WO1997025451A1 - Sputtering targets and method for the preparation thereof - Google Patents

Sputtering targets and method for the preparation thereof Download PDF

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Publication number
WO1997025451A1
WO1997025451A1 PCT/EP1997/000020 EP9700020W WO9725451A1 WO 1997025451 A1 WO1997025451 A1 WO 1997025451A1 EP 9700020 W EP9700020 W EP 9700020W WO 9725451 A1 WO9725451 A1 WO 9725451A1
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Prior art keywords
titanium dioxide
plasma
target
sub
oxygen
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PCT/EP1997/000020
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French (fr)
Inventor
Johan Emile Marie Vanderstraeten
Original Assignee
Bvba Vanderstraeten E
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Priority to IL12510397A priority Critical patent/IL125103A0/en
Priority to BR9706954-0A priority patent/BR9706954A/en
Priority to US09/101,405 priority patent/US6461686B1/en
Application filed by Bvba Vanderstraeten E filed Critical Bvba Vanderstraeten E
Priority to CA002241878A priority patent/CA2241878C/en
Priority to AU14390/97A priority patent/AU716603B2/en
Priority to JP52484597A priority patent/JP4087447B2/en
Priority to EP97900954A priority patent/EP0871794B1/en
Priority to DE69715592T priority patent/DE69715592T2/en
Publication of WO1997025451A1 publication Critical patent/WO1997025451A1/en
Priority to US09/759,661 priority patent/US20010019738A1/en
Priority to US09/899,581 priority patent/US20020071971A1/en
Priority to US09/966,636 priority patent/US20020081465A1/en
Priority to US10/032,901 priority patent/US20020127349A1/en
Priority to US10/417,413 priority patent/US20040069623A1/en
Priority to US11/346,372 priority patent/US20060249373A1/en

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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
  • 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 ⁇ 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 Zr0 2 , TiO-., Si0 2 , Ta 2 0 3 , Al 2 0 3 , Fe-0 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 a 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, ⁇ i° 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, Ti0 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 ⁇ which is solidified by cooling under conditions which prevent the sub- stoichiometric titanium dioxide from combining with oxygen.
  • Sub-stoichiometric titanium dioxide, TiO ⁇ , 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.
  • Ti0 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 micrometres, preferably in the range of from 1 to 20 micrometres.
  • 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 Ti0 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 ⁇ , 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 lOOKw.
  • large target bases e.g. rotatable 3.5 metres long and 150mm in diameter can be coated up to a typical coating thickness of 6mm.
  • 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 133mm and length 800mm was coated to a thickness of from 4 to 10mm with sub-stoichiometric titanium dioxide, TiO ⁇ , 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 litres (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 (2.50m long and 133mm diameter) was prepared by plasma spraying of the above rutile powder using argon as the primary gas and hydrogen as the secondary gas.
  • 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 2.5m/min until a coating 4mm 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 lOOkW 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 Bar using titanium dioxide in the anatase form having a particle size in the range of from 1 to lO ⁇ . 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 4mm.
  • the coated target had an electrical resistivity of 0.5 ohm.cm and thus could be used as a D.C. sputtering target.

Abstract

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.

Description

SPUTTERING TARGETS AND METHOD FOR THE PREPARATION THEREOF
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 TiOχ 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 Zr02, TiO-., Si02, Ta203, Al203, Fe-03 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 TiO_, 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 a 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, τi°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, Ti02, 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 TiOχ which is solidified by cooling under conditions which prevent the sub- stoichiometric titanium dioxide from combining with oxygen.
Sub-stoichiometric titanium dioxide, TiOχ, 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, Ti02 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 micrometres, preferably in the range of from 1 to 20 micrometres. 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 Ti02. 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, TiOχ, 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 lOOKw. The main consequence is that large target bases, e.g. rotatable 3.5 metres long and 150mm in diameter can be coated up to a typical coating thickness of 6mm. 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.
EXAMPLE 1
A rotatable target, water cooled on the inside to 35°C, comprising a tube of stainless steel of diameter 133mm and length 800mm was coated to a thickness of from 4 to 10mm with sub-stoichiometric titanium dioxide, TiOχ, where x is below 2 as hereinbefore described by plasma spraying titanium dioxide (rutile) having a particle size of from 10 to 40μm onto the target using argon as the primary plasma gas and hydrogen as the secondary plasma gas. 72 litres (60% argon, 40% hydrogen) were used. The power level was 45kW (455A, 96V) .
EXAMPLE 2
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 10-40μm. The particles were yellow stoichiometric, non-conductive, titanium dioxide with a rutile crystalline structure. A rotatable target comprising a backing tube of aluminium (2.50m long and 133mm diameter) was prepared by plasma spraying of the above rutile powder using argon as the primary gas and hydrogen as the secondary gas. 75 litres (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 2.5m/min until a coating 4mm 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 lOOkW 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 3
Example 2 was repeated with a low pressure vacuum plasma operating at 200 Bar using titanium dioxide in the anatase form having a particle size in the range of from 1 to lOμ . 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.
EXAMPLE 4
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 2μm 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 40μm.
The powder mixture was then plasma sprayed under the conditions given in Example 2 onto an aluminium backing tube to a coating thickness of 4mm. The coated target had an electrical resistivity of 0.5 ohm.cm and thus could be used as a D.C. sputtering target.

Claims

CLAIMS :
1. A process for the preparation of a sputtering target which comprises sub-stoichiometric titanium dioxide, TiOχ, 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, Ti02, 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 TiOχ 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 micrometres.
7. A process as claimed in any one of the preceding claims wherein the titanium dioxide is plasma sprayed together with Nb203.
8. A process as claimed in any one of the preceding claims wherein the sub-stoichiometric titanium dioxide, TiOχ, 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, TiOχ, 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.
PCT/EP1997/000020 1996-01-05 1997-01-03 Sputtering targets and method for the preparation thereof WO1997025451A1 (en)

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DE69715592T DE69715592T2 (en) 1996-01-05 1997-01-03 SPUTTER TARGETS AND METHOD FOR THE PRODUCTION THEREOF
AU14390/97A AU716603B2 (en) 1996-01-05 1997-01-03 Sputtering targets and method for the preparation thereof
BR9706954-0A BR9706954A (en) 1996-01-05 1997-01-03 Spray targets and method for their preparation
US09/101,405 US6461686B1 (en) 1996-01-05 1997-01-03 Sputtering targets and method for the preparation thereof
EP97900954A EP0871794B1 (en) 1996-01-05 1997-01-03 Sputtering targets and method for the preparation thereof
CA002241878A CA2241878C (en) 1996-01-05 1997-01-03 Sputtering targets and method for the preparation thereof
JP52484597A JP4087447B2 (en) 1996-01-05 1997-01-03 Sputtering target and manufacturing method thereof
IL12510397A IL125103A0 (en) 1996-01-05 1997-01-03 Sputtering targets and method for the preparation thereof
US09/759,661 US20010019738A1 (en) 1996-01-05 2001-01-12 Sputtering targets and method for the preparation thereof
US09/899,581 US20020071971A1 (en) 1996-01-05 2001-07-05 Process for coating a substrate with titanium dioxide
US09/966,636 US20020081465A1 (en) 1996-01-05 2001-09-28 Sputtering targets and method for the preparation thereof
US10/032,901 US20020127349A1 (en) 1996-01-05 2001-10-19 Sputtering targets and method for the preparation thereof
US10/417,413 US20040069623A1 (en) 1996-01-05 2003-04-17 Sputtering targets and method for the preparation thereof
US11/346,372 US20060249373A1 (en) 1996-01-05 2006-02-03 Sputtering targets and method for the preparation thereof

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GB9600210.0 1996-01-05
GBGB9600210.0A GB9600210D0 (en) 1996-01-05 1996-01-05 Improved sputtering targets and method for the preparation thereof

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US2424098A Continuation 1996-01-05 1998-02-17
US09/780,537 Continuation US20010010288A1 (en) 1996-01-05 2001-02-12 Sputtering targets and method for the preparation thereof

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EP (2) EP0871794B1 (en)
JP (3) JP3980643B2 (en)
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AU (2) AU716603B2 (en)
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CA2241878C (en) 2009-07-21
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US20010010288A1 (en) 2001-08-02
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US20040069623A1 (en) 2004-04-15
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US20020125129A1 (en) 2002-09-12
GB9600210D0 (en) 1996-03-06
AU1439097A (en) 1997-08-01
KR19990076990A (en) 1999-10-25
US6461686B1 (en) 2002-10-08
DE69723053D1 (en) 2003-07-31
CN1212026A (en) 1999-03-24
AU716603B2 (en) 2000-03-02
EP0871794B1 (en) 2002-09-18
US20020036135A1 (en) 2002-03-28
IL125103A0 (en) 1999-01-26
JP2000515929A (en) 2000-11-28
US20020071971A1 (en) 2002-06-13
US20020081465A1 (en) 2002-06-27
DE69723053T2 (en) 2004-05-19
EP0871792B1 (en) 2003-06-25
US20020127349A1 (en) 2002-09-12
DE69715592D1 (en) 2002-10-24
JP4087447B2 (en) 2008-05-21
CA2241878A1 (en) 1997-07-17
JP2000503070A (en) 2000-03-14
US20060249373A1 (en) 2006-11-09

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