Mfg Co Ltd | Production of ceramic sputtering target |
JPS63178474A (en) | 1987-01-19 | 1988-07-22 | 日立金属株式会社 | Heater radiating long wavwlength infrared radiation |
US4931213A (en) | 1987-01-23 | 1990-06-05 | Cass Richard B | Electrically-conductive titanium suboxides |
JPH0812302B2 (en) * | 1987-11-02 | 1996-02-07 | 株式会社日立製作所 | Method for producing titanium oxide thin film |
US5618388A (en) * | 1988-02-08 | 1997-04-08 | Optical Coating Laboratory, Inc. | Geometries and configurations for magnetron sputtering apparatus |
US4861680A (en) | 1988-02-11 | 1989-08-29 | Southwall Technologies | Bronze-grey glazing film and window made therefrom |
US5354446A (en) * | 1988-03-03 | 1994-10-11 | Asahi Glass Company Ltd. | Ceramic rotatable magnetron sputtering cathode target and process for its production |
US5605609A (en) | 1988-03-03 | 1997-02-25 | Asahi Glass Company Ltd. | Method for forming low refractive index film comprising silicon dioxide |
US5196400A (en) * | 1990-08-17 | 1993-03-23 | At&T Bell Laboratories | High temperature superconductor deposition by sputtering |
US5105310A (en) | 1990-10-11 | 1992-04-14 | Viratec Thin Films, Inc. | Dc reactively sputtered antireflection coatings |
US5100527A (en) * | 1990-10-18 | 1992-03-31 | Viratec Thin Films, Inc. | Rotating magnetron incorporating a removable cathode |
US5616263A (en) * | 1992-11-09 | 1997-04-01 | American Roller Company | Ceramic heater roller |
US5589280A (en) | 1993-02-05 | 1996-12-31 | Southwall Technologies Inc. | Metal on plastic films with adhesion-promoting layer |
US5489369A (en) | 1993-10-25 | 1996-02-06 | Viratec Thin Films, Inc. | Method and apparatus for thin film coating an article |
GB9324069D0 (en) | 1993-11-23 | 1994-01-12 | Glaverbel | A glazing unit and a method for its manufacture |
US5451457A (en) | 1993-12-20 | 1995-09-19 | Libbey-Owens-Ford Co. | Method and material for protecting glass surfaces |
JPH07215074A (en) | 1994-02-07 | 1995-08-15 | Toyota Motor Corp | Under-cover device for vehicle |
JP3836163B2 (en) * | 1994-02-22 | 2006-10-18 | 旭硝子セラミックス株式会社 | Method for forming high refractive index film |
US5616225A (en) | 1994-03-23 | 1997-04-01 | The Boc Group, Inc. | Use of multiple anodes in a magnetron for improving the uniformity of its plasma |
JPH08134638A (en) | 1994-11-04 | 1996-05-28 | Asahi Glass Co Ltd | Formation of titanium oxide film |
US5593786A (en) | 1994-11-09 | 1997-01-14 | Libbey-Owens-Ford Company | Self-adhering polyvinyl chloride safety glass interlayer |
DE4441206C2 (en) | 1994-11-19 | 1996-09-26 | Leybold Ag | Device for the suppression of rollovers in cathode sputtering devices |
US5574079A (en) | 1994-12-21 | 1996-11-12 | Union Carbide Chemicals & Plastics Technology Corporation | Method for the preparation of water-borne coating compositions using thermoplastic polyhydroxyether resins having narrow polydispersity |
EP0753882B1 (en) | 1995-07-08 | 1998-11-18 | Balzers und Leybold Deutschland Holding Aktiengesellschaft | Cathode assembly for a target sputtering device |
US6455141B1 (en) | 1995-07-24 | 2002-09-24 | Southwall Technologies Inc. | Laminate structure and process for its production |
US5743931A (en) | 1995-08-14 | 1998-04-28 | Libbey-Owens-Ford Co. | Glass sheet conveying and bending apparatus |
EP1452622A3 (en) * | 1995-08-23 | 2004-09-29 | Asahi Glass Ceramics Co., Ltd. | Target and process for its production, and method for forming a film having a high refractive index |
JPH09189801A (en) | 1996-01-09 | 1997-07-22 | Shin Etsu Chem Co Ltd | Optical parts with heat resistant antireflection film |
GB9600210D0 (en) * | 1996-01-05 | 1996-03-06 | Vanderstraeten E Bvba | Improved sputtering targets and method for the preparation thereof |
WO1997025201A1 (en) | 1996-01-11 | 1997-07-17 | Libbey-Owens-Ford Co. | Coated glass article having a solar control coating |
-
1996
- 1996-01-05 GB GBGB9600210.0A patent/GB9600210D0/en active Pending
-
1997
- 1997-01-03 WO PCT/EP1997/000021 patent/WO1997025450A1/en active IP Right Grant
- 1997-01-03 BR BR9706954-0A patent/BR9706954A/en not_active IP Right Cessation
- 1997-01-03 IL IL12510397A patent/IL125103A0/en unknown
- 1997-01-03 CN CNA2005100713029A patent/CN1727514A/en active Pending
- 1997-01-03 EP EP97900954A patent/EP0871794B1/en not_active Revoked
- 1997-01-03 AU AU14390/97A patent/AU716603B2/en not_active Ceased
- 1997-01-03 CN CNB971925933A patent/CN1208495C/en not_active Expired - Fee Related
- 1997-01-03 WO PCT/EP1997/000020 patent/WO1997025451A1/en active IP Right Grant
- 1997-01-03 JP JP52484697A patent/JP3980643B2/en not_active Expired - Fee Related
- 1997-01-03 EP EP97900563A patent/EP0871792B1/en not_active Expired - Lifetime
- 1997-01-03 KR KR10-1998-0705120A patent/KR100510609B1/en not_active IP Right Cessation
- 1997-01-03 US US09/101,405 patent/US6461686B1/en not_active Expired - Lifetime
- 1997-01-03 JP JP52484597A patent/JP4087447B2/en not_active Expired - Fee Related
- 1997-01-03 CA CA002241878A patent/CA2241878C/en not_active Expired - Fee Related
- 1997-01-03 AU AU13100/97A patent/AU1310097A/en not_active Abandoned
- 1997-01-03 DE DE69715592T patent/DE69715592T2/en not_active Revoked
- 1997-01-03 DE DE69723053T patent/DE69723053T2/en not_active Expired - Lifetime
-
2000
- 2000-06-08 US US09/589,098 patent/US6468402B1/en not_active Expired - Fee Related
-
2001
- 2001-01-12 US US09/759,661 patent/US20010019738A1/en not_active Abandoned
- 2001-02-12 US US09/780,537 patent/US20010010288A1/en not_active Abandoned
- 2001-07-05 US US09/899,581 patent/US20020071971A1/en not_active Abandoned
- 2001-09-28 US US09/966,636 patent/US20020081465A1/en not_active Abandoned
- 2001-10-19 US US10/032,901 patent/US20020127349A1/en not_active Abandoned
- 2001-12-05 US US10/001,964 patent/US6511587B2/en not_active Expired - Fee Related
- 2001-12-07 US US10/008,949 patent/US20020125129A1/en not_active Abandoned
-
2003
- 2003-04-17 US US10/417,413 patent/US20040069623A1/en not_active Abandoned
-
2006
- 2006-02-03 US US11/346,372 patent/US20060249373A1/en not_active Abandoned
-
2007
- 2007-08-27 JP JP2007219854A patent/JP2007314892A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040115362A1 (en) * | 2002-01-14 | 2004-06-17 | Klause Hartig | Photocatalytic sputtering targets and methods for the production and use thereof |
US20080280078A1 (en) * | 2006-06-30 | 2008-11-13 | Krisko Annette J | Carbon nanotube glazing technology |
US7754336B2 (en) | 2006-06-30 | 2010-07-13 | Cardinal Cg Company | Carbon nanotube glazing technology |
US20100247820A1 (en) * | 2006-06-30 | 2010-09-30 | Cardinal Cg Company | Carbon nanotube glazing technology |
EP2279986A2 (en) | 2006-06-30 | 2011-02-02 | Cardinal CG Company | Carbon nanotube coating technology |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6511587B2 (en) | Sputtering targets and method for the preparation thereof | |
US6334938B2 (en) | Target and process for its production, and method for forming a film having a high refractive index | |
EP0636589B1 (en) | Sources for deposition of silicon oxide | |
US7431808B2 (en) | Sputter target based on titanium dioxide | |
Löbl et al. | ITO films for antireflective and antistatic tube coatings prepared by dc magnetron sputtering | |
US20040115362A1 (en) | Photocatalytic sputtering targets and methods for the production and use thereof | |
EP1352105A2 (en) | Photocatalytic sputtering targets and methods for the production and use thereof | |
MXPA98005470A (en) | Scurring objectives and method for the preparation of the mis | |
JPH0726370A (en) | Target, its production and film formed by using the target |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |