CN109420758A - In-Cu alloy powder and its preparation method, In-Cu alloy sputtering targets and its preparation method - Google Patents
In-Cu alloy powder and its preparation method, In-Cu alloy sputtering targets and its preparation method Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 193
- 239000000843 powder Substances 0.000 title claims abstract description 158
- 238000005477 sputtering target Methods 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000001301 oxygen Substances 0.000 claims abstract description 96
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 45
- 229910052738 indium Inorganic materials 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000011261 inert gas Substances 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 238000000889 atomisation Methods 0.000 claims abstract description 14
- 230000008676 import Effects 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 70
- 239000000178 monomer Substances 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002441 X-ray diffraction Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 2
- 230000000803 paradoxical effect Effects 0.000 description 26
- 238000004544 sputter deposition Methods 0.000 description 21
- 239000010408 film Substances 0.000 description 17
- 229910052783 alkali metal Inorganic materials 0.000 description 15
- 150000001340 alkali metals Chemical class 0.000 description 15
- 150000001339 alkali metal compounds Chemical class 0.000 description 14
- 238000002347 injection Methods 0.000 description 14
- 239000007924 injection Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003754 machining Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000002159 abnormal effect Effects 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910052792 caesium Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 229910052701 rubidium Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- 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
Abstract
This application involves In-Cu alloy powder and its preparation methods, In-Cu alloy sputtering targets and its preparation method.The In-Cu alloy powder includes In and Cu and oxygen content is 1000 mass ppm or less.The manufacturing method of the In-Cu alloy powder has: vacuumizing process, the heatproof container for having put into the raw metal comprising In and Cu is made to reach 10Pa vacuum degree below；Process is melted, it is 50 volume ppm inert gases below that Xiang Suoshu heatproof container, which imports oxygen concentration, makes the inside of the heatproof container full of the inert gas, is heated to be 1100 DEG C or more then to melt the raw metal so that fused raw material is made；And atomization procedure, 700 DEG C or more at a temperature of with oxygen concentration be 50 volume ppm inert gases below the fused raw material is atomized.The In-Cu alloy sputtering targets are by comprising In and Cu and oxygen content is that 1000 mass ppm sintered bodies below are constituted.In the manufacturing method of In-Cu alloy sputtering targets, the raw material powder comprising the In-Cu alloy powder is sintered.
Description
Technical field
The present invention relates to a kind of In-Cu alloy sputtering targets used when forming the film of In-Cu alloy and its manufacturers
Method.Also, the present invention relates to the In-Cu alloy powders that one kind can be advantageously used when manufacturing the In-Cu alloy sputtering targets
And its manufacturing method.
Background technique
In the past, as the thin-film solar cells of compound semiconductor, one kind is provided extensively and has the conjunction of Cu-In-Ga-Se system
The CIGS-based solar battery of the light absorbing layer of gold.
Moreover it is known that there is a kind of method for forming the light absorbing layer by vapour deposition method.Have through vapour deposition method film forming
The energy conversion efficiency of the solar battery of light absorbing layer is high.But it is not easy on large area substrates equably using vapour deposition method
Film forming, this point consideration is manufactured from large-area substrates not easy to use, and production efficiency is low.
Therefore, as the method for being also formed uniformly light absorbing layer in large-area substrates, a kind of formed comprising In, Cu is provided
And Ga film or the film comprising these elements stacked film, and the film or stacked film are heat-treated in Se atmosphere
In the method for selenizing.Here, when forming film, using the sputtering method for having used the sputtering target containing each element.It is used to form packet
The sputtering target of film containing In and Cu is recorded in following documents.
A kind of Cu containing 0.5~7.5at% is recorded in patent document 1 and remainder is by In and inevitably miscellaneous
Texture at sputtering target.A kind of Cu containing 30~80 atom % is recorded in patent document 2 and remainder is by In and can not
The sputtering target that the impurity avoided is constituted.A kind of Cu containing 5wtppm~10000wtppm is recorded in patent document 3 and oxygen is dense
Degree is the sputtering target that 20wtppm or less and remainder are made of In.
Patent document 1: Japanese Unexamined Patent Publication 2012-052190 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2012-079997 bulletin
Patent document 3: International Publication No. 2015/004958
Manufacturing method in patent document 1,3 as sputtering target, which records, melts the alloy comprising In and Cu and to being obtained
The melting casting that is cast of molten metal.It is possible to melt because of the difference in specific gravity of In and Cu in casting however, melting
Melt the In and Cu segregation in metal and becomes larger there is a possibility that forming unevenness in sputtering target obtained.Especially sputtering is required recent
The enlargement of target, but melt in casting, size becomes bigger, and the molten metal used becomes more, therefore In and Cu is easy
Segregation, sputtering target obtained tend to generate composition unevenness.If the composition unevenness of sputtering target becomes larger, the sputtering target is used
The composition unevenness of the film of formation becomes larger, and as a result the composition unevenness of the light absorbing layer of solar battery becomes larger, and power generation is caused to be imitated
Rate decline.
On the other hand, in patent document 2 as sputtering target record it is a kind of to pure In target encapsulate target made of Cu chip and
In-Cu alloys target.However, In is separated from each other with Cu in the sputtering target through chip package, therefore it is not easy to be formed composition uniformly
Film.On the other hand, if manufacturing In-Cu alloys target by powder sintering, although composition can be prevented uneven, powder raw material contains
Oxygen amount is more, therefore the oxygen content in sputtering target increases, it is possible to which take place frequently paradoxical discharge in sputtering.
Summary of the invention
The present invention is completed in view of afore-mentioned, and its purpose is to provide one kind to splash in manufacture In-Cu alloy
The few In-Cu alloy powder of the In-Cu alloy powder i.e. oxygen content being advantageously used when shooting at the target and its manufacturing method.Also, this
A kind of paradoxical discharge when being designed to provide sputtering of invention few In-Cu alloy sputtering targets and its manufacturing method.
In order to solve the above problems, In-Cu alloy powder involved in a mode of the invention is characterized in that, includes In
And Cu and oxygen content are 1000 mass ppm or less.
In-Cu alloy powder involved in a mode of the invention according to this structure, oxygen content as little as 1000 mass
Ppm is hereinafter, therefore few and be not susceptible to abnormal put by that using the In-Cu alloy powder as raw material, can produce oxygen content
The In-Cu alloy sputtering targets of electricity.
Here, in In-Cu alloy powder involved in a mode of the invention, preferably median particle diameter D50 be 5 μm or more and
150 μm or less.
In this case, the median particle diameter D50 of In-Cu alloy powder is 5 μm or more and 150 μm hereinafter, therefore can will be by
The oxygen content of the In-Cu alloy sputtering targets of In-Cu alloy powder manufacture miniaturize crystal particles while maintaining low.Cause
This, is able to suppress crushing knife when machining, and is able to suppress the paradoxical discharge as caused by crushing knife trace.In addition, crystal particles
Possessed thickness of oxidation film is thinning, therefore is able to suppress the agglomeration generated when sputtering and particle.
Also, in In-Cu alloy powder involved in a mode of the invention, the ratio between preferably D10 and median particle diameter D50
D10/D50 be 1/2 hereinafter, or the ratio between D90 and median particle diameter D50 D90/D50 are 2 or more, or meet the two conditions simultaneously.
In this case, the width of the particle diameter distribution of In-Cu alloy powder is wide, therefore initially filling out when filling In-Cu powder
Density raising is filled, more highdensity sintered body can be obtained.
In addition, in In-Cu alloy powder involved in a mode of the invention, preferably have containing 45 atom % or more and
90 atom % In below and remainder is made of what Cu and inevitable impurity were constituted.
In this case, In-Cu alloy powder has containing 45 atom % or more and 90 atom % In below and remainder
Divide and is made of what Cu and inevitable impurity were constituted.Therefore, the In-Cu alloy sputtering targets manufactured by the In-Cu alloy powder
Tissue in form the Cu harder than In11In9Compound phase.This becomes the starting point destroyed, and adds so as to greatly improve cutting
Work.Further, it is possible to miniaturize the crystal particles of In-Cu alloy sputtering targets, to make its densification.
In addition, preferably there is In monomer phase and Cu in In-Cu alloy powder involved in a mode of the invention11In9Change
Close object phase, and the X-ray diffraction intensity I of the In monomer phaseInWith the Cu11In9The X-ray diffraction intensity of compound phase
ICu11In9Intensity ratio IIn/ICu11In9It is 0.01 or more and 3 or less.
In this case, also become identical phase structure by the In-Cu alloy sputtering targets that the In-Cu alloy powder manufactures, and
With In monomer phase and the Cu harder than In monomer phase11In9Compound phase, therefore machinability can be greatly improved.Also,
In monomer phase and Cu11In9The X-ray diffraction intensity ratio I of compound phaseIn/ICu11In9It is 0.01 or more and 3 or less.Therefore, extend
Property the excellent In monomer phase and Cu that becomes the starting point destroyed11In9Compound is mutually balanced to be existed, when so as to inhibit to process
Fracture and notch, and can reliably improve machinability.
The manufacturing method of In-Cu alloy powder involved in a mode of the invention is characterized in that having: vacuumizing work
Sequence makes the heatproof container for having put into the raw metal comprising In and Cu reach 10Pa vacuum degree below；Melt process, Xiang Suoshu
It is 50 volume ppm inert gases below that heatproof container, which imports oxygen concentration, so that the inside of the heatproof container is full of described lazy
Property gas, is heated to be 1100 DEG C or more then to melt the raw metal so that fused raw material is made；And atomization procedure, 700
DEG C or more at a temperature of with oxygen concentration be 50 volume ppm inert gases below the fused raw material is atomized.
The manufacturing method of In-Cu alloy powder involved in a mode of the invention according to this structure, by resistance to thermal capacitance
Device is evacuated to 10Pa hereinafter, being then directed into oxygen concentration is 50 volume ppm inert gases below, therefore can be greatly reduced resistance to
Oxygen amount inside heat container.Also, inside the heatproof container for significantly reducing oxygen amount, with 1100 DEG C or more of temperature to raw material
Metal carries out heating melting, further 700 DEG C or more at a temperature of with oxygen concentration be that 50 volume ppm inert gas below will
Fused raw material is atomized.Therefore, oxygen content can be obtained and be reduced to 1000 mass ppm In-Cu alloy powder below.
Here, in the manufacturing method of In-Cu alloy powder involved in a mode of the invention, the preferably described inert gas
For nitrogen.
In this case, it is believed that nitrogen is used as inert gas, therefore compared with the rare gas such as argon, possessed by gas
Thermal conductivity is high, therefore the cooling of fused raw material becomes faster, so as to further decrease the oxygen content of In-Cu alloy powder.
The manufacturing method of In-Cu alloy sputtering targets involved in a mode of the invention is characterized in that, to comprising above-mentioned
The raw material powder of In-Cu alloy powder is sintered.
The manufacturing method of In-Cu alloy sputtering targets involved in a mode of the invention according to this structure, to comprising
The raw material powder of the few In-Cu alloy powder of oxygen content is sintered, therefore it is few and be not susceptible to different to produce oxygen content
The sputtering target often to discharge.
In-Cu alloy sputtering targets involved in a mode of the invention are characterized in that, by including In and Cu and oxygen-containing
Amount is that 1000 mass ppm sintered body below is constituted.
In-Cu alloy sputtering targets involved in a mode of the invention according to this structure, oxygen content as little as 1000 matter
Ppm is measured hereinafter, being therefore able to suppress paradoxical discharge.
Here, in In-Cu alloy sputtering targets involved in a mode of the invention, preferably average crystal particle diameter be 5 μm with
It is upper and 150 μm or less.
In this case, average crystal particle diameter is 5 μm or more and 150 μm hereinafter, therefore can be by In-Cu alloy sputtering targets
Oxygen content miniaturize crystal particles while maintaining low.Therefore, it is able to suppress crushing knife when machining, and can be pressed down
Make the paradoxical discharge as caused by crushing knife trace.
Also, in In-Cu alloy sputtering targets involved in a mode of the invention, preferably has and contain 45 atom % or more
And 90 atom % In below and remainder be made of what Cu and inevitable impurity were constituted.
In this case, having containing 45 atom % or more and 90 atom % following range of In and remainder are by Cu and not
The composition that evitable impurity is constituted.Therefore, the Cu harder than In is formed in the tissue of In-Cu alloy sputtering targets11In9Chemical combination
Object phase, this becomes the starting point destroyed, so as to greatly improve machinability.Further, it is possible to make the crystal particles of sputtering target
Miniaturization, to make its densification.
In addition, preferably there is In monomer phase and Cu in In-Cu alloy sputtering targets involved in a mode of the invention11In9
Compound phase, and the X-ray diffraction intensity I of the In monomer phaseInWith the Cu11In9The X-ray diffraction intensity of compound phase
ICu11In9Intensity ratio IIn/ICu11In9It is 0.01 or more and 3 or less.
In this case, there are In monomer phase and the Cus harder than In monomer phase11In9Compound phase, therefore can substantially mention
High machinability.Also, In monomer phase and Cu11In9The X-ray diffraction intensity ratio I of compound phaseIn/ICu11In9For 0.01 with
It is upper and 3 or less.Therefore, the excellent In monomer phase of ductility and the Cu for becoming the starting point destroyed11In9Compound is mutually balanced to be existed,
So as to inhibit the fracture and notch when processing, and it can reliably improve machinability.
A mode according to the present invention is capable of providing a kind of In-Cu alloy powder that oxygen content is few and its manufacturing method.And
And a mode according to the present invention, a kind of paradoxical discharge when being capable of providing sputtering few In-Cu alloy sputtering targets and its manufacture
Method.
Detailed description of the invention
Fig. 1 is the flow chart for indicating the manufacturing method of In-Cu alloy powder involved in one embodiment of the present invention.
Fig. 2 is an example of the X-ray diffraction pattern of In-Cu alloy sputtering targets involved in one embodiment of the present invention.
Fig. 3 is an example of the structure observation photo of In-Cu alloy sputtering targets involved in one embodiment of the present invention.
Fig. 4 is the flow chart for indicating the manufacturing method of In-Cu alloy sputtering targets involved in one embodiment of the present invention.
Specific embodiment
Hereinafter, with reference to attached drawing to the In-Cu alloy powder of embodiments of the present invention, the manufacturer of In-Cu alloy powder
The manufacturing method of method, In-Cu alloy sputtering targets and In-Cu alloy sputtering targets is illustrated.
< In-Cu alloy powder >
In-Cu alloy powder involved in present embodiment includes In and Cu and oxygen content is 1000 mass ppm or less.More
Specifically, In-Cu alloy powder have containing 45 atom % or more and 90 atom % In below and remainder by Cu and
The composition that inevitable impurity is constituted.The median particle diameter D50 of In-Cu alloy powder is 5 μm or more and 150 μm hereinafter, D10 is
1/2 times or less of median particle diameter D50 or D90 for median particle diameter D50 2 times or more or meet the two conditions simultaneously.Also,
In-Cu alloy powder has In monomer phase and Cu11In9Compound phase, and In monomer phase and Cu11In9The peak of the XRD of compound phase
Value ratio IIn/ICu11In9It is 0.01 or more and 3 or less.
Hereinafter, being illustrated to the reasons why In-Cu alloy powder of regulation present embodiment as above.
(oxygen content: 1000 mass ppm or less)
If the oxygen content in In-Cu alloy powder is more than 1000 mass ppm, lead to the sputtering target manufactured using the powder
Oxygen content also above 1000 mass ppm, thus as caused by the oxide being present in tissue agglomeration and particle generation increase
Add, it is possible to be easy to happen paradoxical discharge.Therefore, in present embodiment, the oxygen content in In-Cu alloy powder is set as 1000
Quality ppm or less.
There is no particular restriction for the lower limit of oxygen content, but from needing partial size being set as excessive viewpoint in order to reduce oxygen to examine
Consider, for example, 10 mass ppm.
Oxygen content is preferably 10 mass ppm or more and 500 mass ppm hereinafter, more preferably 20 mass ppm or more and 200
Quality ppm or less.
In addition, specific surface area increases if miniaturizeing the partial size of In-Cu alloy powder, containing in In-Cu alloy powder
Oxygen amount often becomes more, therefore in order to reduce the oxygen content, In-Cu alloy powder is manufactured by aftermentioned manufacturing method.
(In:45 atom % or more and 90 atom % or less)
If manufacturing In-Cu alloy sputtering targets using In-Cu alloy powder made of Cu is added in In, in its tissue
It is middle to form the Cu harder than In11In9Compound phase, so as to greatly improve machinability.Further, it is possible to close In-Cu
The crystal particles of golden sputtering target are miniaturize.
Here, if the content of In mutually tails off less than 45 atom %, In monomers and there is a possibility that the density of sputtering target declines.
On the other hand, if the content of In is more than 90 atom %, it not will be fully formed Cu11In9Compound phase and there is a possibility that cutting plus
Work cannot improve.
Therefore, in present embodiment, the content of In is set as 45 atom % or more and 90 atom % or less.
The content of In is preferably 50 atom % or more and 80 atom % hereinafter, more preferably 55 atom % or more and 70 originals
Sub- % or less.
In addition, if the content of In is set as 70 atom % hereinafter, if be able to carry out rolling processing, so as to greatly improve
The production efficiency of In-Cu alloy sputtering targets.
(D50:5 μm of median particle diameter or more and 150 μm or less)
As described above, in the tissue of sputtering target, there are Cu11In9Compound phase, thus, it is possible to improve machinability.But
It is, if the Cu11In9The average grain diameter of compound phase is more than 150 μm and becomes thick, it is likely that becomes in machining and collapses
The reason of knife.And, it is possible to caused to be abnormal electric discharge in sputtering by the crushing knife trace.If the use of median particle diameter D50 being 150
μm In-Cu alloy powder below manufactures In-Cu alloy sputtering targets, then can be by Cu11In9The average grain diameter of compound phase is set
It is 150 μm or less.
In addition, the median particle diameter D50 of In-Cu alloy powder is preferably set as 100 μm or less in order to be reliably suppressed crushing knife
And by Cu11In9The average grain diameter of compound phase is set as 100 μm or less.
On the other hand, if the median particle diameter D50 of In-Cu alloy powder is less than 5 μm, surface area becomes larger and there is a possibility that containing
Oxygen amount increases.
Therefore, in present embodiment, the median particle diameter D50 of In-Cu alloy powder is set as 5 μm or more and 150 μm or less.
The median particle diameter D50 of In-Cu alloy powder is preferably 10 μm or more and 120 μm hereinafter, more preferably 20 μm or more
And 80 μm or less.
(D10/D50 is 1/2 or less or D90/D50 is 2 or more)
When using In-Cu alloy powder made of the addition Cu in In and with powder sintered manufacture In-Cu alloy sputtering targets,
By powder be filled in filling mold when packed density and sintered density it is closely related.Especially when there are pure In in powder
When (In monomer phase), the fusing point that sintering temperature is set as to In is needed hereinafter, therefore by setting packed density as far as possible high,
More highdensity sintered body can be obtained.
Here, if the ratio between D10 and median particle diameter D50 D10/D50 are more than the ratio between 1/2, D90 and median particle diameter D50 D90/D50
Less than 2, then the packed density being filled in filling mold is lower, and there is a possibility that the density of sputtering target declines.
Therefore, in present embodiment, D10/D50 is set as 1/2 or less or D90/D50 is set as 2 or more or is set as same
When meet the two conditions.
Here, D10 indicates partial size of the accumulated value as 10 volume % in cumulative grain-size distribution curve (under sieve).Median particle diameter
D50 indicates partial size of the accumulated value as 50 volume % in cumulative grain-size distribution curve (under sieve).D90 is indicated in cumulative particle size distribution
Accumulated value becomes the partial size of 90 volume % in curve (under sieve).
(In monomer phase and Cu11In9The peak value ratio I of the XRD of compound phaseIn/ICu11In9: 0.01 or more and 3 or less)
As the I of In-Cu alloy powderIn/ICu11In9When less than 0.01, the sputtering target manufactured using the powder also becomes phase
Same phase structure, since the ratio of the excellent In monomer phase of ductility is few, it is therefore possible to fracture and notch occurs in processing.
On the other hand, work as IIn/ICu11In9When more than 3, Cu11In9The ratio of compound phase tails off and being possible to machinability will not fill
Divide and improves.
Therefore, in present embodiment, by IIn/ICu11In9It is set as 0.01 or more and 3 or less.
IIn/ICu11In9Preferably 0.05 or more and 2 hereinafter, more preferably 0.5 or more and 1 or less.
In addition, in present embodiment, by ICu11In9It is set as belonging to Cu11In9(313) face of (DB card 01-065-4963)
Peak strength.Also, by IInIt is set as belonging to the peak strength in (110) face of In (DB card 01-074-6393).In addition, the master of In
Peak be (101), but due to Cu11In9The peak of (310) be mutually overlapped, therefore calculate IInWhen (110) face is utilized.
The manufacturing method > of < In-Cu alloy powder
The manufacturing method of In-Cu alloy powder involved in present embodiment has as shown in the process of Fig. 1: vacuumizing
Process S01 makes the container for having put into the raw metal comprising In and Cu reach 10Pa vacuum degree below；Process S02 is melted, to
Container imports oxygen concentration and is 50 volume ppm inert gas below and is heated to be 1100 DEG C or more and carrys out fused raw material metal to be made
Fused raw material；And atomization procedure S03,700 DEG C or more at a temperature of fused raw material is atomized.
Hereinafter, being illustrated to each process.
(vacuumizing process S01)
It vacuumizes in process S01, the raw metal comprising In and Cu is put into the heatproof container (earthenware of atomising device first
Crucible) in.As raw metal, such as use the Cu metal block and 99.99 mass % of purity or more of 99.99 mass % of purity or more
In metal block.
Then, the heatproof container for having put into raw metal is made to reach 10Pa vacuum degree below.
Here, the oxygen concentration being present in atmosphere is got higher, and it is therefore possible to can not fill if final vacuum is more than 10Pa
Divide the oxygen content for reducing In-Cu alloy powder.
Therefore, in present embodiment, final vacuum is set as 10Pa or less.The lower limit of final vacuum has no special limit
System, for example, 10-4Pa.Final vacuum is preferably set to 1Pa hereinafter, being more preferably set as 10-1Pa or less.
(melting process S02)
It melts in process S02, importing oxygen concentration in heatproof container is 50 volume ppm inert gases below, makes resistance to thermal capacitance
The inside of device is full of inert gas, is then heated to be 1100 DEG C or more and carrys out fused raw material metal.
Here, the oxygen concentration of powder is got higher when the oxygen concentration of inert gas is more than 50 volume ppm.The oxygen of inert gas
There is no particular restriction for the lower limit of concentration, for example, 1 volume ppm.Oxygen concentration is preferably set to 10 volume ppm hereinafter, being more preferably set as 5
Volume ppm or less.
If heating temperature is lower than 1100 DEG C, it is not easy the oxygen that removal is originated from oxide skin(coating) contained in raw material ingot casting, and is had
It may be unable to fully reduce the oxygen content of In-Cu alloy powder obtained.
Therefore, in present embodiment, heating temperature is set as 1100 DEG C or more.
There is no particular restriction for the upper limit of heating temperature, but examines from the viewpoint for forming deviation caused by the evaporation by indium is generated
Consider, such as is preferably set to 1200 DEG C or less.
Heating temperature be preferably set to 1120 DEG C or more and 1170 DEG C hereinafter, more preferably be set as 1140 DEG C or more and 1160 DEG C with
Under.
In present embodiment, nitrogen is used as the inert gas for being directed in container.Think by using nitrogen, the gas compared with argon
Thermal conductivity possessed by body is high, therefore the cooling of molten metal is accelerated, so as to further decrease containing for In-Cu alloy powder
Oxygen amount.
(atomization procedure S03)
In atomization procedure S03,700 DEG C or more at a temperature of fused raw material is atomized.
Here, nozzle is easy blocking when being atomized if the injection temperation of atomization is lower than 700 DEG C.Also, Cu11In9Compound
The generation ratio of phase increase and there is a possibility that the production quantity of In monomer phase declines.Therefore, when the content of In is 45~55 atom %
And when fewer, it pays particular attention to.
From the above considerations, the injection temperation of atomization is set as 700 DEG C or more in present embodiment.
There is no particular restriction for the upper limit of the injection temperation of atomization, and for example, 900 DEG C.If injection temperation is more than 900 DEG C, institute
The ratio of the In monomer phase of the In-Cu alloy powder of acquisition becomes more compared with the ratio obtained according to In-Cu state diagram, thus
Cu11In9Compound is mutually insufficient, and there is a possibility that machinability is not easy to improve.Also, be atomized when in chamber attaching powder and
There is a possibility that the yield of In-Cu alloy powder declines.
Injection temperation is preferably set to 750 DEG C or more and 880 DEG C hereinafter, being more preferably set as 800 DEG C or more and 850 DEG C or less.
Also, in present embodiment, using oxygen concentration as injection gas is 50 volume ppm inert gases below, and
Injection air pressure is set as 1.5MPa or more and 4.0MPa hereinafter, and nozzle diameter is set as 0.5mm or more and 3.0mm or less.
Here, the oxygen concentration of powder is got higher when the oxygen concentration for spraying gas is more than 50 volume ppm.Spray the oxygen of gas
There is no particular restriction for the lower limit of concentration, for example, 1 volume ppm.Oxygen concentration is preferably set to 10 volume ppm hereinafter, being more preferably set as 5
Volume ppm or less.
If spraying air pressure is lower than 1.5MPa, atomized powder (In-Cu alloy powder) is become thick, and is possible in manufacture target
When machining when generate crushing knife.And, it is possible to electric discharge is abnormal in sputtering due to the crushing knife trace.If spraying air pressure
Higher than 4.0MPa, then atomized powder becomes meticulous, so that increase with the increased oxygen amount of surface area, and being likely to occur becomes abnormal
The agglomeration of the reason of electric discharge.Also, it is more to spray gas flow, therefore is easy to keep nozzle cooling, to be easy to happen in atomization stifled
Plug, becomes to be not easy to obtain atomized powder.
If nozzle diameter is less than 0.5mm, it is easy to happen blocking in atomization, becomes to be not easy to obtain atomized powder.If also,
Nozzle diameter is greater than 3.0mm, then atomized powder becomes thick, and is possible to generate crushing knife when the machining when manufacturing target.And
And, it is possible to electric discharge is abnormal in sputtering due to the crushing knife trace.
Injection air pressure be preferably set to 2.0MPa or more and 3.5MPa hereinafter, more preferably be set as 2.5MPa or more and 3.0MPa with
Under.
Nozzle diameter is preferably set to 0.75mm or more and 2.0mm hereinafter, being more preferably set as 1.0mm or more and 1.5mm or less.
In addition, being classified using 500 μm of sieves below to In-Cu alloy powder obtained in present embodiment.
< In-Cu alloy sputtering targets >
In-Cu alloy sputtering targets involved in present embodiment by comprising In and Cu and oxygen content be 1000 mass ppm with
Under sintered body constitute.More specifically, In-Cu alloy sputtering targets have containing 45 atom % or more and 90 atom % it is below
In and remainder is made of what Cu and inevitable impurity were constituted.The average crystal particle diameter of In-Cu alloy sputtering targets is 5 μm
Above and 150 μm or less.Also, as shown in Figures 2 and 3, In-Cu alloy sputtering targets have In monomer phase and Cu11In9Compound
Phase, and In monomer phase and Cu11In9The peak value ratio I of the XRD of compound phaseIn/ICu11In9It is 0.01 or more and 3 or less.
In addition, in the In-Cu alloy sputtering targets of present embodiment, Cu11In9The average grain diameter of compound phase be 150 μm with
Under, the average grain diameter of In monomer phase is 1mm or less.The theoretical density ratio of sputtering target is (with respect to the calculated theory of composition
The relative density of density) it is 85% or more.
Also, in the In-Cu alloy sputtering targets of present embodiment, alkali metal compound can also be contained.Such as Na
Compound can contain NaF, NaCl, Na2S、Na2Se can contain KF, KCl, K as K compound2S、K2Se, as Rbization
RbF, RbCl, Rb can be contained by closing object2S、Rb2Se can contain CsF, CsCl, Cs as Cs compound2S、Cs2Se.These alkali
Metallic compound can individually contain a kind, can also combine and contain two or more.
The average grain diameter of alkali metal compound is 10 μm or less.Also, about the content of alkali metal, alkali metal (Na, K,
Rb, Cs) total add up to 0.1 atom % or more and 10 atom % or less relative to In, Cu, Na, K, Rb, Cs.
Hereinafter, being illustrated the reasons why regulation executed as described above in the In-Cu alloy sputtering targets of present embodiment.But
It is about the content recorded in the explanation of In-Cu alloy powder, then to omit the description.
(average crystal particle diameter: 5 μm or more and 150 μm or less)
Average crystal particle diameter is 5 μm or more and 150 μm hereinafter, therefore can maintain low by the oxygen content of sputtering target is same
When miniaturize crystal particles.Therefore, it is able to suppress crushing knife when machining, and is able to suppress different as caused by crushing knife trace
Often electric discharge.
Here, needing to make average crystal particle diameter less than 5 μm by the median particle diameter D50 of the In-Cu alloy powder of raw material
If must be small, in this way there is a possibility that the oxygen content of In-Cu alloy powder increases.If average crystal particle diameter is more than 150 μm, it is likely that
Crushing knife occurs in machining and increases paradoxical discharge when sputtering.
Therefore, in present embodiment, average crystal particle diameter is set as 5 μm or more and 150 μm or less.Average crystal particle diameter is excellent
10 μm or more and 100 μm are selected as hereinafter, more preferably 15 μm or more and 50 μm or less.
(average grain diameter of In monomer phase: 1mm or less)
The average grain diameter of In monomer phase is set as 1mm hereinafter, so as to inhibit paradoxical discharge.
Therefore, in present embodiment, the average grain diameter of In monomer phase is set as 1mm or less.
There is no particular restriction for the lower limit of the average grain diameter of In monomer phase, for example, 0.010mm or more.In monomer phase is averaged
Partial size is preferably 0.5mm hereinafter, more preferably 0.1mm or less.
The average grain diameter of In monomer phase can be adjusted by the median particle diameter D50 of the In-Cu alloy powder as raw material,
As long as the median particle diameter D50 of In-Cu alloy powder is set as 150 μm hereinafter, as long as the average grain diameter of In monomer phase can be made to become
1mm or less.
(theoretical density ratio: 85% or more)
If the theoretical density ratio of sputtering target, less than 85%, there are many gaps, and it is therefore possible to be easy hair in sputtering
Raw paradoxical discharge.
Therefore, in present embodiment, theoretical density ratio is set as 85% or more.
There is no particular restriction for the upper limit of theoretical density ratio, and for example, 100%.
Theoretical density is than preferably 90% or more, more preferably 95% or more.
In addition, theoretical density is changed according to composition (Cu/In ratio), therefore in present embodiment, pass through the melting Cu/In
The molten metal of ratio is simultaneously cast the molten metal and Slow cooling (5 DEG C/min or less of cooling velocity) is intact come what is obtained
The density of sunken ingot bar (10cm × 10cm × 10cm) is used as " theoretical density ".
(average grain diameter of alkali metal compound: 10 μm or less)
If the average grain diameter of alkali metal is more than 10 μm, it is likely that be abnormal electric discharge in sputtering.
Therefore, in present embodiment, the average grain diameter of alkali metal compound is set as 10 μm or less.
There is no particular restriction for the lower limit of the average grain diameter of alkali metal compound, and for example, 0.1 μm.The average grain diameter of alkali metal
Preferably 7 μm hereinafter, more preferably 5 μm or less.
(content of alkali metal: 0.1 atom % or more and 10 atom % or less)
When total content of alkali metal (Na, K, Rb, Cs) is less than 0.1 atom %, it is difficult to obtain based on the alkali metal
The improvement effect of the transfer efficiency of addition, when more than 10 atom %, it is possible to which take place frequently the paradoxical discharge as caused by alkali metal.
Therefore, in present embodiment, by the content of alkali metal be set as alkali metal (Na, K, Rb, Cs) it is total relative to In,
Cu, Na, K, Rb, Cs's adds up to 0.1 atom % or more and 10 atom % or less.
The content of alkali metal is preferably 0.2 atom % or more and 3 atom % hereinafter, more preferably 0.3 atom % or more and 1
Atom % or less.
The manufacturing method > of < sputtering target
The sputtering target of present embodiment is by will include that the raw material powder of above-mentioned In-Cu alloy powder is sintered and makes
It makes.
As shown in the process of Fig. 4, the manufacturing method of sputtering target involved in present embodiment has sintering process S11 and machine
Tool manufacturing procedure S12.
Hereinafter, being illustrated to each process.
(sintering process S11)
In sintering process S11, raw material powder is filled in mold and implements pressure sintering.
Raw material powder can be only above-mentioned In-Cu alloy powder, be also possible to be mixed with Cu powder in In-Cu alloy powder
With the mixed-powder of the alkali metal compounds powder such as Na compound powder, K compound powder.
When using Cu powder, being set as purity is 4N or more, and median particle diameter D50 is 5~50 μm, and oxygen content is 1000 mass
Ppm or less.Also, preferably electrolysis Cu powder.Purity is that the reason of 4N or more is, is likely to cause solar energy if purity is low
The performance of battery deteriorates.The reasons why median particle diameter D50 is 5~50 μm is, if increasing with surface area and leading less than 5 μm
It causes oxygen concentration to rise, and is easy to generate the agglomeration for the reason of becoming paradoxical discharge.If median particle diameter D50 is more than 50 μm, with alkali
When metallic compound is pulverized and mixed, paradoxical discharge when generating the cohesion of alkali metal compound and being likely to become sputtering
Reason.Also, density is not easy to improve when being sintered.When oxygen content is more than 1000 mass ppm, oxygen concentration contained in target is got higher,
And the agglomeration for the reason of being easy to happen as paradoxical discharge.
As the condition of mixing In-Cu alloy powder and other powder, φ is used for example, in 10L tank abrading-ball grinding machine
The zirconia ball of 5mm is with the condition of revolving speed 85rpm mixing 24 hours.Wherein, when the composition ratio of In in In-Cu alloy powder
When height, for example, 70 atom % or more, it is possible to which In is easy to attach on zirconia ball.Therefore, as In in In-Cu alloy powder
Composition ratio it is high when, it is preferable to use the soft mixing arrangement such as Rocking Mixer.When using Rocking Mixer, crush
Power is poorer than ball mill, therefore alkali metal compound powder individually is first carried out crushing to be preferred.
In sintering process S11, heating temperature is set as 10~40 DEG C of temperature lower than the fusing point of In (156.6 DEG C), it will
Pressure is set as 20~100MPa, will be set as the retention time 1~3 hour.Also, it is below true that atmosphere when being sintered is set as 10Pa
The inert gases such as empty or Ar to prevent the oxidation of raw material powder, and can also control oxygen content in 1000 matter in sintered body
Measure ppm or less.In addition, having imported inert gas by vacuum displacement when implementing under inert gas atmosphere.The limit at this time
Vacuum degree is set as 10Pa or less.Furthermore using being classified as 500 μm of raw material powder below, therefore average crystal particle diameter can be obtained and be
150 μm of sintered bodies below.By conditions above, theoretical density can be obtained than the sintered body for 85% or more.
(machining operation S12)
In machining operation S12, lathe process, Milling Process are implemented to the sintered body obtained in sintering process S11
Deng machining.The In-Cu alloy sputtering targets of regulation shape are obtained as a result,.
< effect >
Related In-Cu alloy powder according to the present embodiment, therefore oxygen content as little as 1000 mass ppm are hereinafter, lead to
It crosses using the In-Cu alloy powder as raw material, it is few and be not susceptible to the sputtering target of paradoxical discharge that oxygen content can be produced.
In present embodiment, the median particle diameter D50 of In-Cu alloy powder is 5 μm or more and 150 μm hereinafter, therefore can
Keep crystal particles fine while maintaining low by the oxygen content of the In-Cu alloy sputtering targets manufactured by the In-Cu alloy powder
Change.Therefore, it is able to suppress crushing knife when machining, and is able to suppress the paradoxical discharge as caused by crushing knife trace.
In present embodiment, In-Cu alloy powder has containing 45 atom % or more and 90 atom % In below and remains
Remaining part point is made of what Cu and inevitable impurity were constituted.Therefore, in the tissue of the sputtering target manufactured by the alloy powder
Form the Cu harder than In11In9Compound phase, this becomes the starting point destroyed, so as to greatly improve machinability.And
And the crystal particles of sputtering target can be made to miniaturize, to make its densification.
In present embodiment, In-Cu alloy powder has In monomer phase and Cu11In9Compound phase, and In monomer phase and
Cu11In9The peak value ratio I of the XRD of compound phaseIn/ICu11In9It is 0.01 or more and 3 or less.Therefore, it is manufactured by the alloy powder
Sputtering target also becomes identical phase structure, and with In monomer phase and the Cu harder than In monomer phase11In9Compound phase, because
This can greatly improve machinability.
Also, In monomer phase and Cu11In9The peak value ratio I of the XRD of compound phaseIn/ICu11In9It is 0.01 or more and 3 or less.
Therefore, the excellent In monomer phase of ductility and the Cu for becoming the starting point destroyed11In9Compound is mutually balanced to be existed, so as to press down
Fracture and notch when system processing, and can reliably improve machinability.
The manufacturing method of In-Cu alloy powder according to the present embodiment, by container vacuum-pumping to 10Pa hereinafter, then existing
Raw metal is carried out by heating melting with 1100 DEG C or more of temperature under inert gas atmosphere, and will with 700 DEG C or more of temperature
It is atomized.Therefore, oxygen content can be obtained and be reduced to 1000 mass ppm In-Cu alloy powder below.
In present embodiment, it is believed that when due to using nitrogen as inert gas and being compared with argon, the thermal conductivity of gas
Height, therefore the cooling velocity of molten metal becomes faster, so as to further decrease the oxygen content of alloy powder.
In-Cu alloy sputtering targets according to the present embodiment, the effect as alloy powder in addition to the foregoing, are gone back
It can get following effects.
In the In-Cu alloy sputtering targets of present embodiment, Cu11In9The average grain diameter of compound phase be 150 μm hereinafter, because
This is able to suppress paradoxical discharge when crushing knife and sputtering in machining.
In the In-Cu alloy sputtering targets of present embodiment, the average grain diameter of In monomer phase is fine to 1mm or less.Therefore, i.e.,
Make to consume target surface because of the progress of sputtering, the bumps of target surface are also inhibited, so as to inhibit paradoxical discharge.
In the In-Cu alloy sputtering targets of present embodiment, when further containing alkali metal compound, it is capable of forming and includes
The In film of alkali metal.Cu-In-Ga-Se system alloy firm is formed by using the In film, can be improved CIGS-based solar battery
Transfer efficiency.
In addition, the average grain diameter of alkali metal compound is 10 μm hereinafter, being therefore able to suppress paradoxical discharge when sputtering.
The manufacturing method of In-Cu alloy sputtering targets according to the present embodiment, to including the few alloy powder of oxygen content
Raw material powder is sintered, therefore it is few and be not susceptible to the sputtering target of paradoxical discharge to produce oxygen content.
More than, embodiments of the present invention are illustrated, but the present invention is not limited to this, is not departing from the present invention
Technical idea in the range of can suitably change.
For example, having used nitrogen as inert gas, but be not limited in the manufacturing method of the alloy powder of present embodiment
This, also can be used other inert gases such as argon.
Also, in the In-Cu alloy sputtering targets of present embodiment, 1mm or less is set as to by the average grain diameter of In monomer phase
The case where be illustrated, but not limited to this.
In the In-Cu alloy sputtering targets of present embodiment, illustrate that Na chemical combination can also be contained as alkali metal compound
Object, K compound, Rb compound or Cs compound, but also may include these compounds of more than two kinds.
Embodiment
Hereinafter, manufacture of the explanation to In-Cu alloy powder, In-Cu alloy powder involved in embodiments of the present invention
The evaluation test that method, the function and effect of the manufacturing method of In-Cu alloy sputtering targets and In-Cu alloy sputtering targets are evaluated
Result.
< example 1~14 of the present invention and comparative example 1~4:In-Cu alloy powder >
As raw metal, the Cu metal block and 99.99 mass % of purity or more of 99.99 mass % of purity or more are prepared
In metal block.These raw metals are weighed so that overall weight becomes 1200g in terms of the match ratio shown in the table 1.It will
The raw metal of weighing is put into the heatproof container (carbon crucible) of atomising device, and heatproof container is evacuated to shown in table 1
Final vacuum.Then, inert gas recorded in table 1 is imported in heatproof container until the interior pressure of heatproof container reaches
0.1MPa makes the inside of heatproof container full of inert gas, is then heated to be heating temperature recorded in table 1 and carrys out fused raw material gold
Belong to.Then, the fused raw material generated inside heatproof container is subjected to gas atomization with injection temperation shown in table 1, to make
Make In-Cu alloy powder.At this point, as injection gas, using inert gas identical with the gas for importeding into heatproof container,
Injection air pressure and nozzle diameter are set as value recorded in table 1.The stifled of nozzle has occurred also, in comparative example 3, after injection at once
Plug, therefore fail to obtain atomized powder (In-Cu alloy powder).
About In-Cu alloy powder obtained, by following methods to composition, oxygen content, size distribution and In monomer
Mutually exist than being determined.The result is shown in table 2.In addition, showing median particle diameter D50, D10/ about size distribution
D50、D90/D50。
(composition of In-Cu alloy powder)
With acid dissolution In-Cu alloy powder.Solution obtained is determined using inductively coupled plasma body method (ICP)
In In content.Cu and other compositions remainder has been considered as.
(oxygen content of In-Cu alloy powder)
In accordance with the infrared absorption recorded in JIS Z 2613 " the oxygen quantitative approach general rule of metal material ", LECO is used
Corporation TC600 determines oxygen content.
(size distribution of In-Cu alloy powder)
The aqueous solution of the concentration 0.2% of the calgon of 100mL is prepared, adds the In-Cu of 10mg in the aqueous solution
Alloy powder is measured using laser diffraction scattering method (measurement device: Nikkiso Co., Ltd. system, Microtrac MT3000)
Particle diameter distribution.Cumulative grain-size distribution curve is made according to particle diameter distribution obtained, obtains median particle diameter D10, D50, D90,
And D10/D50, D90/D50 are calculated.
(the In monomer of In-Cu alloy powder mutually exist than)
The X-ray diffraction pattern of In-Cu alloy powder is determined with following conditions.
Device: Rigaku Corporation system (RINT-Ultima/PC)
Pipe ball: Cu
Tube voltage: 40kV
Tube current: 40mA
Scanning range (2 θ): 10 °~80 °
Slit sizes: diverging 2/3 degree of (DS), scattering 2/3 degree of (SS), light (RS) 0.8mm
Measure step width: 2 θ, 0.02 degree
Scanning speed: 2 degrees/min
Sample table rotation speed: 30rpm
The X-ray diffraction intensity I of In monomer phase is measured according to X-ray diffraction pattern obtainedInAnd Cu11In9Compound
The X-ray diffraction intensity I of phaseCu11In9, and calculate its intensity ratio IIn/ICu11In9.By intensity ratio IIn/ICu11In9As In monomer
Mutually exist than.
[table 1]
[table 2]
Final vacuum when by vacuumizing to the heatproof container for having put into raw metal is set as being more than 10Pa's
In the comparative example 1 of pressure, the oxygen content for confirming In-Cu alloy powder is more than 1000 mass ppm.Speculate the reason is that taking out
Final vacuum when vacuum is low, and a large amount of oxygen is remained in heatproof container, and the remaining oxygen of institute has been mixed into atomization.
In comparative example 2 of the heating temperature lower than 1100 DEG C, the oxygen content for confirming In-Cu alloy powder is more than 1000 matter
Measure ppm.Think the reason is that oxygen in fused raw material is not sufficiently removed and remains since heating temperature is low.
In comparative example 3 of the injection temperation lower than 700 DEG C, since injection temperation is too low, so that fused raw material is after atomization
It is solidificated in nozzle segment at once, so that nozzle is blocked.Therefore, fail to obtain In-Cu alloy powder.
In having used the comparative example 4 that oxygen concentration is the nitrogen of 60 volume ppm as inert gas, In-Cu alloy is confirmed
The oxygen content of powder is more than 1000 mass ppm.Speculate the reason is that oxygen contained in inert gas has been mixed into atomization.
In contrast, confirming the oxygen content of the In-Cu alloy powder made in example 1~14 of the present invention down to 1000 matter
Measure ppm or less.
< example 21~45 of the present invention and comparative example 5~7:In-Cu alloy sputtering targets >
The In-Cu alloyed powder made in example 1~14 of the present invention and comparative example 1~2,4 is mixed with match ratio shown in table 3
End is mixed with Cu powder (purity: 4N, D50:20 μm of median particle diameter, 700 mass ppm of oxygen concentration) and alkali metal chemical combination as needed
Object powder (purity: D50:100 μm of 2N, median particle diameter).Mixing condition is set as the ball mill of dry type, is set as described above in 10L
It is mixed with 24 hours using the zirconia ball of φ 5mm with revolving speed 85rpm in tank abrading-ball grinding machine.When In is 70 atom % or more,
Using Rocking Mixer, mixing condition is set as with 85rpm mixing 30 minutes.
Then, which pressure sintering has been subjected to condition shown in table 3.It will be obtained using lathe and milling machine
Sintered body is processed into 126mm × 178mm × 6mm (sputtering target of thickness t) size.
< comparative example 8: the In-Cu alloy sputtering targets > of casting
In-Cu alloy sputtering targets are manufactured that by melting casting.
The Cu metal block of 99.99 mass % of purity or more and the In metal block of 99.99 mass % of purity or more are prepared.With
The mode that In:70 atom %, remainder: Cu and overall weight become 3500g is weighed.
The raw material of weighing is filled in carbon crucible, in argon atmospher and the condition of 1150 DEG C of temperature, 10 minutes retention times
Under melted, be then cast into 170mm × 220mm × 11mm (mold of thickness t), and the generation of shrinkage cavity in order to prevent is suitable
When supplemented with molten metal.Later, natural cooling.
In-Cu alloy cast ingot obtained 126mm × 178mm × 6mm (thickness t) has been processed into using lathe and milling machine
The In-Cu alloy sputtering targets of size.
About In-Cu alloy sputtering targets obtained, by following methods to composition, composition unevenness, oxygen content, In monomer
Mutually exist than, average crystal particle diameter, the average grain diameter of In monomer phase, Cu11In9The average grain diameter of compound phase, alkali metal chemical combination
Average grain diameter, theoretical density ratio, the processability (chip attachment, crushing knife size, surface roughness Ra), paradoxical discharge number of object phase
It is determined.Its result is shown in table 4.
(composition)
The a part for cutting In-Cu alloy sputtering targets, is dissolved with acid.Solution obtained is determined by ICP
In In, Na, K, Rb, Cs content.Cu and other compositions remainder has been considered as.
(composition is uneven)
Using x-ray fluorescence analysis (XRF) device (ZSX PrimusII Rigaku Corporation system) to In-Cu
The sputter face (lathe process face: the face 126mm (Y-direction) × 178mm (X-direction)) of alloy sputtering targets has carried out the survey of Cu and In
It is fixed.When the centre coordinate of sputter face is set as (X=0mm, Y=0mm), by (X=-70mm, Y=50mm), (X=-70mm, Y
=-50mm), (X=0mm, Y=0mm), (X=70mm, Y=50mm), (X=70mm, Y=-50mm) this In measured value at 5
Middle maximum value subtracts value obtained by minimum value and is considered as " composition is uneven ".In addition, using the Cu and In that concentration is previously known before measurement
Solution, prepare the solution of 3 kinds of various concentrations respectively, and draw standard curve.
(oxygen content)
Wet type processing is carried out to In-Cu alloy sputtering targets and obtains 10mm × 10mm × 5mm (block of thickness t).Benefit
It is etched with surface of the nitric acid to block obtained, is then cleaned and be dried with pure water, thus as measurement sample.
Other than using measurement sample obtained, with identical with the oxygen content for measuring aforementioned In-Cu alloy powder
Mode determines oxygen content.
(In monomer mutually exist than)
Using micro- fragment for cutting machine acquisition In-Cu alloy sputtering targets, SiC waterproof pouncing paper (SiC-Paper, grit are utilized
1000) to collected fragment carry out wet lapping, be then dried and as measurement sample.
Other than using measurement sample obtained, mutually to exist with the In monomer for measuring aforementioned In-Cu alloy powder
Than identical mode determine In monomer mutually exist than.
(average crystal particle diameter)
Average crystal particle diameter is determined by planimetric method.Sputtering using nitric acid to In-Cu alloy sputtering targets
Face (lathe process face) carries out etching in 1 minute or so, is cleaned with pure water, then by optical microscopy to carrying out at any 5
Observation.Here, when failing clearly to confirm tissue by the observation of optical microscopy, the additional erosion using nitric acid
It carves.
The photo on surface obtained is had taken with 1000 times or so of multiplying power by SEM (scanning electron microscope).
Then, 100 μm of diameter of circle is drawn on photo obtained, and respectively on the crystal particles number (Nc) and circumference in measurement circle
Crystal particles number (Nj), calculated average crystal particle diameter using formula as shown below.Calculate separately out being averaged at above-mentioned 5
Crystal particle diameter, and found out its average value.The average value is shown in " average crystal particle diameter (μm) " column of table 4.
Average crystal particle diameter=2/ (π × Ng)1/2
Crystal particles number Ng=(Nc+ (1/2) × Nj)/A of per unit area
A: round area
Nc: the crystal particles number in circle
Nj: the crystal particles number on circumference
(In monomer phase, Cu11In9The average grain diameter of compound phase, alkali metal compound phase)
Cross section polishing (CP processing) is implemented to the sputter face of In-Cu alloy sputtering targets.For what is processed through CP
Sputter face has taken 5 using electron probe microanalysis (EPMA) (EPMA) device (JEOL Ltd. system) with multiplying power 1000 respectively again and indulges
The photo of 90 μm and the element mapping image (referring to Fig. 3) of horizontal 120 μm of Cu and In.Image is mapped according to element obtained
Photo, by Cu and In, existing region is defined as Cu jointly11In9Compound phase, the region that there will be only In are defined as In monomer
Phase.
About Cu element mapping image 5 photos, by by photo along longitudinal direction it is crosscutting at 4 equal parts in a manner of in every photograph
On piece draws 3 lines, and measures in each line segment that there are In monomer phase and Cu respectively11In9The length and number of compound phase, according to
Following calculating formulas calculate longitudinal partial size and are averaged.By the average value of 5 photographic results as average grain diameter.
(longitudinal partial size of In monomer phase)=(aggregate value of the length of In monomer phase/In monomer phase number)
(Cu11In9Longitudinal partial size of compound phase)=(Cu11In9Aggregate value/Cu of the length of compound phase11In9Change
Close the number of object phase)
Then, same operation is horizontally carried out, and has calculated lateral partial size.It then, will be obtained longitudinal
The average value of partial size and lateral partial size is as In monomer phase and Cu11In9The average grain diameter of compound phase.
Also, about the In-Cu alloy sputtering targets comprising alkali metal compound, shoot the element mapping image of alkali metal
Photo has calculated the average grain diameter of alkali metal compound phase by method same as described above.
(theoretical density ratio)
The theoretical density ratio of In-Cu alloy sputtering targets has proceeded as follows calculating.
By ratio of components corresponding with each In-Cu alloy sputtering targets made in example 21~45 of the present invention and comparative example 5~8
Cu-In metal is melted at 1200 DEG C, and is cast and gradually cooling (5 DEG C/min or less of cooling velocity), from
And obtain flawless ingot bar (10cm × 10cm × 10cm).By the density of the ingot bar as " theoretical density ".Relative to
This, using the weight of made sputtering target divided by the value according to obtained by the volume that size obtains as " measurement density ".
Using the measurement density of the theoretical density and sputtering target obtained, it is calculate by the following formula out theoretical density ratio.
Theoretical density ratio (%)=(measurement density)/(theoretical density) × 100
(processability: the attachment of chip)
Lathe process is carried out to In-Cu alloy sputtering targets, has chipless attachment to be visually observed when to processing.It will add
The attachment of chip occurs on the way and is difficult to continue the target of dry-type processing as "×" for work.Although there is cutting to adhere to but can incite somebody to action
Processing carries out being used as " △ " to last target.Using the target absolutely not adhered to as "○".In addition, processing conditions be set as
Under.Also, for the target for being evaluated as "×" He " △ " of chip attachment, is processed while alcohol is added dropwise and carried out processing
To last.
Tool: carbide chip (Mitsubishi Materials Corporation system, TNMG160404-
MJVP05RT)
Feed speed: 0.7mm/rpm
Revolving speed: 100rpm
1 cutting-in amount: 1mm
Cut environment: dry type
(processability: crushing knife size)
To the ends of the In-Cu alloy sputtering targets after above-mentioned lathe process, whether there is or not crushing knifes to be confirmed.When being collapsed
When knife, the maximum distance from the end face of sputtering target to the part that notch occurs is determined using electronic digital indicator.This
When, the maximum face in part of notch in the face of court, crushing knife institute is determined.In addition, being set as 0 when crushing knife does not occur.
(processability: surface roughness)
Lathe process is carried out under conditions of same as described above, in the direction orthogonal with the toolmark on the surface after processing
Line segment on using Mitutoyo Corporation SURFTEST SV-3000H4 carried out the measurement of surface roughness Ra.
For 1 sample, implement measurement at the end of sputtering target to 15mm is with the 4 of inner region, and by its average value as the sample
Surface roughness (arithmetic average roughness) Ra of product.
(paradoxical discharge)
It is formed a film using In-Cu alloy sputtering targets, and under the following conditions by sputtering.It is filled by DC magnetron sputtering
It sets, uses Ar gas as sputter gas, flow 50sccm, pressure 0.67Pa are set as, as input power with 6W/cm2Power
Sputtering in 180 minutes is carried out, and passes through DC power source apparatus (Kyosan Electric Mfg.Co., Ltd. HPK06Z-SW6)
The electric arc tally function being had counts the number of paradoxical discharge.
[table 3]
[table 4]
It is more than the In-Cu alloy powder of 1000 mass ppm the comparative example 5 that manufactures using oxygen content as raw material powder
In~7 In-Cu alloy sputtering targets, confirms paradoxical discharge number when oxygen content is more than 1000 mass ppm and sputters and become more.
Speculate the reason is that agglomeration and particle are generated because of the oxide in the tissue for being present in In-Cu alloy sputtering targets, to give birth to
At agglomeration or particle be that starting point becomes easy and is abnormal electric discharge.
Also, with melt casting manufacture comparative example 8 In-Cu alloy sputtering targets in, composition unevenness become larger.Speculate
The reason is that producing the concentration difference of In and Cu in the molten metal when melting casting because of the difference in specific gravity of Cu and In.By
It is uneven in the composition that the composition unevenness of In-Cu alloy sputtering targets directly affects film, therefore do not preferably constitute uneven big.
In contrast, using oxygen content to be more than the In-Cu alloy powder of 1000 mass ppm and pass through as raw material powder
In the In-Cu alloy powder of the example of the present invention 21~45 of powder sintered manufacture, confirm oxygen content be 1000 mass ppm with
Under, and paradoxical discharge number when sputtering reduces, and forms uneven small.
By the above content check to example according to the present invention be capable of providing a kind of In-Cu alloy powder that oxygen content is few and its
The few In-Cu alloy sputtering targets and its manufacturing method of paradoxical discharge when manufacturing method and sputtering.
Claims (12)
1. a kind of In-Cu alloy powder, which is characterized in that
Comprising In and Cu and oxygen content is 1000 mass ppm or less.
2. In-Cu alloy powder according to claim 1, which is characterized in that
Median particle diameter D50 is 5 μm or more and 150 μm or less.
3. In-Cu alloy powder according to claim 1 or 2, which is characterized in that
The ratio between D10 and median particle diameter D50 D10/D50 be 1/2 hereinafter, or the ratio between D90 and median particle diameter D50 D90/D50 be 2 with
On, or meet the two conditions simultaneously.
4. In-Cu alloy powder according to any one of claim 1 to 3, which is characterized in that
With containing 45 atom % or more and 90 atom % In below and remainder are made of Cu and inevitable impurity
Composition.
5. In-Cu alloy powder according to any one of claim 1 to 4, which is characterized in that
With In monomer phase and Cu11In9Compound phase, and the X-ray diffraction intensity I of the In monomer phaseInWith the Cu11In9
The X-ray diffraction intensity I of compound phaseCu11In9Intensity ratio IIn/ICu11In9It is 0.01 or more and 3 or less.
6. a kind of manufacturing method of In-Cu alloy powder, which is characterized in that have:
Process is vacuumized, the heatproof container for having put into the raw metal comprising In and Cu is made to reach 10Pa vacuum degree below；
Process is melted, it is 50 volume ppm inert gases below that Xiang Suoshu heatproof container, which imports oxygen concentration, makes the heatproof container
Inside be full of the inert gas, be heated to be 1100 DEG C or more then to melt the raw metal so that fused raw material is made；
And
Atomization procedure, 700 DEG C or more at a temperature of with oxygen concentration be 50 volume ppm inert gases below by melting original
Material is atomized.
7. the manufacturing method of In-Cu alloy powder according to claim 6, which is characterized in that
The inert gas is nitrogen.
8. a kind of manufacturing method of In-Cu alloy sputtering targets, which is characterized in that
Raw material powder comprising In-Cu alloy powder described in any one of claims 1 to 5 is sintered.
9. a kind of In-Cu alloy sputtering targets, which is characterized in that
It is by comprising In and Cu and oxygen content is that 1000 mass ppm sintered bodies below are constituted.
10. In-Cu alloy sputtering targets according to claim 9, which is characterized in that
Average crystal particle diameter is 5 μm or more and 150 μm or less.
11. In-Cu alloy sputtering targets according to claim 9 or 10, which is characterized in that
With containing 45 atom % or more and 90 atom % In below and remainder are made of Cu and inevitable impurity
Composition.
12. the In-Cu alloy sputtering targets according to claim 9 to 11, which is characterized in that
With In monomer phase and Cu11In9Compound phase, and the X-ray diffraction intensity I of the In monomer phaseInWith the Cu11In9
The X-ray diffraction intensity I of compound phaseCu11In9Intensity ratio IIn/ICu11In9It is 0.01 or more and 3 or less.
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| JP2002344033A (en) * | 2001-05-18 | 2002-11-29 | Kyocera Corp | Thermoelectric device and method of manufacturing the same |
| CN102067363A (en) * | 2008-06-25 | 2011-05-18 | 三菱化学株式会社 | Composite graphite particle for nonaqueous secondary battery, and negative electrode material, negative electrode, and nonaqueous secondary battery containing the same |
| CN103619779A (en) * | 2011-06-30 | 2014-03-05 | 日立金属株式会社 | Brazing filler metal, brazing filler metal paste, ceramic circuit substrate, ceramic master circuit substrate, and power semiconductor module |
| CN105358733A (en) * | 2013-08-01 | 2016-02-24 | 三菱综合材料株式会社 | Cu-Ga alloy sputtering target, and method for producing same |
| JP2017082326A (en) * | 2015-10-26 | 2017-05-18 | 三菱マテリアル株式会社 | Sputtering target and manufacturing method of sputtering target |
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| JP2004211156A (en) * | 2002-12-27 | 2004-07-29 | Tamura Kaken Co Ltd | Method for manufacturing metal microparticle, substance containing metal microparticle, and electroconductive coating composition |
| JP5767447B2 (en) * | 2010-06-29 | 2015-08-19 | 株式会社コベルコ科研 | Method for producing powder containing Cu, In, Ga and Se elements, and sputtering target containing Cu, In, Ga and Se elements |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002344033A (en) * | 2001-05-18 | 2002-11-29 | Kyocera Corp | Thermoelectric device and method of manufacturing the same |
| CN102067363A (en) * | 2008-06-25 | 2011-05-18 | 三菱化学株式会社 | Composite graphite particle for nonaqueous secondary battery, and negative electrode material, negative electrode, and nonaqueous secondary battery containing the same |
| CN103619779A (en) * | 2011-06-30 | 2014-03-05 | 日立金属株式会社 | Brazing filler metal, brazing filler metal paste, ceramic circuit substrate, ceramic master circuit substrate, and power semiconductor module |
| CN105358733A (en) * | 2013-08-01 | 2016-02-24 | 三菱综合材料株式会社 | Cu-Ga alloy sputtering target, and method for producing same |
| JP2017082326A (en) * | 2015-10-26 | 2017-05-18 | 三菱マテリアル株式会社 | Sputtering target and manufacturing method of sputtering target |
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