TW201516157A - Method for manufacturing cu-ga alloy sputtering target - Google Patents

Method for manufacturing cu-ga alloy sputtering target Download PDF

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TW201516157A
TW201516157A TW103126585A TW103126585A TW201516157A TW 201516157 A TW201516157 A TW 201516157A TW 103126585 A TW103126585 A TW 103126585A TW 103126585 A TW103126585 A TW 103126585A TW 201516157 A TW201516157 A TW 201516157A
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phase
alloy powder
alloy
powder
sintered body
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Eriko Sato
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Sumitomo Metal Mining Co
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
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    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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    • B22F2207/00—Aspects of the compositions, gradients
    • B22F2207/01—Composition gradients
    • B22F2207/07—Particles with core-rim gradient
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

Provided is a method for manufacturing a Cu-Ga alloy sputtering target, whereby it becomes possible to manufacture a high-density Cu-Ga alloy sputtering target by a pressureless sintering technique. A Cu-Ga alloy powder is prepared by grinding a Cu-Ga alloy powder in such a manner that the resultant Cu-Ga alloy powder can have an average particle diameter of (D50) of 10 to 45 [mu]m, wherein each particle of the Cu-Ga alloy powder to be ground comprises an outer peripheral part and a center part, the Cu-Ga alloy powder to be ground has an average Ga concentration of 20 at.% or more and less than 32 at.%, the outer peripheral part comprises a CuGa2 phase and/or a Cu9Ga4 ([gamma]2, [gamma]3) phase, and the center part comprises a CuGa alloy phase having a lower Ga concentration than that in the outer peripheral part and/or a Cu phase containing Ga in the form of a solid solution and/or a pure Cu phase. Alternatively, a Cu-Ga alloy powder is prepared, of which each particle comprises an outer peripheral part and a center part, and which has an average Ga concentration of 20 at.% or more and less than 32 at.% and an average particle diameter of (D50) of 10 to 45 [mu]m, wherein the outer peripheral part comprises a CuGa2 phase and/or a Cu9Ga4 ([gamma]2, [gamma]3) phase, and the center part comprises a CuGa alloy phase having a lower Ga concentration than that in the outer peripheral part and/or a Cu phase containing Ga in the form of a solid solution and/or a pure Cu phase. Subsequently, the prepared Cu-Ga alloy powder is subjected to press-molding and then pressureless sintering. In this manner, the high-density Cu-Ga alloy sputtering target can be produced.

Description

Cu-Ga合金濺鍍靶的製造方法 Method for manufacturing Cu-Ga alloy sputtering target

本發明係關於一種使用於CIGS(Cu-In-Ga-Se)太陽能電池之光吸收層的形成之Cu-Ga合金濺鍍靶的製造方法。本申請案係將於日本在2013年10月30日所申請之日本專利申請編號特願2013-225773號作為基礎並主張其優先權，此申請案係藉由參見該申請案並併用於本申請案中。 The present invention relates to a method for producing a Cu-Ga alloy sputtering target for forming a light absorbing layer of a CIGS (Cu-In-Ga-Se) solar cell. The application is based on and claims the priority of Japanese Patent Application No. 2013-225773, filed on Jan. In the case.

近年來，作為清潔能源中之一正矚目於太陽能發電。主要是使用結晶系Si的太陽能電池，就供給面及成本的問題而言，矚目於變換效率高CIGS(Cu-In-Ga-Se)系的太陽能電池。 In recent years, one of the clean energy sources is attracting attention to solar power generation. A solar cell using crystalline Si is mainly used, and in terms of a supply surface and cost, a solar cell having a high conversion efficiency CIGS (Cu-In-Ga-Se) system has been attracting attention.

CIGS太陽能電池具備作為基本構造之成為鈉鈣玻璃基板上所形成之背面電極的Mo電極層、與成為此Mo電極層上所形成之光吸收層的Cu-In-Ga-Se四元系合金膜、與由此Cu-In-Ga-Se四元系合金膜所成之光吸收層上所形成之ZnS、CdS等所成之緩衝層、與此緩衝層上所形成之透明電極。 The CIGS solar cell includes a Mo electrode layer which is a back surface electrode formed on a soda lime glass substrate as a basic structure, and a Cu-In-Ga-Se quaternary alloy film which is a light absorbing layer formed on the Mo electrode layer. a buffer layer formed of ZnS, CdS or the like formed on the light absorbing layer formed of the Cu-In-Ga-Se quaternary alloy film, and a transparent electrode formed on the buffer layer.

作為由此Cu-In-Ga-Se四元系合金膜所成之光吸收層的形成方法，已知有蒸著法，為了得到更廣泛的面積且均勻的膜，提案有藉由濺鍍法形成的方法。 As a method of forming the light absorbing layer formed by the Cu-In-Ga-Se quaternary alloy film, a vapor deposition method is known, and in order to obtain a wider and uniform film, a sputtering method is proposed. The method of formation.

作為濺鍍法，有例如首先使用In靶，藉由濺鍍成膜In膜，於此In膜上使用Cu-Ga合金濺鍍靶，藉由濺鍍成膜Cu-Ga合金膜，將由得到的In膜及Cu-Ga合金膜所成之層合膜在Se環境中進行熱處理，而形成Cu-In-Ga-Se四元系合金膜的方法。 As a sputtering method, for example, an In target is first used, and an In film is formed by sputtering, and a Cu-Ga alloy sputtering target is used on the In film, and a Cu-Ga alloy film is formed by sputtering. A method in which a laminated film formed of an In film and a Cu-Ga alloy film is heat-treated in a Se atmosphere to form a Cu-In-Ga-Se quaternary alloy film.

藉由此濺鍍法所形成之Cu-In-Ga-Se四元系合金膜的品質係大大地依賴在Cu-Ga合金濺鍍靶的品質，故期望使用高品質的Cu-Ga合金濺鍍靶。 The quality of the Cu-In-Ga-Se quaternary alloy film formed by this sputtering method is greatly dependent on the quality of the Cu-Ga alloy sputtering target, so it is desirable to use high-quality Cu-Ga alloy sputtering. target.

作為Cu-Ga合金濺鍍靶的製造方法，已知有粉末燒結法。 As a method of producing a Cu-Ga alloy sputtering target, a powder sintering method is known.

例如專利文獻1中記載有調配含有高Ga的Cu-Ga合金粉末、與純Cu或含有低Ga的Cu-Ga合金粉末後，以熱壓法在200℃之低溫度燒結，製造使含有高Ga之Cu-Ga二元系合金粒的周圍被含有低Ga的Cu-Ga二元系合金粒界相被包圍的二相共存組織之濺鍍靶的方法。在200℃之低溫度燒結，係燒結時為了避免液相的出現，但由於以低溫燒結，靶的密度無法上升而成為相對密度低的靶。又，雖於以200℃的燒結時靶中會殘留高Ga合金的CuGa2相，因CuGa2脆弱，殘留於靶中時有靶之強度會變弱的問題。 For example, Patent Document 1 discloses that a Cu-Ga alloy powder containing high Ga is mixed with pure Cu or a Cu-Ga alloy powder containing low Ga, and then sintered at a low temperature of 200 ° C by a hot press method to produce a high Ga content. A method of sputtering a target of a two-phase coexisting structure surrounded by a grain boundary phase of a low-Ga Cu-Ga binary alloy is surrounded by the Cu-Ga binary alloy particles. Sintering at a low temperature of 200 ° C is to avoid the appearance of a liquid phase during sintering, but the density of the target cannot be increased due to sintering at a low temperature, and the target has a relatively low density. In addition, when the CuGa 2 phase of the high Ga alloy remains in the target at the time of sintering at 200 ° C, the CuGa 2 is weak, and there is a problem that the strength of the target is weak when it remains in the target.

又，專利文獻2中亦揭示調配含有高Ga的 Cu-Ga合金粉末，與純Cu或含有低Ga的Cu-Ga合金粉末後，以熱壓法或熱間靜水等熱均壓成型法(HIP法)燒結的技術。專利文獻2中，使含有高Ga的Cu-Ga合金粉末之Ga上限設定於45原子%以下，燒結時抑制液相出現，而較專利文獻1實現高溫下燒結。 Further, Patent Document 2 also discloses that the formulation contains high Ga Cu-Ga alloy powder, after pure Cu or a low-Ga-containing Cu-Ga alloy powder, is sintered by a hot press molding method or a hot isostatic water (HIP method). In Patent Document 2, the upper limit of Ga of the Cu-Ga alloy powder containing high Ga is set to 45 atom% or less, and the liquid phase is suppressed during sintering, and the sintering is performed at a high temperature compared with Patent Document 1.

又，專利文獻3中雖亦揭示混合Cu粉末與Ga並攪拌，熱壓成型得到的Cu-Ga合金粉末，將此成型體在真空中以400℃~800℃燒結的方法，係於如此常壓燒結法無法得到高密度的燒結體。 Further, in Patent Document 3, a Cu-Ga alloy powder obtained by mixing a Cu powder and Ga and being kneaded and hot-pressed is disclosed, and the molded body is sintered at 400 to 800 ° C in a vacuum. A sintered body of high density cannot be obtained by the sintering method.

亦即，記載在專利文獻1或專利文獻2之熱壓法或HIP法的加壓燒結法係高成本的製造方法，被需求以記載在專利文獻3之如常壓燒結法的廉價製法得到的燒結體。然而，在常壓燒結法有無法得到高密度的燒結體之問題。 In other words, the high-cost production method of the hot press method or the HIP method described in Patent Document 1 or Patent Document 2 is required to be obtained by the inexpensive method of the normal pressure sintering method described in Patent Document 3. Sintered body. However, in the normal pressure sintering method, there is a problem that a sintered body having a high density cannot be obtained.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]特開2008-138232號公報 [Patent Document 1] JP-A-2008-138232

[專利文獻2]特開2011-149039號公報 [Patent Document 2] JP-A-2011-149039

[專利文獻3]特開2011-231396號公報 [Patent Document 3] JP-A-2011-231396

本發明鑑於上述狀況而完成者，係提供一種 可藉由常壓燒結法而得到高密度的Cu-Ga合金濺鍍靶之Cu-Ga合金濺鍍靶的製造方法。 The present invention has been made in view of the above circumstances, and provides a A method for producing a Cu-Ga alloy sputtering target of a high-density Cu-Ga alloy sputtering target can be obtained by a normal pressure sintering method.

為了解決上述問題，本發明者深入研究之結果發現，在熱壓法為了得到高密度的燒結體，雖避免了燒結中液相的出現，但在常壓燒結法中，藉由於燒結中使液相出現，反而會減少空孔，燒結體變成高密度，而達成本發明。 In order to solve the above problems, the inventors have intensively studied and found that in the hot pressing method, in order to obtain a high-density sintered body, although the occurrence of a liquid phase in sintering is avoided, in the atmospheric pressure sintering method, the liquid is formed by sintering. When the phase appears, the pores are reduced, and the sintered body becomes high density, and the present invention is achieved.

亦即，本發明之Cu-Ga合金濺鍍靶的製造方法，其特徵為外周部由CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，中心部係由Ga濃度比前述外周部低之CuGa合金相及/或固溶有Ga的Cu相及/或純Cu相所成，且將平均Ga濃度為20原子%以上並未滿32原子%的Cu-Ga合金粉末粉碎至平均粒徑(D50)為10μm~45μm後，進行冷間靜水等冷均壓成型，之後，在真空、惰性氣體或還原環境中於720℃以上850℃以下藉由常壓燒結法燒結。 That is, the method for producing a Cu-Ga alloy sputtering target of the present invention is characterized in that the outer peripheral portion is formed of a CuGa 2 phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase, and the central portion is composed of a Ga concentration. a Cu-Ga alloy powder which is formed by a CuGa alloy phase lower than the outer peripheral portion and/or a Cu phase and/or a pure Cu phase in which Ga is dissolved, and an average Ga concentration of 20 atom% or more and less than 32 atom%. After pulverizing to an average particle diameter (D50) of 10 μm to 45 μm, cold soak molding such as cold room cooling is performed, and then sintering is performed by a normal pressure sintering method in a vacuum, an inert gas or a reducing atmosphere at 720 ° C or more and 850 ° C or less. .

又，本發明之Cu-Ga合金濺鍍靶的製造方法之另一態樣，其特徵為外周部係由CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，中心部係由Ga濃度比前述外周部低之CuGa合金相及/或固溶有Ga的Cu相及/或純Cu相所成，且將平均Ga濃度為20原子%以上並未滿32原子%，平均粒徑(D50)為10μm~45μm之Cu-Ga合金粉末進行冷間靜水等冷均壓成型，之後，在真空、惰性氣體或還原 環境中以720℃以上850℃以下藉由常壓燒結法燒結。 Further, another aspect of the method for producing a Cu-Ga alloy sputtering target according to the present invention is characterized in that the outer peripheral portion is formed of a CuGa 2 phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase. The portion is formed of a CuGa alloy phase having a lower Ga concentration than the outer peripheral portion and/or a Cu phase and/or a pure Cu phase in which Ga is dissolved, and the average Ga concentration is 20 atom% or more and less than 32 atom%. Cu-Ga alloy powder having an average particle diameter (D50) of 10 μm to 45 μm is subjected to cold pressure equalization molding such as cold room static water, and then sintered at normal pressure in a vacuum, an inert gas or a reducing atmosphere at 720 ° C or higher and 850 ° C or lower. Sintering.

本發明中，即使為常壓燒結法，可於燒結中使液相出現而減少燒結體內的空孔，故可得到高密度化的燒結體。 In the present invention, even in the normal pressure sintering method, a liquid phase can be formed during sintering to reduce voids in the sintered body, so that a sintered body having a high density can be obtained.

以下，詳細地說明關於適用本發明之Cu-Ga合金濺鍍靶的製造方法。另外，本發明只要沒有特別限定，就並非以下詳細說明所限定者。 Hereinafter, a method for producing a Cu-Ga alloy sputtering target to which the present invention is applied will be described in detail. In addition, the invention is not limited to the following detailed description unless otherwise specified.

<Cu-Ga合金濺鍍靶> <Cu-Ga alloy sputtering target>

首先，說明關於藉由適用本發明之Cu-Ga合金濺鍍靶的製造方法所得到Cu-Ga合金濺鍍靶。Cu-Ga合金濺鍍靶係可將Cu-Ga合金粉末作為原料，藉由常壓燒結法製造。 First, a Cu-Ga alloy sputtering target obtained by a method for producing a Cu-Ga alloy sputtering target to which the present invention is applied will be described. The Cu-Ga alloy sputtering target system can be produced by a normal pressure sintering method using Cu-Ga alloy powder as a raw material.

作為此CuGa合金粉末，可使用外周部由CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，中心部係由Ga濃度比外周部低之CuGa合金相及/或固溶有Ga的Cu相及/或純Cu相所成，且將平均Ga濃度為20原子%以上並未滿32原子%的Cu-Ga合金粉末作為原料粉末，再將此原料粉末粉碎至平均粒徑(D50)為10μm~45μm之Cu-Ga合金粉末者，或可使用外周部係由CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，中心部係由Ga濃度比外周部 低之CuGa合金相及/或固溶有Ga的Cu相及/或純Cu相所成，且平均Ga濃度為20原子%以上並未滿32原子%，平均粒徑(D50)為10μm~45μm之Cu-Ga合金粉末。 As the CuGa alloy powder, a CuGa 2 phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase may be used in the outer peripheral portion, and a CuGa alloy phase and/or a solid portion having a lower Ga concentration than the outer peripheral portion may be used. a Cu-phase and/or a pure Cu phase in which Ga is dissolved, and a Cu-Ga alloy powder having an average Ga concentration of 20 at% or more and less than 32 at% is used as a raw material powder, and the raw material powder is pulverized to an average particle. The Cu-Ga alloy powder having a diameter (D50) of 10 μm to 45 μm may be formed of a CuGa 2 phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase in the outer peripheral portion, and a Ga concentration in the center portion. It is formed by a CuGa alloy phase lower than the outer peripheral portion and/or a Cu phase and/or a pure Cu phase in which Ga is dissolved, and the average Ga concentration is 20 atom% or more and less than 32 atom%, and the average particle diameter (D50) is Cu-Ga alloy powder of 10 μm to 45 μm.

Cu-Ga合金濺鍍靶係燒結此Cu-Ga合金粉末而得到者，燒結之際CuGa2相及/或Cu9Ga4(γ2、γ3)相藉由成為液相進入空孔，而變成高密度。Cu-Ga合金濺鍍靶，係相對密度為95%以上的高密度者。 The Cu-Ga alloy sputtering target system is obtained by sintering the Cu-Ga alloy powder, and the CuGa 2 phase and/or the Cu 9 Ga 4 (γ 2 , γ 3 ) phase enters the void by the liquid phase during sintering. Become high density. The Cu-Ga alloy sputtering target is a high density with a relative density of 95% or more.

<1.Cu-Ga合金粉末的製造方法> <1. Method for Producing Cu-Ga Alloy Powder>

首先，說明關於Cu-Ga合金粉末的製造方法。 First, a method of producing a Cu-Ga alloy powder will be described.

此處製作的Cu-Ga合金粉末係為了促進後續步驟之燒結，而使平均粒徑(D50)為10μm~45μm。Cu-Ga合金粉末的平均粒徑(D50)超過45μm時，燒結無法邁進，Cu-Ga合金濺鍍靶的相對密度會變低。另外，平均粒徑(D50)未滿10μm之Cu-Ga合金粉末，將用於得到Cu-Ga合金粉末的起始原料之Cu粉末的粒徑做成極細，如後述有必要在合金化後將Cu-Ga合金粉末微細地粉碎，需要另外的粉碎步驟，不僅製造步驟變得複雜，且Cu-Ga合金粉末變成高成本，没有經濟的優點。平均粒徑(D50)為10μm~45μm的範圍時，Cu-Ga合金濺鍍靶的相對密度變成95%以上，濺鍍過程中的電弧會減低。藉由後述之Cu粉末的粒徑或粉碎來調整Cu-Ga合金粉末的平均粒徑(D50)。 The Cu-Ga alloy powder produced here has an average particle diameter (D50) of 10 μm to 45 μm in order to promote sintering in the subsequent step. When the average particle diameter (D50) of the Cu-Ga alloy powder exceeds 45 μm, the sintering cannot proceed, and the relative density of the Cu-Ga alloy sputtering target becomes low. Further, the Cu-Ga alloy powder having an average particle diameter (D50) of less than 10 μm is extremely fine in the particle size of the Cu powder for obtaining the starting material of the Cu-Ga alloy powder, and it is necessary to be alloyed as described later. The Cu-Ga alloy powder is finely pulverized, and an additional pulverization step is required. Not only the manufacturing steps become complicated, but the Cu-Ga alloy powder becomes high in cost, and there is no economic advantage. When the average particle diameter (D50) is in the range of 10 μm to 45 μm, the relative density of the Cu-Ga alloy sputtering target becomes 95% or more, and the arc during sputtering is reduced. The average particle diameter (D50) of the Cu-Ga alloy powder is adjusted by the particle diameter or pulverization of the Cu powder described later.

Cu-Ga合金粉末的平均粒徑係以雷射繞射法測 定合金粉末之粒度分佈，由小徑側累積計算存在比例(體積基準)，其值為跨及全部粒徑的存在比例之累積計算值的一半時之粒徑(D50)。 The average particle size of Cu-Ga alloy powder is measured by laser diffraction method. The particle size distribution of the alloy powder is calculated by accumulating the existence ratio (volume basis) from the small diameter side, and the value is the particle diameter (D50) at half the cumulative calculation value of the existence ratio of the entire particle diameter.

(原料) (raw material)

作為Cu-Ga合金粉末的原料，使用Cu粉末及Ga。Cu粉末及Ga的純度，在不會對由Cu-Ga合金濺鍍靶所形成之CIGS光吸收層的特性造成影響之下，可適當地選擇。 As a raw material of the Cu-Ga alloy powder, Cu powder and Ga are used. The purity of the Cu powder and Ga can be appropriately selected without affecting the characteristics of the CIGS light absorbing layer formed by the Cu-Ga alloy sputtering target.

Cu粉末可使用例如藉由電解法或噴霧法製造之電解Cu粉或噴霧Cu粉。電解Cu粉係在硫酸銅溶液等電解液中利用電分解於陰極上析出海綿狀或樹枝狀形狀之Cu而製造。噴霧Cu粉係藉由氣體噴霧法、水噴霧法、離心噴霧法、熔融萃取法等製造球狀或不定型形狀之Cu粉末。再者，Cu粉末亦可使用以該等方法以外所製造者。 As the Cu powder, for example, electrolytic Cu powder or spray Cu powder produced by an electrolytic method or a spray method can be used. The electrolytic Cu powder is produced by electrolyzing an electrolytic solution such as a copper sulfate solution onto the cathode to deposit a sponge or a dendritic shape of Cu. The sprayed Cu powder is produced by a gas spray method, a water spray method, a centrifugal spray method, a melt extraction method, or the like to produce a spherical or amorphous Cu powder. Further, Cu powder can also be used in addition to those manufactured by these methods.

Cu粉末的平均粒徑(D50)，係5μm~150μm為佳。CuGa合金化後不粉碎Cu-Ga合金粉末而直接使用時，將Cu粉末的平均粒徑(D50)設為5μm~23μm，CuGa合金化後粉碎Cu-Ga合金粉末時，Cu粉末的平均粒徑(D50)設為超過23μm並150μm以下。 The average particle diameter (D50) of the Cu powder is preferably 5 μm to 150 μm. When CuGa is alloyed and the Cu-Ga alloy powder is not pulverized and used as it is, the average particle diameter (D50) of the Cu powder is set to 5 μm to 23 μm, and the average particle diameter of the Cu powder when the CuGa alloy is pulverized by CuGa alloying. (D50) is set to exceed 23 μm and 150 μm or less.

Cu粉末的平均粒徑(D50)未滿5μm時，不僅粉末本身高價，而且需要防止Cu粉末之飛散的特別操作，同時會增加Cu粉末的鬆容量，使合金粉末之製造裝置大型化，變成需求昂貴裝置。另外，若Cu粉末的平均 粒徑(D50)為5μm以上，則合金化後Cu-Ga合金粉末的平均粒徑(D50)會成為10μm以上。 When the average particle diameter (D50) of the Cu powder is less than 5 μm, not only the powder itself is expensive, but also a special operation for preventing the scattering of the Cu powder, and the looseness of the Cu powder is increased, and the manufacturing apparatus of the alloy powder is enlarged and becomes a demand. Expensive device. In addition, if the average of Cu powder When the particle diameter (D50) is 5 μm or more, the average particle diameter (D50) of the Cu—Ga alloy powder after alloying is 10 μm or more.

Cu粉末的平均粒徑(D50)超過150μm時，減少Ga不得不被覆Cu粉末的比表面積(BET法)，減少以Ga被覆Cu粉末所必須之Ga量，因而，剩餘未反應Ga之液相剩下，無法有效地利用Ga。並且，擴散Ga的進行亦變慢，很多Cu芯存在，即使粉碎亦變為難以將Cu-Ga合金粉末的平均粒徑(D50)設為45μm以下。Cu-Ga合金粉末的平均粒徑(D50)超過45μm時，粉末彼此的接觸面積變小，無法進行燒結，Cu-Ga合金濺鍍靶的空孔率變高，降低Cu-Ga合金濺鍍靶的密度。 When the average particle diameter (D50) of the Cu powder exceeds 150 μm, the specific surface area (BET method) in which the Ga powder has to be coated with the Cu powder is reduced, and the amount of Ga necessary for coating the Cu powder with Ga is reduced, so that the remaining unreacted Ga liquid remains. Under, it is impossible to use Ga efficiently. Further, the progress of the diffusion Ga is also slow, and many Cu cores are present, and even if pulverized, it becomes difficult to set the average particle diameter (D50) of the Cu-Ga alloy powder to 45 μm or less. When the average particle diameter (D50) of the Cu-Ga alloy powder exceeds 45 μm, the contact area between the powders becomes small, sintering is impossible, and the porosity of the Cu-Ga alloy sputtering target becomes high, and the Cu-Ga alloy sputtering target is lowered. Density.

因此，藉由將Cu粉末的平均粒徑(D50)設為5μm~150μm，不需要防止Cu粉末之飛散的操作，而可防止合金粉末製造裝置大型化，又，可減少未反應之液相Ga，而可有效地利用Ga。 Therefore, by setting the average particle diameter (D50) of the Cu powder to 5 μm to 150 μm, it is not necessary to prevent the scattering of the Cu powder, and it is possible to prevent the alloy powder manufacturing apparatus from being enlarged, and to reduce the unreacted liquid phase Ga. , and can effectively utilize Ga.

又，Cu粉末之平均粒徑係以雷射繞射法測定Cu粉末之粒度分佈，由小徑側累積計算存在比例(體積基準)，其值為跨及全部粒徑的存在比例之累積計算值的一半時之粒徑(D50)。 Further, the average particle diameter of the Cu powder is measured by a laser diffraction method, and the particle size distribution of the Cu powder is measured, and the ratio (volume basis) is calculated from the small-diameter side cumulative value, and the value is the cumulative calculated value of the ratio of the existence of all the particle diameters. Half the particle size (D50).

Ga為熔點低的金屬(熔點：29.78℃)，可藉由加熱容易地熔解。經熔解Ga係被覆Cu粉末而二元系合金化。Ga之形狀並無限制，但小片時容易秤量。Ga小片可在室溫附近熔解Ga並鑄造，且將鑄造物粉碎而得到。因Ga係在低溫變成液體，關於調配之Ga的平均粒 徑(大小)係就Cu-Ga合金粉末的平均粒徑之觀點而言沒有限制。因此，選擇為了容易調配的秤量或容易處理的形狀之Ga。 Ga is a metal having a low melting point (melting point: 29.78 ° C) and can be easily melted by heating. The Ga-based coated Cu powder is melted and the binary system is alloyed. There is no limit to the shape of the Ga, but it is easy to measure when the piece is small. The Ga pellet can be obtained by melting Ga and casting at around room temperature, and pulverizing the cast. Since the Ga system becomes a liquid at a low temperature, the average particle of the formulated Ga The diameter (size) is not limited in terms of the average particle diameter of the Cu-Ga alloy powder. Therefore, Ga is selected for easy weighing or a shape that is easy to handle.

(調配) (provisioning)

在原子量比計以80：20~68：32之比例調配Cu粉末與Ga。藉由Ga量為20原子%以上，變成有藉由Ga的Cu粉末之均勻被覆的可能性，Cu-Ga合金粉末的外周部係比低熔點的CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，有將得到的粉末燒結之際成為均勻合金組織的可能性。另外，藉由使Ga量為未滿32原子%，可防止因Cu粉末間存在之大量Ga造成Cu粉末彼此結合成為塊狀，而可提高Cu-Ga合金粉末的收率。 The Cu powder and Ga are formulated in an atomic ratio of 80:20 to 68:32. When the amount of Ga is 20 atom% or more, it is possible to uniformly coat the Cu powder by Ga. The outer peripheral portion of the Cu-Ga alloy powder is lower than the low melting point CuGa 2 phase and/or Cu 9 Ga 4 (γ). 2 , γ 3 ) phase, there is a possibility that the obtained powder will become a uniform alloy structure when sintered. Further, by setting the amount of Ga to less than 32 atom%, it is possible to prevent the Cu powder from being bonded to each other due to a large amount of Ga existing between the Cu powders, thereby increasing the yield of the Cu-Ga alloy powder.

(合金化) (alloying)

使以上述原子量比調配Cu粉末與Ga而成之混合粉末在真空或惰性氣體環境中於110℃以上350℃以下之溫度攪拌而合金化。作為環境真空為佳，具體而言，使以上述原子量比秤量之Cu粉末與Ga小片投入混合設置，將環境設為真空後，藉由以加熱手段將溫度控制在110℃以上並350℃以下的範圍，用攪拌機攪拌並混合Cu粉末與Ga，而製作Cu粉末之外周部及內部分散有Ga的Cu-Ga二元系合金粉末。 The mixed powder obtained by blending Cu powder and Ga in the above atomic ratio is stirred and alloyed in a vacuum or an inert gas atmosphere at a temperature of 110 ° C or more and 350 ° C or less. It is preferable to use an environmental vacuum, and specifically, the Cu powder and the Ga piece which are weighed by the atomic weight ratio are mixed, and after the environment is set to a vacuum, the temperature is controlled to 110° C. or more and 350° C. or less by heating means. In the range, the Cu powder and Ga were stirred and mixed with a stirrer to prepare a Cu-Ga binary alloy powder in which Ga was dispersed in the peripheral portion and the inside of the Cu powder.

Cu-Ga合金粉末被認為係經過如下過程而形成 者。使超過熔點而成為液體之Ga邊利用混合之剪斷運動成為小的液滴邊均一分散於Cu粉末間。分散之Ga液滴附著在Cu粉末之周圍，Cu粉末與Ga液滴接觸時Ga開始擴散於Cu粉末中，邊提高Ga濃度同時生成CuGa金屬間化合物邊進行合金化反應。 Cu-Ga alloy powder is considered to be formed by the following process By. The Ga side which becomes a liquid beyond the melting point is uniformly dispersed in the Cu powder by the shearing motion of the mixing. The dispersed Ga droplets adhere to the periphery of the Cu powder, and when the Cu powder is in contact with the Ga droplets, Ga starts to diffuse into the Cu powder, and the alloying reaction is performed while increasing the Ga concentration and simultaneously forming the CuGa intermetallic compound.

此時，成為Cu-Ga合金粉末的外周部係由Ga濃度高之CuGa金屬間化合物層的CuGa2(θ)相及/或Cu9Ga4(γ2、γ3)相所成，中心部係Ga濃度為20.5原子%~22.5原子%的ζ相或Ga濃度為29.8原子%~37.4原子%的γ1相之比外周部Ga濃度低的CuGa合金相、Ga固熔之Cu相或純Cu相所成。 In this case, the outer peripheral portion of the Cu-Ga alloy powder is formed of a CuGa 2 (θ) phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase of a CuGa intermetallic compound layer having a high Ga concentration, and a central portion thereof. Department Ga concentration was 20.5 atomic% to 22.5 atomic% of ζ phase or Ga concentration of 29.8 at% to 37.4 at% of γ 1 relative to the phase of the outer peripheral portion Ga low concentration CuGa alloy, Ga solid solution of the Cu phase or pure Cu The result is.

藉由將Cu-Ga合金粉末的合金化溫度控制在110℃以上並350℃以下的範圍，可使Cu-Ga合金粉末的外周部形成CuGa2(θ)相或Cu9Ga4(γ2、γ3)相，又，可使中心部形成Cu9Ga4(γ1)相、Cu3Ga(ζ)相、固溶有Ga之Cu相、純Cu相。另外，一般攪拌溫度為254℃以上時，因超過θ相的熔點而自θ相溶出Ga，而變態為γ3相(Ga：37.5原子%~42.7原子%)或γ2相(Ga：33.9原子%~37.7原子%)。 By controlling the alloying temperature of the Cu—Ga alloy powder to a range of 110° C. or more and 350° C. or less, CuGa 2 (θ) phase or Cu 9 Ga 4 (γ 2 , Cu 2 Ga 2 (θ 2 ) can be formed in the outer peripheral portion of the Cu—Ga alloy powder. In the γ 3 ) phase, a Cu 9 Ga 4 (γ 1 ) phase, a Cu 3 Ga (ζ) phase, a Cu phase in which a solution is dissolved, and a pure Cu phase can be formed in the center portion. Further, when the general stirring temperature is 254 ° C or higher, Ga is eluted from the θ phase by exceeding the melting point of the θ phase, and the metamorphosis is γ 3 phase (Ga: 37.5 atom% to 42.7 atom%) or γ 2 phase (Ga: 33.9 atom). %~37.7 atom%).

又，藉由將Cu-Ga合金粉末的合金化在真空環境中或Ar等惰性氣體環境中等進行，可抑制Cu-Ga合金粉末內的氧含有量。 Further, by alloying the Cu-Ga alloy powder in a vacuum atmosphere or an inert gas atmosphere such as Ar, the oxygen content in the Cu-Ga alloy powder can be suppressed.

該Cu粉末與Ga之混合使均一之合金化反應有效地進行。且，混合之剪斷運動被認為是藉由粉末彼此 之固著亦可抑制塊狀物之生成。塊狀物生成時，在熱壓等燒結步驟中，燒結體中生成空孔，會使密度變得不均一。 The mixing of the Cu powder and Ga allows the uniform alloying reaction to proceed efficiently. And the mixed shearing motion is considered to be by powder with each other The fixation also inhibits the formation of the mass. When the lump is formed, in the sintering step such as hot pressing, voids are formed in the sintered body, and the density becomes uneven.

在為了Cu粉末與Ga之混合及合金化的加熱，可使用使攪拌翼或攪拌葉片等攪拌機在容器內運動之混合裝置。另外，亦可使用圓筒、雙錐體、雙筒混合機等旋轉容器型之混合裝置。另外，亦可於容器之內部投入球體而強化混合。 In order to heat and mix the Cu powder and Ga, it is possible to use a mixing device that moves a stirrer such as a stirring blade or a stirring blade in a container. Further, a rotary container type mixing device such as a cylinder, a double cone, or a double cylinder mixer can also be used. In addition, it is also possible to inject a sphere into the interior of the container to enhance mixing.

容器材質可由對加熱之耐熱性、與Ga及Cu-Ga合金之附著抑制的觀點加以選擇。作為容器例如可使用硼矽酸玻璃、石英玻璃等玻璃容器，氧化鋁或氧化鋯等陶瓷容器、鐵氟龍(註冊商標)樹脂容器、被覆鐵氟龍(註冊商標)之容器、搪瓷容器等。 The material of the container can be selected from the viewpoints of heat resistance to heating and adhesion inhibition with Ga and a Cu-Ga alloy. As the container, for example, a glass container such as borosilicate glass or quartz glass, a ceramic container such as alumina or zirconia, a Teflon (registered trademark) resin container, a container coated with Teflon (registered trademark), or an enamel container can be used.

如此所製作Cu-Ga合金粉末係強度或成型性等優異，同時因製作溫度為低溫而變成在製作使用簡單的裝置，具有可廉價製作合金粉末之優點。 The Cu-Ga alloy powder produced in this manner is excellent in strength, moldability, and the like, and has a low temperature to make it easy to manufacture and use, and has an advantage that the alloy powder can be produced at low cost.

如以上之Cu-Ga合金粉末的製造方法中，在原子量比計以80：20~68：32之比例調配Cu粉末與Ga，在110℃以上並350℃以下的範圍，且藉由真空中或Ar環境中加熱並進行合金化，可得到具有優異之成型性的Cu-Ga合金粉末。有藉由攪拌溫度調整得到之合金相的可能性。 In the method for producing a Cu-Ga alloy powder as described above, Cu powder and Ga are blended in an atomic ratio of 80:20 to 68:32, in a range of 110 ° C or more and 350 ° C or less, and by vacuum or Heating and alloying in an Ar environment can obtain a Cu-Ga alloy powder having excellent moldability. There is a possibility of adjusting the alloy phase obtained by stirring the temperature.

在CuGa合金相的特定係將粉末以樹脂埋入後進行剖面研磨，藉由使用EPMA(Electron Probe Micro Analyser)之定性分析就可得知。 In the specific system of the CuGa alloy phase, the powder was embedded in a resin and then subjected to cross-section polishing, which was known by qualitative analysis using EPMA (Electron Probe Micro Analyser).

(粉碎) (crush)

在合金化步驟所得到Cu-Ga合金粉末的平均粒徑為10μm~45μm時，可不經粉碎步驟直接進入Cu-Ga合金濺鍍靶製造步驟。又，平均粒徑超過45μm時，以下述說明的粉碎步驟調整Cu-Ga合金粉末的粒徑。 When the average particle diameter of the Cu-Ga alloy powder obtained in the alloying step is 10 μm to 45 μm, the Cu-Ga alloy sputtering target manufacturing step can be directly entered without the pulverization step. Moreover, when the average particle diameter exceeds 45 μm, the particle diameter of the Cu—Ga alloy powder is adjusted by the pulverization step described below.

Cu-Ga合金化物的粉碎之環境，係大氣中或Ar等惰性氣體環境為佳。作為進行粉碎的裝置，可使用球磨機。使用於球磨機的球，係可使用被覆Al2O3、被覆ZrO2、被覆SUS球或被覆鐵氟龍(註冊商標)的SUS球，直徑為5mm~20mm左右。又，使用球磨機時，旋轉數為50rpm~250rpm左右。 The pulverized environment of the Cu-Ga alloy is preferably in the atmosphere or an inert gas atmosphere such as Ar. As a device for pulverizing, a ball mill can be used. For the ball used in the ball mill, a SUS ball coated with Al 2 O 3 , coated with ZrO 2 , coated with a SUS ball or coated with Teflon (registered trademark), and having a diameter of about 5 mm to 20 mm can be used. Further, when a ball mill is used, the number of rotations is about 50 rpm to 250 rpm.

球磨機之外，在粉碎可使用噴射磨機或鎚磨機等。又，亦可將球置入在Cu粉末與Ga的合金化之際的攪拌所使用燒杯使翼旋轉進行粉碎。 In addition to the ball mill, a jet mill or a hammer mill or the like can be used for the pulverization. Further, the ball may be placed in a beaker for agitation during the alloying of Cu powder and Ga, and the blade may be rotated and pulverized.

如此，粉碎Cu-Ga合金化物可將Cu-Ga合金粉末的平均粒徑調整至10μm~45μm，而可製作高密度的Cu-Ga合金濺鍍靶。 Thus, the Cu-Ga alloy can be pulverized to adjust the average particle diameter of the Cu-Ga alloy powder to 10 μm to 45 μm, and a high-density Cu-Ga alloy sputtering target can be produced.

<2.Cu-Ga合金濺鍍靶的製造方法> <2. Method for Producing Cu-Ga Alloy Sputtering Target>

接著，說明關於上述使用Cu-Ga合金粉末之Cu-Ga合金濺鍍靶的製造方法。 Next, a method of producing the Cu-Ga alloy sputtering target using the Cu-Ga alloy powder described above will be described.

(成型) (forming)

首先，將Cu-Ga合金粉末饋送至橡膠型。並沒有限制橡膠型的形狀，平板型者、圓筒系型者均有可適用的可能性。 First, the Cu-Ga alloy powder was fed to a rubber type. There is no restriction on the shape of the rubber type, and both the flat type and the cylindrical type are applicable.

成型步驟中將Cu-Ga合金粉末以300MPa以上的壓力進行加壓成型，得到成型體。低於300MPa的低壓力係難以去除存在粒子間的空孔，導致燒結體的密度降低。又，成型體強度亦變小，變成難以安定地製造。在加壓成型時，期望使用可獲得高壓力之冷間靜水等冷均壓(CIP：Cold Isostatic Press)。 In the molding step, the Cu—Ga alloy powder is press-molded at a pressure of 300 MPa or more to obtain a molded body. A low pressure of less than 300 MPa is difficult to remove voids between the particles, resulting in a decrease in the density of the sintered body. Moreover, the strength of the molded body is also small, and it becomes difficult to manufacture stably. At the time of press molding, it is desirable to use a cold isostatic press (CIP: Cold Isostatic Press) which can obtain a high pressure.

(燒結) (sintering)

燒結係藉由常壓燒結法(含真空燒結)進行。具體而言，期望於真空中，惰性氣體環境、或還原環境中進行。藉由於真空中、惰性氣體環境、或還原環境中進行Cu-Ga合金粉末的燒結，可減低Cu-Ga合金粉末之燒結體的氧含有量。 The sintering is carried out by a normal pressure sintering method (including vacuum sintering). Specifically, it is desirable to carry out in a vacuum, an inert gas atmosphere, or a reducing environment. The oxygen content of the sintered body of the Cu-Ga alloy powder can be reduced by sintering the Cu-Ga alloy powder in a vacuum, an inert gas atmosphere, or a reducing atmosphere.

又，燒結步驟中，依Ga濃度而邊調整燒結溫度，邊於720℃以上並850℃以下的溫度範圍進行燒結。燒結溫度未滿720℃時，燒結體的密度不會變高，而不佳。又，燒結溫度超過850℃時，因燒結時出現很多液相，有自燒結體流出的情形，難以得到高密度的燒結體之同時，有些情況下與燒結爐的爐底板黏固，而不佳。 Further, in the sintering step, the sintering temperature is adjusted in accordance with the Ga concentration, and sintering is performed in a temperature range of 720 ° C or more and 850 ° C or less. When the sintering temperature is less than 720 ° C, the density of the sintered body does not become high, which is not preferable. Further, when the sintering temperature exceeds 850 ° C, many liquid phases appear during sintering, and there is a case where the sintered body flows out, and it is difficult to obtain a high-density sintered body, and in some cases, it is stuck to the furnace floor of the sintering furnace, which is not preferable. .

因此，燒結步驟中使用上述特定的Cu-Ga合金粉末，以常壓燒結法於真空中、惰性氣體環境、或還原 環境中，且控制在720℃以上850℃以下的溫度範圍之方式進行燒結，使液相適度地出現，並此液相變成可進入成型體的空孔。其結果，可使燒結體高密度化。 Therefore, the specific Cu-Ga alloy powder described above is used in the sintering step, in a vacuum, an inert gas atmosphere, or a reduction by a normal pressure sintering method. In the environment, and sintering is controlled in a temperature range of 720 ° C or more and 850 ° C or less, the liquid phase is moderately formed, and the liquid phase becomes a void which can enter the molded body. As a result, the sintered body can be made denser.

(完工) (Completed)

燒結後進行完工處理。完工係藉由研削CuGa合金燒結體表面，使其成為平面，而黏固在Cu製背襯板上。 Finished after sintering. The finishing is performed by grinding the surface of the sintered body of the CuGa alloy to make it flat and adhering to the Cu backing plate.

(評價) (Evaluation)

Cu-Ga合金濺鍍靶的製造方法中，關於得到的Cu-Ga合金濺鍍靶，使用濺鍍裝置並由有沒有發生電弧的現象，而進行Cu-Ga合金濺鍍靶之性能的評價。具體而言，連接於濺鍍裝置，真空排氣至1.0×10-4Pa以下為止之後，使Ar氣體(純度：99.99%)流通，在Ar氣壓0.5Pa、DC100W的條件下濺鍍，成膜濺鍍膜。使用微小型電弧監視器(LANDMARK TECHNOLOGY CORPORATION製)計數1分鐘平均的異常放電。 In the method for producing a Cu-Ga alloy sputtering target, the performance of the Cu-Ga alloy sputtering target was evaluated by using a sputtering apparatus and the presence or absence of an arc in the obtained Cu-Ga alloy sputtering target. Specifically, after being connected to a sputtering apparatus and evacuated to 1.0×10 −4 Pa or less, Ar gas (purity: 99.99%) is passed, and sputtering is performed under the conditions of an Ar gas pressure of 0.5 Pa and DC 100 W to form a film. Sputtered film. An abnormal discharge of 1 minute average was counted using a micro-small arc monitor (manufactured by LANDMARK TECHNOLOGY CORPORATION).

如以上，Cu-Ga合金濺鍍靶的製造方法中，其係將下述二種Cu-Ga合金粉末進行加壓成型，並藉由常壓燒結，而可製造高密度的Cu-Ga合金濺鍍靶，一種係外周部由CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，中心部係由Ga濃度比外周部低之CuGa合金相及/或固溶有Ga的Cu相及/或純Cu相所成，且將平均Ga濃度為20原子%以上並未滿32原子%的Cu-Ga合金粉末粉碎至平均粒徑 (D50)為10μm~45μm，或另一種係外周部係由CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，中心部係由Ga濃度比外周部低之CuGa合金相及/或固溶有Ga的Cu相及/或純Cu相所成，且平均Ga濃度為20原子%以上並未滿32原子%，平均粒徑(D50)為10μm~45μm之Cu-Ga合金粉末。 As described above, in the method for producing a Cu-Ga alloy sputtering target, the following two Cu-Ga alloy powders are subjected to pressure molding, and a high-density Cu-Ga alloy splash can be produced by normal pressure sintering. The plating target is formed by a CuGa 2 phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase, and a central portion is a CuGa alloy phase having a lower Ga concentration than the outer peripheral portion and/or a solid solution of Ga. The Cu-Ga alloy powder having an average Ga concentration of 20 at% or more and less than 32 at% is pulverized to an average particle diameter (D50) of 10 μm to 45 μm, or the other is formed by a Cu phase and/or a pure Cu phase. The outer peripheral portion is formed of a CuGa 2 phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase, and the central portion is a CuGa alloy phase having a lower Ga concentration than the outer peripheral portion and/or a Cu phase having a solid solution of Ga. And a Cu-Ga alloy powder obtained by a pure Cu phase and having an average Ga concentration of 20 at% or more and less than 32 at%, and an average particle diameter (D50) of 10 μm to 45 μm.

亦即，本發明中，並非熱壓法或HIP法等加壓燒結法，因藉由常壓燒結法製造Cu-Ga合金粉末的燒結體，燒結中低熔點的CuGa2相及/或Cu9Ga4(γ2、γ3)相變成液相，藉由液相進入成型體的空孔促進高密度化，而可提高燒結體的相對密度。其結果，可製造高密度的Cu-Ga合金濺鍍靶。 That is, in the present invention, it is not a pressure sintering method such as a hot press method or a HIP method, in which a sintered body of a Cu-Ga alloy powder is produced by a normal pressure sintering method, and a low-melting CuGa 2 phase and/or Cu 9 are sintered. The Ga 4 (γ 2 , γ 3 ) phase changes into a liquid phase, and the liquid phase enters the pores of the molded body to promote high density, and the relative density of the sintered body can be increased. As a result, a high-density Cu-Ga alloy sputtering target can be produced.

又，常壓燒結法中，因在燒結時沒有使用模型而一次可燒結大量張數的燒結體，可使生產性提升，同時亦有可以低成本製造燒結體的優點。 Further, in the normal pressure sintering method, since a large number of sintered bodies can be sintered at a time without using a mold at the time of sintering, productivity can be improved, and the sintered body can be manufactured at low cost.

[實施例] [Examples]

接著，藉由實施例更詳細地說明本發明之Cu-Ga合金濺鍍靶的製造方法，但本發明並非限定於該等實施例者，不脫離本發明之要旨的範圍內可添加種種變更。另外，將實施例1~11及比較例1~4之Cu-Ga合金製作步驟、成型‧燒結步驟及濺鍍評價的各條件及評價結果總結在以下的表1、表2及表3。 Next, the method for producing the Cu-Ga alloy sputtering target of the present invention will be described in more detail by way of examples. However, the present invention is not limited to the embodiments, and various modifications can be added without departing from the scope of the invention. Further, the conditions and evaluation results of the Cu-Ga alloy production steps, the molding, the sintering step, and the sputtering evaluation of Examples 1 to 11 and Comparative Examples 1 to 4 are summarized in Tables 1, 2, and 3 below.

(實施例1) (Example 1)

(合金粉製作步驟) (alloy powder production steps)

合金粉製作步驟中，使平均粒徑(D50)為100μm的Cu粉末與Ga成為Ga濃度為30原子%的方式準備Cu粉末2040g與Ga960g，加熱至250℃，在真空環境(200Pa以下)中，混合攪拌40分鐘而合金化Cu及Ga。將得到的Cu-Ga合金粉末埋入樹脂，進行剖面研磨後，用EPMA分析，確認γ3相、γ2相、γ1相、Cu固溶體相、及純Cu相的存在。 In the alloy powder production step, Cu powder of 2040 g and Ga960 g of Cu powder having an average particle diameter (D50) of 100 μm and Ga having a Ga concentration of 30 atom% were prepared and heated to 250 ° C in a vacuum environment (200 Pa or less). The mixture was stirred for 40 minutes to alloy Cu and Ga. The obtained Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of a γ 3 phase, a γ 2 phase, a γ 1 phase, a Cu solid solution phase, and a pure Cu phase.

以直径10mm的ZrO2球與Cu-Ga合金粉末為同質量的方式將得到的Cu-Ga合金粉末裝進聚乙烯製10L容器，以球磨機進行混合‧粉碎3小時。得到的粉碎合金粉末之平均粒徑(D50)為45μm。 10mm in diameter The Cu-Ga alloy powder obtained by charging the ZrO 2 ball and the Cu-Ga alloy powder in the same mass was placed in a 10 L container made of polyethylene, mixed by a ball mill, and pulverized for 3 hours. The obtained pulverized alloy powder had an average particle diameter (D50) of 45 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

將粉碎合金粉末鋪在220mm×330mm×25mm的橡膠型，以300MPa的壓力CIP成型，得到成型體。將得到的成型體在800℃、Ar環境下燒結24小時，製作燒結體。 The pulverized alloy powder was spread on a rubber type of 220 mm × 330 mm × 25 mm, and molded at a pressure of 300 MPa CIP to obtain a molded body. The obtained molded body was sintered at 800 ° C for 24 hours in an Ar atmosphere to prepare a sintered body.

研磨燒結體後，用EPMA分析，確認γ1相(Cu9Ga4)單相的存在。又，Ga濃度為30原子%。 After the sintered body was polished, the presence of a single phase of the γ 1 phase (Cu 9 Ga 4 ) was confirmed by EPMA analysis. Further, the Ga concentration was 30 atom%.

將光學顯微鏡得到的圖像使用圖像分析軟件Image J求出燒結體的空隙率時，其為4.82%，相對密度為96%。此外，作為相對密度係自100%減去空隙率的值。 When the image obtained by the optical microscope was used to obtain the porosity of the sintered body using the image analysis software Image J, it was 4.82% and the relative density was 96%. Further, the relative density is a value obtained by subtracting the void ratio from 100%.

(濺鍍評價) (splash evaluation)

將燒結體接合於Cu製背襯板而製作靶，連接與濺鍍裝置(ULVAC CORPORATION製SH450)。在濺鍍電源使用DC電源。 The sintered body was bonded to a Cu backing plate to prepare a target, and connected to a sputtering apparatus (SH450 manufactured by ULVAC CORPORATION). Use a DC power supply for the sputtered power supply.

作為基板使用25mm×76mm的不含鈉之玻璃，到達真空度為5×10-4Pa、Ar氣壓為0.5Pa、DC100W的條件下進行濺鍍成膜30分鐘。濺鍍中的電弧係用微小型電弧監視器(ADVANCED TECHNOLOGY CORPORATION製)測定。通常濺鍍開始後立即靶面的加工污垢等影響會發生電弧，濺鍍開始時，5分鐘係將靶略上的快門關閉，設為在基板未進行成膜的狀態，之後打開快門25分鐘在基板上進行濺鍍成膜。電弧測定亦打開快門設為進行25分鐘。其結果，不會發生電弧。 As a substrate, 25 mm × 76 mm of sodium-free glass was used, and the film was sputter-deposited for 30 minutes under conditions of a vacuum of 5 × 10 -4 Pa, an Ar gas pressure of 0.5 Pa, and a DC 100 W. The arc during sputtering was measured using a micro-small arc monitor (manufactured by ADVANCED TECHNOLOGY CORPORATION). Normally, immediately after the start of sputtering, arcing occurs due to the influence of processing dirt on the target surface. When the sputtering starts, the shutter on the target is closed for 5 minutes, and the substrate is not formed in the film, and then the shutter is opened for 25 minutes. Sputtering is performed on the substrate to form a film. The arc measurement also opens the shutter for 25 minutes. As a result, no arcing occurs.

(實施例2) (Example 2)

(合金粉製作步驟) (alloy powder production steps)

使Ga濃度成為31.9原子%的方式準備Cu粉末1982g與Ga1018g以外，與實施例1的條件同樣地合金化Cu及Ga。將得到的Cu-Ga合金粉末埋入樹脂、進行剖面研磨後，用EPMA分析，確認θ相、γ3相、及純Cu相的存在。 Cu and Ga were alloyed in the same manner as in the example 1 except that Cu powder 1982 g and Ga 1018 g were prepared so that the Ga concentration was 31.9 atom%. The obtained Cu-Ga alloy powder was embedded in a resin and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of the θ phase, the γ 3 phase, and the pure Cu phase.

將Cu-Ga合金粉末與實施例1的條件同樣地以球磨機進行混合‧粉碎。得到的粉碎合金粉末之平均粒 徑(D50)為40μm。 The Cu-Ga alloy powder was mixed and pulverized in a ball mill in the same manner as in the case of Example 1. Average particle size of the obtained pulverized alloy powder The diameter (D50) was 40 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末，750℃、真空中燒結24小時，製作燒結體。 The sintered alloy powder was sintered at 750 ° C for 24 hours in a vacuum to prepare a sintered body.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為31原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 31 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的空隙率求出相對密度時，其為95%。 When the relative density was determined from the void ratio of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 95%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例3) (Example 3)

(合金粉製作步驟) (alloy powder production steps)

使Ga濃度成為20原子%的方式準備Cu粉末2354g與Ga 646g的條件，以及將合金化溫度設為150℃，合金化時間設為50分鐘的條件以外，與實施例1的條件同樣地合金化Cu及Ga。將得到的Cu-Ga合金粉末埋入樹脂，進行剖面研磨後，用EPMA分析，確認θ相、γ2相、及純Cu相的存在。 In the same manner as in the case of Example 1, the conditions of the Cu powder of 2354 g and Ga 646 g and the alloying temperature of 150 ° C and the alloying time of 50 minutes were prepared so that the Ga concentration was 20 atomic %. Cu and Ga. The obtained Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of the θ phase, the γ 2 phase, and the pure Cu phase.

與實施例1的條件同樣地將Cu-Ga合金粉末 以球磨機進行混合‧粉碎。得到的粉碎合金粉末之平均粒徑(D50)為15μm。 Cu-Ga alloy powder was used in the same manner as in the case of Example 1. Mix and pulverize with a ball mill. The obtained pulverized alloy powder had an average particle diameter (D50) of 15 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末，將燒結環境設為真空、燒結溫度設為800℃以外，與實施例1的條件同樣地製作燒結體。 A sintered body was produced in the same manner as in the example 1 except that the pulverized alloy powder was used as a vacuum and the sintering temperature was set to 800 °C.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認Cu固溶體相及ζ相(Cu3Ga)的存在。又，Ga濃度為20原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the Cu solid solution phase and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 20 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的空隙率求出相對密度時，其為98%。 When the relative density was determined from the void ratio of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 98%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例4) (Example 4)

(合金粉製作步驟) (alloy powder production steps)

將Cu粉末之平均粒徑設為150μm的條件、合金化溫度設為350℃、合金化時間設為30分鐘的條件以外，與實施例1的條件同樣地合金化Cu及Ga。將得到的Cu-Ga合金粉末埋入樹脂，進行剖面研磨後，用EPMA分析，確認γ3相、γ2相、γ1相、ζ相、及純Cu相的存在。 Cu and Ga were alloyed in the same manner as in the example 1 except that the average particle diameter of the Cu powder was 150 μm, the alloying temperature was 350 ° C, and the alloying time was 30 minutes. The obtained Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of a γ 3 phase, a γ 2 phase, a γ 1 phase, a ζ phase, and a pure Cu phase.

將Cu-Ga合金粉末與實施例1的條件同樣地 以球磨機進行混合‧粉碎。得到的粉碎合金粉末之平均粒徑(D50)為10μm。 The Cu-Ga alloy powder was the same as the conditions of Example 1. Mix and pulverize with a ball mill. The obtained pulverized alloy powder had an average particle diameter (D50) of 10 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末，750℃、真空中燒結24小時，製作燒結體。 The sintered alloy powder was sintered at 750 ° C for 24 hours in a vacuum to prepare a sintered body.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為99% When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 99%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例5) (Example 5)

(合金粉製作步驟) (alloy powder production steps)

將Cu粉末之平均粒徑設為30μm以外，與實施例1的條件同樣地合金化Cu及Ga。將得到的Cu-Ga合金粉末埋入樹脂，進行剖面研磨後，用EPMA分析，確認γ3相、γ2相、Cu固溶體相及純Cu相的存在。 Cu and Ga were alloyed in the same manner as in the example 1 except that the average particle diameter of the Cu powder was 30 μm. The obtained Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of a γ 3 phase, a γ 2 phase, a Cu solid solution phase, and a pure Cu phase.

將Cu-Ga合金粉末與實施例1的條件同樣地以球磨機進行混合‧粉碎。得到的粉碎合金粉末之平均粒 徑(D50)為20μm。 The Cu-Ga alloy powder was mixed and pulverized in a ball mill in the same manner as in the case of Example 1. Average particle size of the obtained pulverized alloy powder The diameter (D50) was 20 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末，800℃、真空中燒結24小時，製作燒結體。 The sintered alloy powder was sintered at 800 ° C for 24 hours in a vacuum to prepare a sintered body.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為96%。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 96%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例6) (Example 6)

(合金粉製作步驟) (alloy powder production steps)

與實施例5的條件同樣地將Cu-Ga合金粉末進行製作，接著，與實施例1的條件同樣地用EPMA進行Cu-Ga合金粉末的分析時，確認γ3相、γ2相、Cu固溶體相及純Cu相的存在。 The Cu-Ga alloy powder was produced in the same manner as in the case of Example 5, and when the Cu-Ga alloy powder was analyzed by EPMA in the same manner as in the example 1, the γ 3 phase, the γ 2 phase, and the Cu solid were confirmed. The presence of a solution phase and a pure Cu phase.

與實施例1的條件同樣地將Cu-Ga合金粉末進行混合‧粉碎。得到的粉碎合金粉末之平均粒徑(D50)為20μm。 The Cu-Ga alloy powder was mixed and pulverized in the same manner as in the case of Example 1. The obtained pulverized alloy powder had an average particle diameter (D50) of 20 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末850℃、真空中燒結24小時，製作燒結體。 The sintered body was produced by sintering at 850 ° C in a vacuum for 24 hours.

與實施例1的條件同樣地用EPMA分析燒結體的剖面，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為97%。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 97%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例7) (Example 7)

(合金粉製作步驟) (alloy powder production steps)

與實施例1的條件同樣地將Cu-Ga合金粉末進行製作，接著，與實施例1的條件同樣地用EPMA進行Cu-Ga合金粉末的分析時，確認γ3相、γ2相、γ1相、Cu固溶體相及純Cu相的存在。 The Cu-Ga alloy powder was produced in the same manner as in the case of Example 1, and the γ 3 phase, the γ 2 phase, and the γ 1 were confirmed when the Cu-Ga alloy powder was analyzed by EPMA in the same manner as in the case of Example 1. The presence of phase, Cu solid solution phase and pure Cu phase.

與實施例1的條件同樣地將Cu-Ga合金粉末進行混合‧粉碎。得到的粉碎合金粉末之平均粒徑(D50)為45μm。 The Cu-Ga alloy powder was mixed and pulverized in the same manner as in the case of Example 1. The obtained pulverized alloy powder had an average particle diameter (D50) of 45 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末，720℃、真空中燒結24小時，製作燒結體。 The sintered alloy powder was sintered at 720 ° C for 24 hours in a vacuum to prepare a sintered body.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為95%。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 95%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例8) (Example 8)

(合金粉製作步驟) (alloy powder production steps)

將Cu粉末之平均粒徑設為23μm，沒有進行混合‧粉碎以外，與實施例1的條件同樣地合金化Cu及Ga。得到的Cu-Ga合金粉末的平均粒徑(D50)為45μm。又，Cu-Ga合金粉末埋入樹脂、進行剖面研磨後，用EPMA分析，確認γ3相及純Cu相的存在。 Cu and Ga were alloyed in the same manner as in the case of Example 1, except that the average particle diameter of the Cu powder was 23 μm. The obtained Cu-Ga alloy powder had an average particle diameter (D50) of 45 μm. Further, the Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of the γ 3 phase and the pure Cu phase.

(成型‧燒結步驟) (forming ‧ sintering step)

使用Cu-Ga合金粉末，750℃、真空中燒結24小時，製作燒結體。 The sintered body was produced by sintering at 750 ° C for 24 hours in a vacuum using Cu-Ga alloy powder.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為95%。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 95%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例9) (Example 9)

將Cu粉末之平均粒徑設為10μm，沒有進行混合‧粉碎以外，與實施例1的條件同樣地合金化Cu及Ga。得到的粉碎合金粉末之平均粒徑(D50)為19μm。又，Cu-Ga合金粉末埋入樹脂、進行剖面研磨後，用EPMA分析，確認γ3相、Cu固溶體相及純Cu相的存在。 The average particle diameter of the Cu powder was set to 10 μm, and Cu and Ga were alloyed in the same manner as in the case of Example 1 except that the mixing and the pulverization were carried out. The obtained pulverized alloy powder had an average particle diameter (D50) of 19 μm. Further, the Cu-Ga alloy powder was embedded in a resin and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of the γ 3 phase, the Cu solid solution phase, and the pure Cu phase.

(成型‧燒結步驟) (forming ‧ sintering step)

使用Cu-Ga合金粉末，750℃、真空中燒結24小時，製作燒結體。 The sintered body was produced by sintering at 750 ° C for 24 hours in a vacuum using Cu-Ga alloy powder.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯 微鏡照片的孔隙率求出相對密度時，其為98%。 The optical display from the sintered body is the same as the condition of Example 1. When the relative density was determined as the porosity of the micrograph, it was 98%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例10) (Embodiment 10)

將Cu粉末之平均粒徑設為5μm的條件、合金化溫度設為110℃、合金化時間設為60分鐘的條件以外，以及沒有進行混合‧粉碎以外，與實施例1的條件同樣地合金化Cu及Ga。得到的Cu-Ga合金粉末之平均粒徑(D50)為10μm。又，將Cu-Ga合金粉末埋入樹脂，進行剖面研磨後，用EPMA分析，確認θ相、γ3相及純Cu相的存在。 Alloying was carried out in the same manner as in Example 1 except that the average particle diameter of the Cu powder was 5 μm, the alloying temperature was 110 ° C, and the alloying time was 60 minutes. Cu and Ga. The obtained Cu-Ga alloy powder had an average particle diameter (D50) of 10 μm. Further, the Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of the θ phase, the γ 3 phase, and the pure Cu phase.

(成型‧燒結步驟) (forming ‧ sintering step)

使用Cu-Ga合金粉末，藉由含800℃、4體積%的H2氣體之N2氣體的還原環境中燒結24小時，製作燒結體。 A sintered body was produced by sintering a Cu-Ga alloy powder in a reducing atmosphere containing N 2 gas of H 2 gas at 800 ° C and 4% by volume for 24 hours.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡的孔隙率求出相對密度時，其為99%。 When the relative density was determined from the porosity of the optical microscope of the sintered body in the same manner as in the case of Example 1, it was 99%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(實施例11) (Example 11)

(合金粉製作步驟) (alloy powder production steps)

將合金化的環境設為Ar環境以外，與實施例1的條件同樣地合金化Cu及Ga。將得到的Cu-Ga合金粉末埋入樹脂、進行剖面研磨後，用EPMA分析，確認γ3相、γ2相、純Cu相的存在。 Cu and Ga were alloyed in the same manner as in the example 1 except that the alloying environment was changed to the Ar atmosphere. The obtained Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of a γ 3 phase, a γ 2 phase, and a pure Cu phase.

將Cu-Ga合金粉末與實施例1的條件同樣地以球磨機進行混合‧粉碎。得到的粉碎合金粉末之平均粒徑(D50)為35μm。 The Cu-Ga alloy powder was mixed and pulverized in a ball mill in the same manner as in the case of Example 1. The obtained pulverized alloy powder had an average particle diameter (D50) of 35 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末，750℃、真空中燒結24小時，製作燒結體。 The sintered alloy powder was sintered at 750 ° C for 24 hours in a vacuum to prepare a sintered body.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為96%。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 96%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，不會發生電弧放電。 When the sintered body was sputtered in the same manner as in the case of Example 1, arc discharge did not occur.

(比較例1) (Comparative Example 1)

(合金粉製作步驟) (alloy powder production steps)

使Ga濃度成為15原子%的方式準備Cu粉末2513g與Ga487g的條件以外，與實施例1的條件同樣地合金化Cu及Ga。將得到的Cu-Ga合金粉末埋入樹脂，進行剖面研磨後，用EPMA分析，確認γ1相、Cu固溶體相及純Cu相的存在。 Cu and Ga were alloyed in the same manner as in the example 1 except that the conditions of the Cu powder of 2513 g and Ga 487 g were prepared so that the Ga concentration was 15 atom%. The obtained Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of a γ 1 phase, a Cu solid solution phase, and a pure Cu phase.

將Cu-Ga合金粉末、與實施例1的條件同樣地以球磨機進行混合‧粉碎。得到的粉碎合金粉末之平均粒徑(D50)為30μm。 The Cu-Ga alloy powder was mixed and pulverized in a ball mill in the same manner as in the case of Example 1. The obtained pulverized alloy powder had an average particle diameter (D50) of 30 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末800℃，真空中燒結24小時，製作燒結體。 The sintered alloy powder was sintered at 800 ° C for 24 hours in a vacuum to prepare a sintered body.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認Cu固溶體相及ζ相(Cu3Ga)的存在。又，Ga濃度為15原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the Cu solid solution phase and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 15 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為90%。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 90%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，會發生電弧放電。 When the sintered body is sputtered in the same manner as in the case of the first embodiment, arc discharge occurs.

(比較例2) (Comparative Example 2)

(合金粉製作步驟) (alloy powder production steps)

將Cu粉末之平均粒徑設為30μm的條件及沒有進行混合‧粉碎的條件以外，與實施例1的條件同樣地合金化Cu及Ga。得到的Cu-Ga合金粉末之平均粒徑(D50)為59μm。又，Cu-Ga合金粉末埋入樹脂，進行剖面研磨後，用EPMA分析，確認γ2相、Cu固溶體相及純Cu相的存在。 Cu and Ga were alloyed in the same manner as in the case of Example 1, except that the average particle diameter of the Cu powder was 30 μm and the conditions of mixing and pulverization were not performed. The obtained Cu-Ga alloy powder had an average particle diameter (D50) of 59 μm. Further, the Cu-Ga alloy powder was embedded in a resin, and subjected to cross-section polishing, and then analyzed by EPMA to confirm the presence of the γ 2 phase, the Cu solid solution phase, and the pure Cu phase.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末800℃，真空中燒結24小時，製作燒結體。 The sintered alloy powder was sintered at 800 ° C for 24 hours in a vacuum to prepare a sintered body.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為88%。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 88%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，會發生電弧放電。 When the sintered body is sputtered in the same manner as in the case of the first embodiment, arc discharge occurs.

(比較例3) (Comparative Example 3)

(合金粉製作步驟) (alloy powder production steps)

與實施例1的條件同樣地將Cu-Ga合金粉末進行製作，接著，與實施例1的條件同樣地用EPMA進行Cu-Ga合金粉末的分析時，確認γ3相、γ2相、γ1相、Cu固溶體相及純Cu相的存在。 The Cu-Ga alloy powder was produced in the same manner as in the case of Example 1, and the γ 3 phase, the γ 2 phase, and the γ 1 were confirmed when the Cu-Ga alloy powder was analyzed by EPMA in the same manner as in the case of Example 1. The presence of phase, Cu solid solution phase and pure Cu phase.

與實施例1的條件同樣地將Cu-Ga合金粉末進行混合‧粉碎。得到的粉碎合金粉末之平均粒徑(D50)為45μm。 The Cu-Ga alloy powder was mixed and pulverized in the same manner as in the case of Example 1. The obtained pulverized alloy powder had an average particle diameter (D50) of 45 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末，860℃、真空中燒結24小時，製作燒結體時，燒結中液相溶出，燒結體的一部分黏固在爐底板。 The pulverized alloy powder was sintered at 860 ° C for 24 hours in a vacuum to form a sintered body, and the liquid phase was eluted during sintering, and a part of the sintered body was adhered to the furnace floor.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，雖有95%之高密度部分，藉由液相溶出亦有極為低密度部分的存在。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, the 95% high density portion was present in the liquid phase, and the extremely low density portion was present.

(濺鍍評價) (splash evaluation)

燒結體固著在爐底板，無法只取出燒結體，亦無法進 行濺鍍。 The sintered body is fixed on the bottom of the furnace, and it is impossible to take out only the sintered body, and it is impossible to enter Line sputtering.

(比較例4) (Comparative Example 4)

(合金粉製作步驟) (alloy powder production steps)

與實施例1的條件同樣地將Cu-Ga合金粉末進行製作，接著，與實施例1的條件同樣地用EPMA進行Cu-Ga合金粉末的分析時，確認γ3相、γ2相、γ1相、Cu固溶體相及純Cu相的存在。 The Cu-Ga alloy powder was produced in the same manner as in the case of Example 1, and the γ 3 phase, the γ 2 phase, and the γ 1 were confirmed when the Cu-Ga alloy powder was analyzed by EPMA in the same manner as in the case of Example 1. The presence of phase, Cu solid solution phase and pure Cu phase.

與實施例1的條件同樣地將Cu-Ga合金粉末進行混合‧粉碎。得到的粉碎合金粉末之平均粒徑(D50)為45μm。 The Cu-Ga alloy powder was mixed and pulverized in the same manner as in the case of Example 1. The obtained pulverized alloy powder had an average particle diameter (D50) of 45 μm.

(成型‧燒結步驟) (forming ‧ sintering step)

使用粉碎合金粉末，700℃、真空中燒結24小時，製作燒結體。 The sintered alloy powder was sintered at 700 ° C for 24 hours in a vacuum to prepare a sintered body.

與實施例1的條件同樣地將燒結體的剖面用EPMA分析，確認γ1相(Cu9Ga4)及ζ相(Cu3Ga)的存在。又，Ga濃度為30原子%。 The cross section of the sintered body was analyzed by EPMA in the same manner as in the case of Example 1, and the presence of the γ 1 phase (Cu 9 Ga 4 ) and the ζ phase (Cu 3 Ga) was confirmed. Further, the Ga concentration was 30 atom%.

與實施例1的條件同樣地自燒結體之光學顯微鏡照片的孔隙率求出相對密度時，其為90%。 When the relative density was determined from the porosity of the optical micrograph of the sintered body in the same manner as in the case of Example 1, it was 90%.

(濺鍍評價) (splash evaluation)

與實施例1的條件同樣地進行燒結體的濺鍍時，會發生電弧放電。 When the sintered body is sputtered in the same manner as in the case of the first embodiment, arc discharge occurs.

Claims (2)

一種Cu-Ga合金濺鍍靶的製造方法，其特徵為：外周部係由CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，中心部係由Ga濃度比前述外周部低之CuGa合金相及/或固溶有Ga的Cu相及/或純Cu相所成，其係將平均Ga濃度為20原子%以上並未滿32原子%的Cu-Ga合金粉末粉碎至平均粒徑(D50)為10μm~45μm後，進行冷間靜水等冷均壓成型，之後，在真空、惰性氣體或還原環境中於720℃以上850℃以下藉由常壓燒結法燒結。 A method for producing a Cu-Ga alloy sputtering target, characterized in that the outer peripheral portion is formed of a CuGa 2 phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase, and the central portion is composed of a Ga concentration than the aforementioned outer circumference. a low CuGa alloy phase and/or a solid Cu phase and/or a pure Cu phase, wherein the Cu-Ga alloy powder having an average Ga concentration of 20 atom% or more and less than 32 atom% is pulverized to After the average particle diameter (D50) is from 10 μm to 45 μm, cold equalization molding such as cold room cooling is performed, and then sintering is performed by a normal pressure sintering method at 720 ° C or higher and 850 ° C or lower in a vacuum, an inert gas or a reducing atmosphere. 一種Cu-Ga合金濺鍍靶的製造方法，其特徵為：外周部係由CuGa2相及/或Cu9Ga4(γ2、γ3)相所成，中心部係由Ga濃度比前述外周部低之CuGa合金相及/或固溶有Ga的Cu相及/或純Cu相所成，將平均Ga濃度為20原子%以上並未滿32原子%，且平均粒徑(D50)為10μm~45μm之Cu-Ga合金粉末進行冷間靜水等冷均壓成型，之後，在真空、惰性氣體或還原環境中於720℃以上850℃以下藉由常壓燒結法燒結。 A method for producing a Cu-Ga alloy sputtering target, characterized in that the outer peripheral portion is formed of a CuGa 2 phase and/or a Cu 9 Ga 4 (γ 2 , γ 3 ) phase, and the central portion is composed of a Ga concentration than the aforementioned outer circumference. a low CuGa alloy phase and/or a solid Cu phase and/or a pure Cu phase are formed, and the average Ga concentration is 20 atom% or more and less than 32 atom%, and the average particle diameter (D50) is 10 μm. The ~45 μm Cu-Ga alloy powder is subjected to cold pressure equalization molding such as cold room static water, and then sintered by a normal pressure sintering method at 720 ° C or higher and 850 ° C or lower in a vacuum, an inert gas or a reducing atmosphere.
TW103126585A 2013-10-30 2014-08-04 Method for manufacturing cu-ga alloy sputtering target TW201516157A (en)

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