TW201425620A - Sputtering target and method of producing the same - Google Patents
Sputtering target and method of producing the same Download PDFInfo
- Publication number
- TW201425620A TW201425620A TW102139946A TW102139946A TW201425620A TW 201425620 A TW201425620 A TW 201425620A TW 102139946 A TW102139946 A TW 102139946A TW 102139946 A TW102139946 A TW 102139946A TW 201425620 A TW201425620 A TW 201425620A
- Authority
- TW
- Taiwan
- Prior art keywords
- powder
- film
- sputtering target
- alloy powder
- mixed
- Prior art date
Links
- 238000005477 sputtering target Methods 0.000 title claims abstract description 97
- 238000004544 sputter deposition Methods 0.000 title description 33
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 261
- 239000010408 film Substances 0.000 claims description 142
- 239000011812 mixed powder Substances 0.000 claims description 51
- 229910001370 Se alloy Inorganic materials 0.000 claims description 41
- 230000015572 biosynthetic process Effects 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 30
- 229910052738 indium Inorganic materials 0.000 claims description 27
- 229910052733 gallium Inorganic materials 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 229910052787 antimony Inorganic materials 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 229910000807 Ga alloy Inorganic materials 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000000956 alloy Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 18
- 229910002059 quaternary alloy Inorganic materials 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 14
- 229910000846 In alloy Inorganic materials 0.000 claims description 13
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 31
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000011669 selenium Substances 0.000 description 164
- 239000010949 copper Substances 0.000 description 78
- 238000000034 method Methods 0.000 description 48
- 239000002994 raw material Substances 0.000 description 45
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000000758 substrate Substances 0.000 description 31
- 239000002184 metal Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- 238000005245 sintering Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 238000001513 hot isostatic pressing Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000009725 powder blending Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910017518 Cu Zn Inorganic materials 0.000 description 3
- 229910017752 Cu-Zn Inorganic materials 0.000 description 3
- 229910017943 Cu—Zn Inorganic materials 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000110 cooling liquid Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 229910017932 Cu—Sb Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本發明係關於用以形成薄膜，尤其是用於形成具有高光電轉換效率之太陽能電池之光吸收層之濺鍍靶，且係形成Cu-In-Ga-Se合金膜時使用之濺鍍靶及其製造方法。 The present invention relates to a sputtering target for forming a thin film, in particular, a light absorbing layer for forming a solar cell having high photoelectric conversion efficiency, and a sputtering target used for forming a Cu-In-Ga-Se alloy film and Its manufacturing method.
本申請案係基於2012年11月5日申請之日本特願2012-243471號主張優先權，本文援用其內容。 The present application claims priority based on Japanese Patent Application No. 2012-243471, filed on Nov. 5, 2012, which is incorporated herein.
近年來，由化合物半導體獲得之薄膜太陽能電池已經供實用，該由化合物半導體獲得之薄膜太陽能電池具有在鈉鈣玻璃(soda-lime glass)基板上形成成為正電極之Mo電極層，於該Mo電極層上形成由Cu(In，Ga)Se2化合物膜(以下亦稱為CIGS膜)所成之光吸收層，在該光吸收層上形成由ZnS、CdS等所成之緩衝層，在該緩衝層上形成成為負電極之透明電極層之基本構造。 In recent years, a thin film solar cell obtained from a compound semiconductor having a Mo electrode layer formed as a positive electrode on a soda-lime glass substrate has been put to practical use, and the Mo electrode is formed on the soda-lime glass substrate. A light absorbing layer made of a Cu(In,Ga)Se 2 compound film (hereinafter also referred to as a CIGS film) is formed on the layer, and a buffer layer made of ZnS, CdS or the like is formed on the light absorbing layer, and the buffer layer is formed thereon. The basic structure of the transparent electrode layer serving as a negative electrode is formed on the layer.
作為上述光吸收層之形成方法已知有利用蒸鍍法成膜之方法，藉由該方法所得之光吸收層雖獲得高的 能量轉換效率，但隨著基板之大型化利用蒸鍍法之成膜中，膜厚之面內分布之均勻性上無法稱為充分。因此，已提案藉由濺鍍法形成光吸收層之方法。 As a method of forming the light absorbing layer, a method of forming a film by an evaporation method is known, and the light absorbing layer obtained by the method is obtained high. Energy conversion efficiency, but in the film formation by the vapor deposition method as the substrate is enlarged, the uniformity of the in-plane distribution of the film thickness cannot be said to be sufficient. Therefore, a method of forming a light absorbing layer by sputtering has been proposed.
光電轉換效率高的CIGS膜之組成已知為Cuy(InxGa1-x)Se2。此處，已提案藉由使用複數之蒸鍍製程之蒸鍍工法使目的之Cuy(InxGa1-x)Se2成膜(參照例如專利文獻1)。而且，除此以外，作為藉由濺鍍法成膜之方法，已提案首先藉由使用利用Cu-Ga二元合金之濺鍍靶之濺鍍使Cu-Ga膜成膜，且於該Cu-Ga膜上藉由使用In靶材之濺鍍使In膜成膜，並在Se氛圍中熱處理所得之由In膜及Cu-Ga二元系合金膜所成之層合膜而形成CIGS膜之方法(所謂硒化法)(參照例如專利文獻2)。 The composition of the CIGS film having high photoelectric conversion efficiency is known as Cu y (In x Ga 1-x )Se 2 . Here, it has been proposed to form a target Cu y (In x Ga 1-x )Se 2 by a vapor deposition method using a plurality of vapor deposition processes (see, for example, Patent Document 1). Further, in addition to this, as a method of forming a film by a sputtering method, it has been proposed to first form a Cu-Ga film by sputtering using a sputtering target using a Cu-Ga binary alloy, and in the Cu- Method for forming a CIGS film by forming a film of an In film by sputtering using an In target on a Ga film, and heat-treating the laminated film formed by the In film and the Cu-Ga binary alloy film in a Se atmosphere (The selenization method) (refer to, for example, Patent Document 2).
此外，上述CIGS膜之成膜方法由於需要使用In靶材及Cu-Ga二元合金靶材之2片濺鍍靶，進而需要用於在Se氛圍中熱處理之熱處理爐及將層合膜搬送到熱處理爐之步驟等之許多裝置及步驟，故難以降低成本。因此，已嘗試製作Cu-In-Ga-Se合金濺鍍靶，且使用該靶藉由1次濺鍍進行CIGS膜之成膜(參照例如專利文獻3、4)。 In addition, the film formation method of the CIGS film requires two sputtering targets of the In target and the Cu-Ga binary alloy target, and further requires a heat treatment furnace for heat treatment in the Se atmosphere and transporting the laminated film. It is difficult to reduce the cost by replacing many devices and steps such as the steps of the heat treatment furnace. Therefore, an attempt has been made to produce a Cu-In-Ga-Se alloy sputtering target, and a CIGS film is formed by one sputtering using the target (see, for example, Patent Documents 3 and 4).
另一方面，為了提高由CIGS膜所成之光吸收層之發電效率，而要求對該光吸收層添加Na、Sb、Bi、Al等。例如提案有添加Na時，使Na自成為太陽能電池之成膜用基板之藍板玻璃擴散到CIGS膜中(參照例如專利文獻5、非專利文獻1)。該提案中，膜中之Na含量一 般設為0.1%左右，於CIGS製造製程中，形成前驅體膜後，藉由進行高溫熱處理，使Na自基板之玻璃擴散到光吸收層。且，膜中將Sb、Bi添加於藉由以共蒸鍍技術之蒸鍍法作成之CIGS光吸收膜中，已確認膜之高品質化(參照例如非專利文獻2)。再者，於添加Al所得之CIGS光吸收層中，亦報導有同樣效果(參照例如非專利文獻3、4)。 On the other hand, in order to increase the power generation efficiency of the light absorbing layer formed by the CIGS film, it is required to add Na, Sb, Bi, Al, or the like to the light absorbing layer. For example, when Na is added, Na is diffused into the CIGS film from the blue plate glass which is a substrate for film formation of a solar cell (see, for example, Patent Document 5 and Non-Patent Document 1). In this proposal, the Na content in the film is one Generally, it is set to about 0.1%. After the precursor film is formed in the CIGS manufacturing process, Na is diffused from the glass of the substrate to the light absorbing layer by high-temperature heat treatment. Further, in the film, Sb and Bi are added to the CIGS light absorbing film which is formed by the vapor deposition method of the co-evaporation technique, and the quality of the film is confirmed to be high (see, for example, Non-Patent Document 2). Further, the same effect is also reported in the CIGS light absorbing layer obtained by adding Al (see, for example, Non-Patent Documents 3 and 4).
[專利文獻1]日本專利公開2004-342678 [Patent Document 1] Japanese Patent Publication No. 2004-342678
[專利文獻2]日本專利第3249408號公報 [Patent Document 2] Japanese Patent No. 3249408
[專利文獻3]日本專利公開2008-163367號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-163367
[專利文獻4]日本專利公開2011-111641號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-111641
[專利文獻5]日本專利公開2011-009287號公報 [Patent Document 5] Japanese Patent Publication No. 2011-009287
[非專利文獻1] A. Romeo, 「Development of Thin-film Cu (In,Ga) Se2 and CdTe Solar Cells」 , Prog. Photovolt: Res. Appl. 2004; 12:93-111 (DOI:10. 1002/pip.527 [Non-Patent Document 1] A. Romeo, "Development of Thin-film Cu (In, Ga) Se2 and CdTe Solar Cells", Prog. Photovolt: Res. Appl. 2004; 12:93-111 (DOI: 10.1002) /pip.527
[非專利文獻2] Honishi, Y.: Yatsushiro, Y.; Nakakoba, H., Impacts of Sb and Bi incorporations on CIGS thin films and solar cells, Photovoltaic Specialists Conference (PVSC) , 2011 37th IEEE [Non-Patent Document 2] Honishi, Y.: Yatsushiro, Y.; Nakakoba, H., Impacts of Sb and Bi incorporations on CIGS thin films and solar cells, Photovoltaic Specialists Conference (PVSC), 2011 37th IEEE
[非專利文獻3] P. D. Paulsion等人，J. Appl. Phys. Vol. 91 No.12 (2002) 10153-10156 [Non-Patent Document 3] P. D. Paulsion et al., J. Appl. Phys. Vol. 91 No.12 (2002) 10153-10156
[非專利文獻4] S.Marsillac等人，Appl. Phys. Lett. Vol.81 No.7 (2002) 1350-1352 [Non-Patent Document 4] S. Marsillac et al., Appl. Phys. Lett. Vol. 81 No. 7 (2002) 1350-1352
上述之過去技術仍有以下課題。 The above-mentioned past technologies still have the following problems.
使用Cu-In-Ga-Se合金濺鍍靶形成CIGS膜之主要優點為藉由省略在Se氛圍中之長時間高溫熱處理，故可使製造製程之成本減低化。 The main advantage of forming a CIGS film using a Cu-In-Ga-Se alloy sputtering target is that the cost of the manufacturing process can be reduced by omitting the long-time high-temperature heat treatment in the Se atmosphere.
然而，使用Cu-In-Ga-Se合金濺鍍靶形成CIGS膜之情況，為形成轉換效率高之CIGS化合物結晶膜，仍然需要成膜時之基板加熱或成膜後之後退火。形成該膜時，已知亦須使基板加熱溫度處於400~500℃左右。該情況下，所形成之膜中之Se含量變得比濺鍍靶中之Se含量更少，所生成之CIGS化合物無法成為Cuy(InxGa1-x)Se2之組成，而使太陽能電池之光電轉換效率降低。藉由於成膜中使用專利文獻3所記載之濺鍍靶，亦即將構成元素作成Cu-In-Ga-Se單相合金之濺鍍靶，雖可減少膜中Se之缺損量，但仍殘留其Se之缺損狀態。 However, in the case of forming a CIGS film using a Cu-In-Ga-Se alloy sputtering target, in order to form a CIGS compound crystal film having high conversion efficiency, substrate heating at the time of film formation or annealing after film formation is still required. When the film is formed, it is known that the substrate heating temperature is about 400 to 500 °C. In this case, the Se content in the formed film becomes less than the Se content in the sputtering target, and the generated CIGS compound cannot be composed of Cu y (In x Ga 1-x ) Se 2 , and the solar energy is made. The photoelectric conversion efficiency of the battery is lowered. By using the sputtering target described in Patent Document 3 for film formation, that is, the constituent element is a sputtering target of a Cu-In-Ga-Se single-phase alloy, and the amount of Se in the film can be reduced, but it remains. Se's defect status.
本發明係鑑於前述課題而完成者，其目的係提供一種用於形成具有高的光電轉換效率之太陽能電池之光吸收層之CIGS膜時使用之由Cu-In-Ga-Se合金所成之濺鍍靶。 The present invention has been made in view of the above problems, and an object thereof is to provide a Cu-In-Ga-Se alloy which is used for forming a CIGS film of a light absorbing layer of a solar cell having high photoelectric conversion efficiency. Plating target.
本發明人等對於使用Cu-In-Ga-Se合金濺鍍靶形成CIGS膜時，用於形成轉換效率高之CIGS化合物結晶膜之基板加熱條件、或成膜後之後退火等之條件進行檢討。結果，查明了藉由使濺鍍靶中之Se含量比成為目的之膜中的Se預計含量[組成式：Cuy(InxGa1-x)Se2]更多，可滿足適當之Cuy(InxGa1-x)Se2之組成式，且於基板加熱成膜或熱處理後，可獲得滿足適當之Cuy(InxGa1-x)Se2之組成式，且光電轉換效率最高之Cuy(InxGa1-x)Se2膜。 When the inventors of the present invention form a CIGS film using a Cu-In-Ga-Se alloy sputtering target, the conditions for forming a substrate heating condition of a CIGS compound crystal film having high conversion efficiency or annealing after film formation are examined. As a result, it was found that more suitable Cu can be satisfied by making the Se content in the sputtering target a desired content of the composition of the composition [composition formula: Cu y (In x Ga 1-x ) Se 2 ]. a composition formula of y (In x Ga 1-x )Se 2 , and after heating or forming a film or heat treatment of the substrate, a composition formula satisfying appropriate Cu y (In x Ga 1-x )Se 2 can be obtained, and photoelectric conversion efficiency is obtained. The highest Cu y (In x Ga 1-x ) Se 2 film.
因此，本發明係基於上述見解而得者，且為解決前述課題而採用以下之構成。 Therefore, the present invention has been made based on the above findings, and the following configuration is adopted to solve the above problems.
(1)本發明之一樣態的濺鍍靶，係具有Cu、In、Ga、Se及由不可避免之雜質所成之成分組成之燒結體，其特徵為該燒結體中之Se以Se/(Se+Cu+In+Ga)之原子比計含有50.1~60.0%。 (1) A sputtering target in the same state of the present invention is a sintered body composed of Cu, In, Ga, Se, and a component composed of unavoidable impurities, characterized in that Se in the sintered body is Se/( The atomic ratio of Se+Cu+In+Ga) is 50.1 to 60.0%.
(2)如前述(1)之濺鍍靶，其中前述燒結體中之Cu以Cu/(In+Ga)之原子比計含有0.9~1.0%。 (2) The sputtering target according to (1) above, wherein Cu in the sintered body contains 0.9 to 1.0% in terms of an atomic ratio of Cu/(In+Ga).
(3)如前述(1)或(2)之濺鍍靶，其中前述燒結體中以化合物含有Na，且前述Na以Na/(Cu+In+Ga+Se+Na)之原子比計含有0.05~5%。 (3) The sputtering target according to (1) or (2) above, wherein the sintered body contains Na in a compound, and the Na contains 0.05 in an atomic ratio of Na/(Cu+In+Ga+Se+Na). ~5%.
(4)如前述(3)之濺鍍靶，其中前述Na之化合物為NaF、Na2S、Na2Se及Na2SeO3中之至少1種。 (4) The sputtering target according to (3) above, wherein the compound of Na is at least one of NaF, Na 2 S, Na 2 Se, and Na 2 SeO 3 .
(5)如前述(1)至(4)中任一項之濺鍍靶，其中 前述燒結體中，由Bi、Sb、Al、Zn選出之至少1種元素以M/(Cu+In+Ga+Se+M)：(其中，M表示選自Bi、Sb、Al、Zn之至少1種元素)之原子比計含有0.05~5%。 (5) The sputtering target according to any one of (1) to (4) above, wherein In the sintered body, at least one element selected from Bi, Sb, Al, and Zn is M/(Cu+In+Ga+Se+M): (wherein M represents at least one selected from the group consisting of Bi, Sb, Al, and Zn. The atomic ratio of one element) is 0.05 to 5%.
(6)本發明之另一樣態的濺鍍靶之製造方法，其特徵係具備下述步驟：將由Cu、In、Ga及Se所組成之具有黃銅礦(chalcopyrite)型結晶構造之四元系合金粉末與Se或其合金粉末，以Se/(Se+Cu+In+Ga)之原子比計Se含有50.1~60%之量混合，獲得混合粉末之步驟，及在真空或惰性氣體氛圍中熱加壓前述混合粉末而製作燒結體之步驟。 (6) A method of producing a sputtering target according to another aspect of the present invention, characterized by comprising the step of forming a quaternary system having a chalcopyrite type crystal structure composed of Cu, In, Ga, and Se. The alloy powder is mixed with Se or its alloy powder in an atomic ratio of Se/(Se+Cu+In+Ga) in an amount of 50.1 to 60% to obtain a mixed powder, and is heated in a vacuum or an inert gas atmosphere. The step of pressing the mixed powder to form a sintered body.
(7)如前述(6)之製造方法，其中前述獲得混合粉末之步驟係混合Sb、Bi、Al及Zn中之1種粉末。 (7) The production method according to the above (6), wherein the step of obtaining the mixed powder is a method of mixing one of Sb, Bi, Al, and Zn.
(8)本發明之另一樣態的濺鍍靶之製造方法，其特徵係具備下述步驟：將Cu-In合金粉末、In粉末、Cu-Ga合金粉末、Se或其合金粉末，以Se/(Se+Cu+In+Ga)之原子比計Se含有50.1~60%之量混合，獲得混合粉末之步驟，及在真空或惰性氣體氛圍中熱加壓(hot press)該混合粉末而製作燒結體之步驟。 (8) A method for producing a sputtering target according to another aspect of the present invention, comprising the steps of: Cu-In alloy powder, In powder, Cu-Ga alloy powder, Se or alloy powder thereof, Se/ The atomic ratio (Se+Cu+In+Ga) is mixed in an amount of 50.1 to 60% to obtain a mixed powder, and the mixed powder is hot pressed in a vacuum or an inert gas atmosphere to prepare a sintered powder. The steps of the body.
(9)本發明之另一樣態的濺鍍靶之製造方法，其特徵係具備下述步驟：將Cu-Se合金粉末、In-Bi合金粉末、Cu-Ga合金粉末、Se或其合金粉末，以Se/(Se+Cu+In+Ga)之原子比計Se含有50.1~60%之量混合，獲得混合粉末之步驟，及在真空或惰性氣體氛圍中熱 加壓(hot press)該混合粉末而製作燒結體之步驟。 (9) A method of producing a sputtering target according to another aspect of the present invention, comprising the steps of: Cu-Se alloy powder, In-Bi alloy powder, Cu-Ga alloy powder, Se or alloy powder thereof, Se is mixed in an amount of 50.1 to 60% by the atomic ratio of Se/(Se+Cu+In+Ga) to obtain a mixed powder, and is heated in a vacuum or an inert gas atmosphere. The step of preparing the sintered body by hot pressing the mixed powder.
(10)本發明之另一樣態的濺鍍靶之製造方法，其特徵係具備下述步驟：將Cu-In合金粉末、Cu粉末、Cu-In-Ga合金粉末、Se粉末或其合金粉末，以Se/(Se+Cu+In+Ga)之原子比計Se含有50.1~60%之量混合，獲得混合粉末之步驟，及在真空或惰性氣體氛圍中熱加壓前述混合粉末而製作燒結體之步驟。 (10) A method for producing a sputtering target according to another aspect of the present invention, comprising the steps of: Cu-In alloy powder, Cu powder, Cu-In-Ga alloy powder, Se powder or alloy powder thereof, The Se is contained in an amount of 50.1 to 60% by the atomic ratio of Se/(Se+Cu+In+Ga) to obtain a mixed powder, and the mixed powder is thermally pressed in a vacuum or an inert gas atmosphere to prepare a sintered body. The steps.
(11)如前述(6)至(10)中任一項之製造方法，其中前述獲得混合粉末之步驟係混合NaF、Na2S、Na2Se及Na2SeO3中之至少1種化合物粉末。 (11) The production method according to any one of (6) to (10) above, wherein the step of obtaining the mixed powder is to mix at least one compound powder of NaF, Na 2 S, Na 2 Se and Na 2 SeO 3 .
如上述，本發明之一樣態的濺鍍靶(以下稱為「本發明之濺鍍靶」)含有Cu、In、Ga及Se，且以Se/(Cu+In+Ga+Se)之原子比計，以50.1~60%之比例含有Se，故藉由濺鍍法之成膜中，於藉由進行基板加熱形成CIGS化合物之製程、或成膜後以高溫熱處理形成CIGS化合物之製程中，可無Se缺損地形成Cuy(InxGa1-x)Se2化合物。Se含有比例未達50.1%時，所形成之CIGS化合物膜中之Se有缺損，無法形成Cuy(InxGa1-x)Se2結晶。另一方面，Se超過60at%時，藉基板加熱或成膜後之高溫熱處理無法去除多餘之Se，於Cuy(InxGa1-x)Se2結晶以外，會形成Se含有相。因此，Cuy(InxGa1-x)Se2結晶以外存在之Se含有相會導致太陽能電池之轉換效率降低。 As described above, the sputtering target of the present invention (hereinafter referred to as "the sputtering target of the present invention") contains Cu, In, Ga, and Se, and has an atomic ratio of Se/(Cu + In + Ga + Se). In the film formation by the sputtering method, the process of forming a CIGS compound by substrate heating or the process of forming a CIGS compound by high-temperature heat treatment after film formation can be performed by a sputtering method. A Cu y (In x Ga 1-x )Se 2 compound is formed without Se defect. When the Se content is less than 50.1%, Se in the formed CIGS compound film is defective, and Cu y (In x Ga 1-x ) Se 2 crystal cannot be formed. On the other hand, when Se exceeds 60 at%, excess Se cannot be removed by high-temperature heat treatment after substrate heating or film formation, and a Se-containing phase is formed in addition to Cu y (In x Ga 1-x )Se 2 crystal. Therefore, the Se-containing phase existing outside the Cu y (In x Ga 1-x )Se 2 crystal causes a decrease in the conversion efficiency of the solar cell.
再者，本發明之濺鍍靶，其特徵為濺鍍靶中之Cu含量以原子比計，Cu/(In+Ga)=0.9~1.0。不僅Se， In或Ga亦為低熔點金屬，藉高溫成膜或成膜後之熱處理形成Cuy(InxGa1-x)Se2時，由於蒸氣壓高故容易有缺損，使比較不易蒸發之Cu變豐富，不易形成Cuy(InxGa1-x)Se2結晶。因此，濺鍍靶中之Cu含量以原子比計成為：Cu/(In+Ga)=0.9~1.0，可獲得安定之高轉換效率化合物。且，Cu含量相對於In與Ga之含量之比少於0.9時，所形成之膜中，Cu較Cuy(InxGa1-x)Se2之理論比更缺損，另一方面，其含量比超過1.0時，Cu變豐富，於特性上不適宜。 Further, the sputtering target of the present invention is characterized in that the Cu content in the sputtering target is Cu/(In + Ga) = 0.9 to 1.0 in terms of atomic ratio. Not only Se, In or Ga is also a low-melting-point metal. When Cu y (In x Ga 1-x )Se 2 is formed by high-temperature film formation or heat treatment after film formation, it is easy to be defective due to high vapor pressure, making it relatively difficult to evaporate. Cu is rich in Cu, and it is difficult to form Cu y (In x Ga 1-x ) Se 2 crystal. Therefore, the Cu content in the sputtering target is, in atomic ratio, Cu/(In+Ga) = 0.9 to 1.0, and a stable high conversion efficiency compound can be obtained. Further, when the ratio of the Cu content to the content of In and Ga is less than 0.9, in the formed film, Cu is more deficient than the theoretical ratio of Cu y (In x Ga 1-x )Se 2 , and on the other hand, the content thereof When the ratio exceeds 1.0, Cu becomes rich and is not suitable in terms of characteristics.
再者，由Cu、Ga、In及Se所成之濺鍍靶原材中以化合物含有Na，Na含量以原子比計設為Na/(Cu+In+Ga+Se+Na)×100=0.05~5%之理由，係因為Na具有促進Cuy(InxGa1-x)Se2結晶形成之效果，藉由添加Na，使Cuy(InxGa1-x)Se2結晶較早形成，且有減低Se缺損之效果。Na未達0.05%時，結晶形成促劑效果不明確，超過5%時，Na容易集中在CIGS膜與Mo膜之界面，而容易發生CIGS膜自Mo電極剝離。 Further, in the sputtering target material formed of Cu, Ga, In, and Se, the compound contains Na, and the Na content is set to Na/(Cu + In + Ga + Se + Na) × 100 = 0.05 in atomic ratio. to 5% of the reason, because the system has the effect of promoting formation of Na Cu y (In x Ga 1- x) Se 2 crystals, by addition of Na, so that Cu y (In x Ga 1- x) Se 2 crystals formed earlier And has the effect of reducing the Se defect. When Na is less than 0.05%, the effect of the crystal formation promoter is not clear. When it exceeds 5%, Na tends to concentrate on the interface between the CIGS film and the Mo film, and the CIGS film is likely to be peeled off from the Mo electrode.
本發明人等對製造含有Na之Cu-In-Ga-Se合金濺鍍靶進行研究。結果，查明了若不以金屬Na之狀態，而是以如NaF、Na2S、Na2Se或Na2SeO3之化合物狀態，則可良好地添加Na。因此，本發明之濺鍍靶係添加NaF、Na2S、Na2Se及Na2SeO3中之至少1種作為Na化合物代替金屬Na。 The present inventors conducted research on the production of a Cu-In-Ga-Se alloy sputtering target containing Na. As a result, it was found that Na can be favorably added unless it is in the state of the metal Na but in the state of a compound such as NaF, Na 2 S, Na 2 Se or Na 2 SeO 3 . Therefore, in the sputtering target of the present invention, at least one of NaF, Na 2 S, Na 2 Se and Na 2 SeO 3 is added as a Na compound instead of the metal Na.
且，本發明之濺鍍靶係在由Cu、Ga、In、Se 所成之濺鍍靶原材中含有由Bi、Sb、Al、Zn選出之至少1種元素，且該元素之含量以原子比計，設為M/(Cu+In+Ga+Se+M)×100=0.05~5%。與Na同樣，Bi、Sb、Al、Zn亦具有促進Cuy(InxGa1-x)Se2結晶形成之效果，藉由添加元素M，使Cuy(InxGa1-x)Se2結晶較早形成，而有減低Se缺損之效果。 Further, the sputtering target of the present invention contains at least one element selected from Bi, Sb, Al, and Zn in a sputtering target material made of Cu, Ga, In, and Se, and the content of the element is atomic. The ratio is M/(Cu+In+Ga+Se+M)×100=0.05-5%. Like Na, Bi, Sb, Al, and Zn also have an effect of promoting the formation of Cu y (In x Ga 1-x )Se 2 crystal, and by adding the element M, Cu y (In x Ga 1-x ) Se 2 Crystallization is formed earlier and has the effect of reducing Se defect.
製造以上之濺鍍靶時，作為原料粉末，係準備Cu-In-Ga-Se四元系合金粉末、Cu-In合金粉末、Cu-Ga合金粉末、Cu-Se合金粉末、In-Bi合金粉末、Cu-In-Ga合金粉末、In粉末、Cu粉末、進而Se粉末、In-Se合金粉末、Ga-Se合金粉末。接著，以使成為目的之CIGS膜成為Cuy(InxGa1-x)Se2之組成式之方式，混合由上述粉末群中選出之粉末，獲得混合粉末，在真空或惰性氣體氛圍中熱加壓該混合粉末，製作燒結體。 When the above sputtering target is produced, Cu-In-Ga-Se quaternary alloy powder, Cu-In alloy powder, Cu-Ga alloy powder, Cu-Se alloy powder, and In-Bi alloy powder are prepared as raw material powders. Cu-In-Ga alloy powder, In powder, Cu powder, further Se powder, In-Se alloy powder, Ga-Se alloy powder. Next, the powder selected from the above powder group is mixed so that the intended CIGS film becomes a composition formula of Cu y (In x Ga 1-x )Se 2 to obtain a mixed powder, which is heated in a vacuum or an inert gas atmosphere. The mixed powder was pressurized to prepare a sintered body.
具體而言，選擇Cu-In-Ga-Se四元系合金粉末(Cu、Ga、In及Se所組成之黃銅礦型四元合金粉末)時，係以獲得成為目的之Cuy(InxGa1-x)Se2組成式之方式，調整該四元系粉末及Se合金粉末或Se粉末之量並混合。該情況下，亦可進而添加In粉末。或者，以獲得Cuy(InxGa1-x)Se2之組成式之方式，自Cu-In合金粉末、Cu-Ga合金粉末、Cu-Se合金粉末、In-Bi合金粉末、Cu-In-Ga合金粉末、In粉末、Cu粉末之群組中選擇3種時，係調整所選擇之各粉末及Se粉末之量並混合。此處，任一情況均為以Se/(Se+Cu+In+Ga)之原子比計，使Se含 有50.1~60%之量混合者。 Specifically, when a Cu-In-Ga-Se quaternary alloy powder (a chalcopyrite-type quaternary alloy powder composed of Cu, Ga, In, and Se) is selected, the desired Cu y (In x is obtained). In the form of a composition of Ga 1-x )Se 2 , the amount of the quaternary powder and the Se alloy powder or the Se powder is adjusted and mixed. In this case, In powder may be further added. Alternatively, a method of obtaining a composition formula of Cu y (In x Ga 1-x )Se 2 from Cu-In alloy powder, Cu-Ga alloy powder, Cu-Se alloy powder, In-Bi alloy powder, Cu-In When three types of -Ga alloy powder, In powder, and Cu powder are selected, the amount of each selected powder and Se powder is adjusted and mixed. Here, in any case, the Se is contained in an atomic ratio of Se/(Se+Cu+In+Ga), and the Se is contained in an amount of 50.1 to 60%.
以上之本發明之濺鍍靶製造所用之由金屬元素Cu、In、Ga、Se、Bi、Sb、Al、Zn所成之粉末(Se粉末、In粉末、Cu粉末、Bi粉末、Sb粉末、Al粉末、Zn粉末、Cu-Se合金粉末、In-Se粉末、Ga-Se粉末、Cu-In合金粉末、Cu-Ga合金粉末、Cu-Bi合金粉末、Cu-Sb合金粉末、Cu-Al合金粉末、Cu-Zn合金粉末、Cu-Ga-Bi粉末、Cu-Ga-Sb粉末、Cu-Ga-Al粉末、Cu-Ga-Zn粉末、Cu-In-Ga三元系合金粉末、由Cu、In、Ga及Se所成之Cu-In-Ga-Se四元系合金粉末、Cu-In-Ga-Se四元系黃銅礦型合金粉末、及其他由Cu、In、Ga、Se、Bi、Sb、Al、Zn元素之一部份或全部所成之粉末之一種或複數種)之純度為99.9%以上，粉末之平均粒徑較好為250nm~5μm，更好為100nm~30μm。 The powder of the metal element Cu, In, Ga, Se, Bi, Sb, Al, Zn used for the manufacture of the sputtering target of the present invention (Se powder, In powder, Cu powder, Bi powder, Sb powder, Al) Powder, Zn powder, Cu-Se alloy powder, In-Se powder, Ga-Se powder, Cu-In alloy powder, Cu-Ga alloy powder, Cu-Bi alloy powder, Cu-Sb alloy powder, Cu-Al alloy powder , Cu-Zn alloy powder, Cu-Ga-Bi powder, Cu-Ga-Sb powder, Cu-Ga-Al powder, Cu-Ga-Zn powder, Cu-In-Ga ternary alloy powder, Cu, In Cu-In-Ga-Se quaternary alloy powder, Cu-In-Ga-Se quaternary chalcopyrite alloy powder formed by Ga and Se, and other Cu, In, Ga, Se, Bi, The purity of one or more of the powders of part or all of the Sb, Al, and Zn elements is 99.9% or more, and the average particle diameter of the powder is preferably from 250 nm to 5 μm, more preferably from 100 nm to 30 μm.
上述之Cu-In-Ga-Se四元系黃銅礦型合金粉末之製造中，可較好地使用例如由熔融液作成粉末之霧化法或將合金鑄塊粉碎作成粉之粉碎法。尤其，由Cu、In、Ga及Se所成之Cu-In-Ga-Se四元系黃銅礦型合金粉末亦可根據專利文獻3所記載之製法製作。 In the production of the Cu-In-Ga-Se quaternary chalcopyrite type alloy powder described above, for example, an atomization method in which a molten liquid is used as a powder or a pulverization method in which an alloy ingot is pulverized into a powder can be preferably used. In particular, a Cu-In-Ga-Se quaternary chalcopyrite type alloy powder composed of Cu, In, Ga, and Se can also be produced by the method described in Patent Document 3.
另外，製造本發明之含Na薄膜形成用濺鍍靶時，係使預先準備之構成濺鍍靶之上述金屬元素Cu、In、Ga、Se、Bi、Sb、Al、Zn所成之粉末、與Na化合物(NaF、Na2S、Na2Se、Na2SeO3之至少1種)粉末混合後，進行熱加壓燒結。進行該熱加壓燒結時之壓力由於亦 對燒結體之密度造成較大影響，故於熱壓法(HP法)時，較佳之壓力為100~500kg/cm2，熱等壓燒結法(HIP法)時，較佳之壓力為500~1500kgf/cm2。加壓之時間點可為開始燒結升溫前開始加壓，亦可在到達一定溫度後開始加壓。 Further, when the sputtering target for forming a Na-containing thin film of the present invention is produced, a powder of the above-mentioned metal elements Cu, In, Ga, Se, Bi, Sb, Al, and Zn which constitute a sputtering target prepared in advance is prepared. The Na compound (at least one of NaF, Na 2 S, Na 2 Se, and Na 2 SeO 3 ) is mixed and then subjected to hot press sintering. The pressure during the hot press sintering also has a large influence on the density of the sintered body. Therefore, in the hot pressing method (HP method), the pressure is preferably 100 to 500 kg/cm 2 , and the hot isostatic pressing method (HIP) In the case of the method, the preferred pressure is 500 to 1500 kgf/cm 2 . The time point of pressurization may be started before the start of sintering temperature rise, or may be started after reaching a certain temperature.
接著，以上述熱加壓燒結法燒結之濺鍍靶用燒結體係使用一般之放電加工、切削或研削工法，加工成作為靶之指定形狀。此時，於含Na之薄膜形成用濺鍍靶時，由於Na化合物溶解於水中，故加工時較好為不使用冷卻液之乾式法或使用不含水之冷卻液之濕式法。且，亦可為以濕式法對表面粗加工後，再以乾式法對表面精密加工之方法。 Next, the sputtering system for a sputtering target sintered by the above-described hot press sintering method is processed into a predetermined shape as a target using a general electric discharge machining, cutting or grinding method. At this time, in the case of a sputtering target for forming a film containing Na, since the Na compound is dissolved in water, it is preferably a dry method in which no cooling liquid is used or a wet method in which a cooling liquid containing no water is used. Further, it may be a method of rough processing the surface by a wet method and then precision-processing the surface by a dry method.
接著，加工後之濺鍍靶以In作為焊料，接合於由Cu或SUS(不銹鋼)或其他金屬(例如Mo)所成之背襯板上，並供給於濺鍍裝置。又，為測定該接合效果(接合率)，而將濺鍍靶全體浸漬於水中，利用超音波特定出濺鍍靶或焊料層中之氣體或缺陷。然而，含Na之薄膜形成用濺鍍靶之情況，由於例如NaF會溶於水中，故如上述在水中進行測定時，需要不使濺鍍法於水直接接觸之操作。例如有將非水溶之油脂類塗佈於靶材整面上，測定後去除該油脂之方法，或以防水薄片覆蓋靶之方法等。又，為防止已加工之濺鍍靶之氧化、吸濕，較好對靶全體施以真空包裝或經惰性氣體置換之包裝。 Next, the processed sputtering target is bonded to a backing plate made of Cu or SUS (stainless steel) or another metal (for example, Mo) using In as a solder, and supplied to a sputtering apparatus. Further, in order to measure the bonding effect (bonding ratio), the entire sputtering target is immersed in water, and a gas or a defect in the sputtering target or the solder layer is specified by ultrasonic waves. However, in the case of a sputtering target containing a film containing Na, since NaF is dissolved in water, for example, when it is measured in water as described above, an operation of not directly contacting the sputtering method with water is required. For example, there is a method of applying a non-water-soluble fat or oil to the entire surface of the target, a method of removing the grease after the measurement, or a method of covering the target with a waterproof sheet. Further, in order to prevent oxidation and moisture absorption of the processed sputtering target, it is preferred to apply a vacuum package or an inert gas replacement package to the entire target.
本發明之濺鍍靶之製造方法可藉由在真空或 惰性氣體氛圍中以熱加壓等熱加壓上述混合粉末，獲得本發明之濺鍍靶。進行熱加壓燒結時之壓力亦會對燒結體之密度造成較大影響，故於HP法時，較佳之壓力為100~500kg/cm2，於HIP法時，較佳之壓力為500~1500kgf/cm2。 In the method for producing a sputtering target of the present invention, the sputtering target of the present invention can be obtained by thermally pressing the mixed powder by heat or the like in a vacuum or an inert gas atmosphere. The pressure during hot press sintering also has a large effect on the density of the sintered body. Therefore, in the HP method, the preferred pressure is 100 to 500 kg/cm 2 , and in the HIP method, the preferred pressure is 500 to 1500 kgf / Cm 2 .
本發明之含Na之濺鍍靶之製造方法係混合作為原料粉末之NaF粉末、Na2S粉末、Na2Se粉末或Na2SeO3粉末之至少1種、及Cu-In-Ga-Se四元系合金粉末、由Cu-In合金粉末、Cu-Ga合金粉末、Cu-Se合金粉末、In-Se合金粉末、Ga-Se合金粉末、In-Bi合金粉末、Cu-In-Ga合金粉末、In粉末、Cu粉末、Se粉末之群組選出之2種以上，製作混合粉末，且使該混合粉末在真空或惰性氣體氛圍中熱加壓而燒結。 The method for producing a sputtering target containing Na of the present invention is to mix at least one of NaF powder, Na 2 S powder, Na 2 Se powder or Na 2 SeO 3 powder as a raw material powder, and Cu-In-Ga-Se 4 Element alloy powder, Cu-In alloy powder, Cu-Ga alloy powder, Cu-Se alloy powder, In-Se alloy powder, Ga-Se alloy powder, In-Bi alloy powder, Cu-In-Ga alloy powder, Two or more types of In powder, Cu powder, and Se powder are selected, and a mixed powder is produced, and the mixed powder is sintered by hot pressing in a vacuum or an inert gas atmosphere.
再者，本發明之含Bi、Sb、Al、Zn之濺鍍靶之製造方法，係將該等金屬元素之粉末添加於上述之混合粉末中並混合，或者，使Bi、Sb、Al、Zn與Cu、In、Ga、Se合金化後作成粉末，或將該等粉末作成目的之混合粉末，在真空或惰性氣體氛圍中藉由熱加壓而燒結。 Further, in the method for producing a sputtering target containing Bi, Sb, Al or Zn according to the present invention, a powder of the metal element is added to the mixed powder and mixed, or Bi, Sb, Al, and Zn are added. A powder which is alloyed with Cu, In, Ga, or Se, or a powder of the same powder, is sintered by hot pressing in a vacuum or an inert gas atmosphere.
以上所示之本發明之濺鍍靶之製造方法，在以熱加壓燒結所得混合粉末時，較好將燒結溫度設定在100℃~350℃。藉此，獲得異常放電少、具有更良好耐濺鍍破裂性之靶。且，加壓之時點可在開始燒結升溫前開始加壓，亦可在到達一定溫度後開始加壓。 In the method for producing a sputtering target of the present invention shown above, when the mixed powder obtained by hot press sintering is used, the sintering temperature is preferably set to 100 ° C to 350 ° C. Thereby, a target having less abnormal discharge and having better resistance to sputter cracking is obtained. Further, at the time of pressurization, the pressurization may be started before the start of the sintering temperature rise, or the pressurization may be started after reaching a certain temperature.
又，亦可使用本發明之濺鍍靶，於基板表面 上濺鍍形成Cuy(InxGa1-x)Se2膜時，可使用磁控直流(DC)濺鍍與高頻(RF)濺鍍之任一種。此時，較好在Ar氛圍中進行。且，濺鍍時之投入電力較好為1~10W/cm2。而且，以本發明之濺鍍靶作成之膜厚可為500~2000nm，成膜時基板溫度較好為室溫~550℃，成膜後之熱處理溫度較好為~600℃。 Further, when the Cu y (In x Ga 1-x ) Se 2 film is sputtered on the surface of the substrate by using the sputtering target of the present invention, magnetron direct current (DC) sputtering and high frequency (RF) can be used. Any of the sputtering. In this case, it is preferably carried out in an Ar atmosphere. Further, the input power at the time of sputtering is preferably 1 to 10 W/cm 2 . Further, the film thickness of the sputtering target of the present invention may be 500 to 2000 nm, the substrate temperature during film formation is preferably room temperature to 550 ° C, and the heat treatment temperature after film formation is preferably ~600 ° C.
如上述，依據本發明，可提供一種形成用以形成具有高的光電轉換效率之太陽能電池之光吸收層的CIGS膜時所用之由Cu-In-Ga-Se合金所成之濺鍍靶。 As described above, according to the present invention, it is possible to provide a sputtering target made of a Cu-In-Ga-Se alloy used for forming a CIGS film for forming a light absorbing layer of a solar cell having high photoelectric conversion efficiency.
亦即，依據本發明之濺鍍靶，由於以特定比例含有Se，故可無Se缺陷地形成目的之CIGS膜之Cuy(InxGa1-x)Se2化合物。依據本發明之濺鍍靶之製造方法，可適當地製造本發明之濺鍍靶。 That is, according to the sputtering target of the present invention, since Se is contained in a specific ratio, the Cu y (In x Ga 1-x ) Se 2 compound of the intended CIGS film can be formed without Se defects. According to the method for producing a sputtering target of the present invention, the sputtering target of the present invention can be suitably produced.
接著，針對本發明之濺鍍靶及其製造方法，以下列舉實施例具體加以說明，但針對該實施例，根據製造方法中之各粉末之混合規格，分成第1實施形態、第2實施形態及第3實施形態。亦即，第1實施形態係使Cu-In-Ga-Se四元系合金粉末(由Cu、Ga、In及Se所成之黃銅礦型四元合金粉末)、與Se粉末或In-Se合金粉末、Ga-Se合金粉末、Cu-Se合金粉末混合之情況，第2實施 形態係使由Cu-In合金粉末、Cu-Ga合金粉末、Cu-Se合金粉末、In-Se合金粉末、Ga-Se合金粉末、In-Bi合金粉末、Cu-In-Ga合金粉末、In金屬粉末、Cu粉末之群組中選擇3種之各粉末與Se粉末混合之情況，且，第3實施形態係於第1及第2實施形態之混合中，進一步添加Na化合物粉末之情況。 Next, the sputtering target of the present invention and the method for producing the same will be specifically described below by way of examples. However, the embodiment is divided into the first embodiment and the second embodiment according to the mixing specifications of the respective powders in the production method. The third embodiment. In other words, the first embodiment is a Cu-In-Ga-Se quaternary alloy powder (chalbergite-type quaternary alloy powder composed of Cu, Ga, In, and Se), and Se powder or In-Se. Alloy powder, Ga-Se alloy powder, Cu-Se alloy powder mixed, second implementation The morphology is made of Cu-In alloy powder, Cu-Ga alloy powder, Cu-Se alloy powder, In-Se alloy powder, Ga-Se alloy powder, In-Bi alloy powder, Cu-In-Ga alloy powder, In metal In the group of the powder and the Cu powder, the powder of the three types is mixed with the Se powder, and the third embodiment is a case where the Na compound powder is further added to the mixing of the first and second embodiments.
以上之各實施形態中，進而可混合Bi、Sb、Al、Zn之各粉末，而於濺鍍靶中添加Bi、Sb、Al、Zn之各元素。 In each of the above embodiments, each of the powders of Bi, Sb, Al, and Zn may be mixed, and each element of Bi, Sb, Al, and Zn may be added to the sputtering target.
第1實施形態之本發明之濺鍍靶的製造中，作為第一原料粉末，係準備由Cu、Ga、In及Se所成之黃銅礦型四元合金粉末(Cuy(InxGa1-x)Se2合金粉末)，而且作為第二原料粉末，係準備Se粉末或In-Se合金粉末、Ga-Se合金粉末，再者，為第三原料粉末，係準備Bi、Sb、Al、In、Zn、Cu-Se合金粉末之各粉末。該Cu-In-Ga-Se四元合金粉末可在惰性氣體中加熱熔解Cu粉末、In粉末、Ga粉末及Se粉末，將所得之Cu-In-Ga-Se四元系合金熔融液鑄造於鑄模中製作鑄塊，將該鑄塊粉碎而獲得。又，上述各粉末較好為純度3N以上者。 In the production of the sputtering target of the present invention according to the first embodiment, a chalcopyrite-type quaternary alloy powder (Cu y (In x Ga 1) made of Cu, Ga, In, and Se is prepared as the first raw material powder. -x ) Se 2 alloy powder), and as the second raw material powder, Se powder, In-Se alloy powder, Ga-Se alloy powder, and third material powder, Bi, Sb, Al, Each powder of In, Zn, Cu-Se alloy powder. The Cu-In-Ga-Se quaternary alloy powder can be used to melt and melt Cu powder, In powder, Ga powder and Se powder in an inert gas, and the obtained Cu-In-Ga-Se quaternary alloy melt is cast into a mold. An ingot was produced and the ingot was pulverized and obtained. Further, each of the above powders preferably has a purity of 3N or more.
因此，調整作為第一原料粉末之Cu-In-Ga-Se四元合金粉末，與作為第二原料粉末之Se粉末之量並混合，製作實施例1、2之混合粉末。再者，調整作為第一 原料粉末之Cu-In-Ga-Se四元合金粉末與作為第二原料粉末之Se粉末或In2Se3粉末，及作為第三原料粉末之Bi、Sb、Al、In、Zn中之任一種粉末之量並混合，製作實施例3~12之混合粉末。再者，調整作為第一原料粉末之Cu-In-Ga-Se四元合金粉末，作為第二原料粉末之In2Se3或Ga2Se3粉末、及作為第三原料粉末之CuSe2粉末之量並混合，製作實施例13及14之混合粉末。藉由使用In2Se3粉末、Ga2Se3粉末或CuSe2粉末代替Se粉末，可在更高之燒結溫度下燒結，可有效提高靶之密度。實施例1~14之混合粉末之粉末調配量示於表1。粉末原料之純度為99.9%，粒徑為100網目以下。 Therefore, the Cu-In-Ga-Se quaternary alloy powder as the first raw material powder was adjusted and mixed with the amount of Se powder as the second raw material powder to prepare mixed powders of Examples 1 and 2. Further, the Cu-In-Ga-Se quaternary alloy powder as the first raw material powder and the Se powder or In 2 Se 3 powder as the second raw material powder, and Bi, Sb, Al as the third raw material powder are adjusted. The amount of any one of In and Zn was mixed and mixed to prepare a mixed powder of Examples 3 to 12. Further, the Cu-In-Ga-Se quaternary alloy powder as the first raw material powder, the In 2 Se 3 or Ga 2 Se 3 powder as the second raw material powder, and the CuSe 2 powder as the third raw material powder are adjusted. The mixed powders of Examples 13 and 14 were prepared by mixing and mixing. By using In 2 Se 3 powder, Ga 2 Se 3 powder or CuSe 2 powder instead of Se powder, sintering can be performed at a higher sintering temperature, and the density of the target can be effectively increased. The powder blending amounts of the mixed powders of Examples 1 to 14 are shown in Table 1. The powder raw material has a purity of 99.9% and a particle size of 100 mesh or less.
此外，為與實施例比較，製作比較例1、2之混合粉末作為僅由第一原料粉末的Cu-In-Ga-Se四元合金粉末而成之情況。再者，分別製作比較例3、4之混合粉末作為使作為第一原料粉末的Cu-In-Ga-Se四元合金粉末、與作為第二原料粉末的Se粉末混合而成之情況，接著製作比較例5、6之混合粉末作為使作為第一原料粉的Cu-In-Ga-Se四元合金粉末、與作為第二原料粉末的Se粉末、及作為第三原料粉末的Sb、Al中之任1種粉末混合而成之情況。比較例1~6之混合粉末之粉末調配量示於表1。 Further, in comparison with the examples, the mixed powders of Comparative Examples 1 and 2 were produced as Cu-In-Ga-Se quaternary alloy powder of only the first raw material powder. Further, the mixed powders of Comparative Examples 3 and 4 were prepared as a mixture of Cu-In-Ga-Se quaternary alloy powder as the first raw material powder and Se powder as the second raw material powder, and then produced. The mixed powder of Comparative Examples 5 and 6 was used as the Cu-In-Ga-Se quaternary alloy powder as the first raw material powder, the Se powder as the second raw material powder, and the Sb and Al as the third raw material powder. Any of a mixture of powders. The powder blending amounts of the mixed powders of Comparative Examples 1 to 6 are shown in Table 1.
接著，以表2所示之壓力、溫度、保持時間之條件燒結如表1所示般調配之實施例1~14及比較例 1~6之混合粉末。 Next, Examples 1 to 14 and Comparative Examples prepared as shown in Table 1 were sintered under the conditions of pressure, temperature, and holding time shown in Table 2. Mixed powder of 1~6.
熱壓法(HP法)時(表2表示為HP)係將混合粉末填充於鐵製之模具中，在Ar氛圍中進行。熱等壓燒結法(HIP法)時(表2中表示為HIP)係首先將混合粉末填充於金屬製模具中，在室溫下以1500kg/cm2加壓成形，再將所得成形體裝入0.5mm厚之不銹鋼容器中之後，經真空脫氣，進行HIP處理。 In the hot press method (HP method) (indicated as HP in Table 2), the mixed powder was filled in a mold made of iron and carried out in an Ar atmosphere. In the hot isostatic sintering method (HIP method) (indicated as HIP in Table 2), the mixed powder is first filled in a metal mold, and formed at a pressure of 1500 kg/cm 2 at room temperature, and the obtained shaped body is loaded. After a 0.5 mm thick stainless steel container, the HIP treatment was carried out by vacuum degassing.
接著，利用乾式切削將該燒結後之燒結體加工成直徑125(mm)×厚度5(mm)之大小，製作實施例1~14及比較例1~6之濺鍍靶。 Next, the sintered body after sintering was processed into a diameter of 125 (mm) × a thickness of 5 (mm) by dry cutting, and sputtering targets of Examples 1 to 14 and Comparative Examples 1 to 6 were produced.
又，加工後之濺鍍靶以In作為焊料，接合於無氧銅製之背襯板上，供於濺鍍裝置中。 Further, the processed sputtering target was bonded to an anti-oxidation copper backing plate using In as a solder for use in a sputtering apparatus.
此處，針對所製作之上述實施例1~14及比較例1~6之濺鍍靶進行組成分析。該組成分析係使用將實際製作之濺鍍靶之一部分粉碎而成者，且以高頻感應耦合電漿(ICP)法進行。其結果示於表3。又，針對表3中之 靶組成測定結果，金屬元素Cu、In、Ga、Se、Bi、Sb、Al、Zn之各金屬元素之原子比(at%)係由以下之式計算。 Here, composition analysis was performed on the sputtering targets of the above-described Examples 1 to 14 and Comparative Examples 1 to 6 which were produced. This composition analysis was carried out by partially pulverizing one of the actually produced sputtering targets, and was carried out by a high frequency inductively coupled plasma (ICP) method. The results are shown in Table 3. Also, for the table 3 As a result of the measurement of the target composition, the atomic ratio (at%) of each of the metal elements Cu, In, Ga, Se, Bi, Sb, Al, and Zn was calculated by the following formula.
金屬元素之莫耳數/(Cu+In+Ga+Se+Na+Sb+Bi+Al+Zn)各元素之莫耳數×100% Moir number of metal elements / (Cu + In + Ga + Se + Na + Sb + Bi + Al + Zn) Moire number of each element × 100%
又，基於計算所得之各金屬元素之原子比，計算Cu相對於In及Ga之比。 Further, the ratio of Cu to In and Ga was calculated based on the calculated atomic ratio of each metal element.
使用如上述製作之實施例1~14及比較例1~6之濺鍍靶進行濺鍍，試驗由Cu-In-Ga-Se所成之膜(CIGS膜)之成膜。該成膜試驗係藉以下條件進行。 Sputtering was carried out using the sputtering targets of Examples 1 to 14 and Comparative Examples 1 to 6 prepared as described above, and film formation of a film (CIGS film) made of Cu-In-Ga-Se was tested. This film formation test was carried out under the following conditions.
使用實施例1~14及比較例1~6之濺鍍靶之成膜試驗中，於形成有熱氧化膜之矽晶圓表面上進行濺鍍成膜。其膜厚為1500nm。 In the film formation test using the sputtering targets of Examples 1 to 14 and Comparative Examples 1 to 6, sputtering was performed on the surface of the germanium wafer on which the thermal oxide film was formed. The film thickness was 1500 nm.
觀察CIGS膜之剖面，確認CIGS結晶之成長狀況時，於經成膜有Mo膜之Conning公司製之XG無鹼玻璃基板上進行濺鍍。此時，成膜為1500nm。又，Mo膜之厚度為500nm。 When the cross section of the CIGS film was observed and the growth state of the CIGS crystal was confirmed, sputtering was performed on an XG alkali-free glass substrate manufactured by Conning Co., Ltd. having a Mo film formed thereon. At this time, the film formation was 1500 nm. Further, the thickness of the Mo film was 500 nm.
該濺鍍係使用高頻電源(RF電源)，到達真空度為5×10-4Pa以下，濺鍍時之投入電力為400W，濺鍍氣體僅為Ar，Ar總壓設為0.67Pa。成膜時之基板溫度及成膜後之熱處理溫度示於表4。 This sputtering system uses a high-frequency power source (RF power source) to reach a vacuum of 5 × 10 -4 Pa or less, an input power of 400 W at the time of sputtering, a sputtering gas of only Ar, and a total Ar pressure of 0.67 Pa. The substrate temperature at the time of film formation and the heat treatment temperature after film formation are shown in Table 4.
接著，針對使用實施例1~14及比較例1~6之濺鍍靶濺鍍所得之成膜之樣品，在真空度為5×10-3Pa以下之真空度進行30分鐘之紅外線熱處理後，針對成膜於矽晶圓上之樣品，自基板剝離膜後，進行金屬元素定量分析(ICP法)。所得膜中之各金屬元素(包含Se)之含量示於表4。此處，表4中之膜組成測定結果之金屬元素Cu、In、Ga、Se、Bi、Sb、Al、Zn之各原子比(%)係由以下之式計算。 Next, the film-formed samples obtained by sputtering using the sputtering targets of Examples 1 to 14 and Comparative Examples 1 to 6 were subjected to infrared heat treatment for 30 minutes under a vacuum of 5 × 10 -3 Pa or less. For the sample formed on the tantalum wafer, the film was peeled off from the substrate, and then quantitative analysis of the metal element (ICP method) was performed. The content of each metal element (including Se) in the obtained film is shown in Table 4. Here, the atomic ratio (%) of the metal elements Cu, In, Ga, Se, Bi, Sb, Al, and Zn as a result of the measurement of the film composition in Table 4 is calculated by the following formula.
M元素之莫耳數/(Cu+In+Ga+Se+Na+Sb+Bi+Al+Zn)各元素之莫耳數×100 Molar number of M element / (Cu + In + Ga + Se + Na + Sb + Bi + Al + Zn) Moire number of each element × 100
又，對以所得之實施例1~14及比較例1~6之濺鍍靶濺鍍之膜的結晶構造解析，係使用X射線繞射裝置(XRD)，分析於已成膜Mo膜之玻璃基板上成膜之 CIGS膜。 Further, the crystal structures of the films sputtered by the sputtering targets of Examples 1 to 14 and Comparative Examples 1 to 6 were analyzed by X-ray diffraction apparatus (XRD) and analyzed on the glass of the formed Mo film. Film formation on the substrate CIGS film.
膜之剖面觀察係將於附有Mo膜之玻璃基板上成膜之CIGS膜浸漬於液態氮後，使附膜之玻璃基板迅速破裂，以電解發射型電子顯微鏡(FE-SEM)對其剖面進行觀察。以實施例1之情況作為評價基準，確認並比較CIGS膜之結晶成長狀況。 The cross-section observation of the film is performed by immersing the CIGS film formed on the glass substrate with the Mo film in liquid nitrogen, and then rapidly cracking the film-attached glass substrate, and performing the profile by electrolytic emission electron microscope (FE-SEM). Observed. Based on the case of Example 1, the crystal growth state of the CIGS film was confirmed and compared.
因此，針對基板加熱成膜或熱處理後之膜，以XRD進行結晶解析，確認該膜為單一相或為二相以上。 Therefore, the film after heating or forming a film on the substrate was subjected to crystal analysis by XRD, and it was confirmed that the film was a single phase or two or more phases.
該等結果示於表4。 These results are shown in Table 4.
由以上之結果判知，利用由實施例1~14之Cu-In-Ga-Se四元系元素所成之濺鍍靶進行濺鍍，獲得具有Cu0.95~1.05(In1-xGax)Se1.95~2.05之組成之膜，確認為成為目的組成之良好Cu-In-Ga-Se四元系膜，所有實施例之情況均係結晶粒徑均勻。相對於此，利用比較例1~4之濺鍍靶濺鍍所得之膜，結晶粒徑不均勻，較小，而且成為二相以上，且確認存在Se含有相，未獲得成為目的組成之膜。再者，以比較例5、6之濺鍍靶進行濺鍍時，不僅結晶粒徑不均勻，亦見到膜剝離發生。因此，無法以XRD進行測定。 From the above results, it was found that sputtering was performed using the sputtering target formed of the Cu-In-Ga-Se quaternary elements of Examples 1 to 14 to obtain Cu 0.95 to 1.05 (In 1-x Ga x ). The film of the composition of Se 1.95 to 2.05 was confirmed to be a good Cu-In-Ga-Se quaternary film which is a target composition, and in all the cases, the crystal grain size was uniform. On the other hand, the film obtained by the sputtering target sputtering of Comparative Examples 1 to 4 had a small crystal grain size, was small, and was two or more phases, and it was confirmed that the Se-containing phase was present, and a film having a desired composition was not obtained. Further, when sputtering was performed by the sputtering targets of Comparative Examples 5 and 6, not only the crystal grain size was uneven, but also film peeling occurred. Therefore, the measurement cannot be performed by XRD.
第2實施形態係於製造本發明之濺鍍靶時，使用使由Cu-In合金粉末、Cu-Ga合金粉末、Cu-Se合金粉末、In-Se合金粉末、Ga-Se合金粉末、Cu-Zn合金粉末、In-Bi合金粉末、In金屬粉末、Sb金屬粉末之群組中選擇3種以上之各粉末與Se粉末混合之混合粉末之情況。 In the second embodiment, when the sputtering target of the present invention is produced, Cu-In alloy powder, Cu-Ga alloy powder, Cu-Se alloy powder, In-Se alloy powder, Ga-Se alloy powder, Cu- are used. In the group of Zn alloy powder, In-Bi alloy powder, In metal powder, and Sb metal powder, a mixed powder of three or more kinds of powders mixed with Se powder is selected.
因此，作為第一原料粉末係準備Cu-In合金粉末、Cu-Se合金粉末、Cu-Zn合金粉末，作為第二原料粉末係準備Se粉末，作為第三原料粉末係準備In金屬粉末，而且作為第四原料粉末係準備Cu-Ga合金粉末，再者，作為第五原料粉末係準備Sb金屬粉末。上述各粉末係將經鑄造之鑄塊粉碎所得之一般者即可，較好為純度3N以上者。 Therefore, Cu-In alloy powder, Cu-Se alloy powder, and Cu-Zn alloy powder are prepared as the first raw material powder, Se powder is prepared as the second raw material powder, and In metal powder is prepared as the third raw material powder, and The fourth raw material powder is a Cu-Ga alloy powder, and further, a Sb metal powder is prepared as a fifth raw material powder. Each of the above powders may be obtained by pulverizing the cast ingot, and preferably has a purity of 3N or more.
接著，調整作為第一原料粉末之Cu-In合金粉末、作為第二原料粉末之Se粉末、作為第四原料粉末之Cu-Ga合金粉末之量並混合，製作實施例15、16之混合粉末，調整作為第一原料粉末之Cu-Se合金粉末、作為第二原料粉末之Se粉末、作為第四原料粉末之Cu-Ga合金粉末之量並混合，製作實施例17、18之混合粉末。再者，調整作為第一原料粉末之Cu-Zn合金粉末、作為第二原料粉末之Se粉末、作為第三原料粉末之In金屬粉末、作為第四原料粉末之Cu-Ga合金粉末、與作為第五原料粉末之Sb金屬粉末之量並混合，製作實施例19之混合粉末。實施例15~19之混合粉末之粉末調配量示於表5。各粉末之純度為99.9%，粒徑為100網目以下。 Next, the Cu-In alloy powder as the first raw material powder, the Se powder as the second raw material powder, and the Cu-Ga alloy powder as the fourth raw material powder were adjusted and mixed to prepare the mixed powders of Examples 15 and 16, The Cu-Se alloy powder as the first raw material powder, the Se powder as the second raw material powder, and the Cu-Ga alloy powder as the fourth raw material powder were adjusted and mixed to prepare mixed powders of Examples 17 and 18. Further, the Cu-Zn alloy powder as the first raw material powder, the Se powder as the second raw material powder, the In metal powder as the third raw material powder, the Cu-Ga alloy powder as the fourth raw material powder, and the The amount of the Sb metal powder of the five raw material powders was mixed and the mixed powder of Example 19 was produced. The powder blending amounts of the mixed powders of Examples 15 to 19 are shown in Table 5. Each powder had a purity of 99.9% and a particle size of 100 mesh or less.
接著，以表6所示之壓力、溫度、保持時間之條件燒結如表5所示般調配之實施例15~19之混合粉末。 Next, the mixed powders of Examples 15 to 19 prepared as shown in Table 5 were sintered under the conditions of pressure, temperature and holding time shown in Table 6.
對於實施例15~19之混合粉末，採用熱等壓燒結法(HIP法：表6中記為HIP)，製作實施例15~19之濺鍍靶。首先，將各混合粉末填充於金屬製模具中，在室溫以1500kg/cm2加壓成形，且將所得成形體裝入0.5mm厚之不銹鋼容器之後，經真空脫氣，進行HIP處理。 For the mixed powders of Examples 15 to 19, sputtering targets of Examples 15 to 19 were produced by a hot isostatic sintering method (HIP method: HIP in Table 6). First, each mixed powder was filled in a metal mold, and it was press-molded at 1500 kg/cm 2 at room temperature, and the obtained molded body was placed in a stainless steel container having a thickness of 0.5 mm, and then subjected to HIP treatment by vacuum degassing.
接著，藉由乾式切削將該燒結後之燒結體加工成直徑125(mm)×厚度5(mm)之大小，製作實施例15~19之濺鍍靶。又，加工後之濺鍍靶以In作為焊料，接合於無氧銅製之背襯板上，供於濺鍍裝置中。 Next, the sintered body after sintering was processed into a diameter of 125 (mm) × a thickness of 5 (mm) by dry cutting to prepare sputtering targets of Examples 15 to 19. Further, the processed sputtering target was bonded to an anti-oxidation copper backing plate using In as a solder for use in a sputtering apparatus.
此處，針對所製作之上述實施例15~19之濺鍍靶，與上述第一實施形態之情況同樣，進行組成分析。該組成分析之結果示於表7。又，針對表7中之靶組成測定結果，亦藉第一實施形態之情況中使用之式計算，接著 基於計算所得之各金屬元素之原子比，計算Cu相對於In及Ga之比。 Here, the composition analysis of the sputter targets of the above-described Examples 15 to 19 produced in the same manner as in the first embodiment described above was carried out. The results of this composition analysis are shown in Table 7. Further, the measurement results of the target composition in Table 7 are also calculated by the formula used in the case of the first embodiment, and then The ratio of Cu to In and Ga is calculated based on the calculated atomic ratio of each metal element.
使用如上述製作之實施例15~19之濺鍍靶進行濺鍍，試驗由Cu-In-Ga-Se所成之膜(CIGS膜)之成膜。該成膜試驗係以與上述第一實施形態之情況相同條件進行。成膜時之基板溫度及成膜後之熱處理溫度示於表8。 Sputtering was carried out using the sputtering targets of Examples 15 to 19 prepared as described above, and film formation of a film (CIGS film) made of Cu-In-Ga-Se was tested. This film formation test was carried out under the same conditions as those in the first embodiment described above. The substrate temperature at the time of film formation and the heat treatment temperature after film formation are shown in Table 8.
接著，針對使用實施例15~19之濺鍍靶濺鍍所得之成膜之樣品，在真空度為5×10-3Pa以下之真空度進行30分鐘之紅外線熱處理後，針對成膜於矽晶圓上之樣品，自基板剝離膜後，進行金屬元素定量分析(ICP法)。所得膜中之各金屬元素(包含Se)之含量示於表8。此處，表8中之膜組成測定結果之各金屬元素的各原子比(%)係由第一實施形態之情況所使用之式計算。 Next, the film-formed sample obtained by sputtering using the sputtering target of Examples 15 to 19 was subjected to infrared heat treatment for 30 minutes under a vacuum of 5 × 10 -3 Pa or less, and then formed into a twin film. The sample on the circle was subjected to quantitative analysis of metal elements (ICP method) after peeling off the film from the substrate. The content of each metal element (including Se) in the obtained film is shown in Table 8. Here, the atomic ratio (%) of each metal element of the film composition measurement result in Table 8 is calculated by the formula used in the case of the first embodiment.
又，對以所得實施例15~19之濺鍍靶濺鍍之 膜之結晶構造解析，係使用X射線繞射裝置(XRD)，分析於成膜有Mo膜之玻璃基板上成膜之CIGS膜。 Further, the sputtering target of the obtained Examples 15 to 19 was sputtered. The crystal structure analysis of the film was carried out by using an X-ray diffraction apparatus (XRD) to analyze a CIGS film formed on a glass substrate on which a Mo film was formed.
膜之剖面觀察係將於附Mo膜之玻璃基板上成膜之CIGS膜浸漬於液態氮後，附膜之玻璃基板迅速破裂，以電解發射型電子顯微鏡(FE-SEM)對其剖面進行觀察。以實施例1之情況作為評價基準，確認並比較CIGS膜之結晶成長狀況。 The cross-section of the film was observed after the CIGS film formed on the glass substrate with the Mo film was immersed in liquid nitrogen, and the glass substrate attached to the film was rapidly broken, and its cross section was observed by an electron emission electron microscope (FE-SEM). Based on the case of Example 1, the crystal growth state of the CIGS film was confirmed and compared.
因此，針對基板加熱成膜或熱處理後之膜，以XRD進行結晶解析，確認該膜為單一相或為二相以上。 Therefore, the film after heating or forming a film on the substrate was subjected to crystal analysis by XRD, and it was confirmed that the film was a single phase or two or more phases.
該等結果示於表8。 These results are shown in Table 8.
由以上之結果判知，利用由實施例15~19之由Cu-In-Ga-Se四元系元素所成之濺鍍靶進行濺鍍，獲得具有Cu0.95~1.05(In1-xGax)Se1.95~2.05之組成的膜，確認係成為目的組成之良好Cu-In-Ga-Se四元系膜，所有實施例之情況均係結晶粒徑均勻。 From the above results, it was found that sputtering was carried out by using a sputtering target made of Cu-In-Ga-Se quaternary elements of Examples 15 to 19 to obtain Cu 0.95 to 1.05 (In 1-x Ga x ). The film of the composition of Se 1.95 to 2.05 was confirmed to be a good Cu-In-Ga-Se quaternary film having the desired composition, and in all of the examples, the crystal grain size was uniform.
第3實施形態係於第1及第2實施形態之混合中，進而添加Na化合物粉末之情況。如上述，此係因為於由Cu、Ga、In及Se所成之濺鍍靶原材料中，將Na作為化合物，以Na含量以原子比計為Na/(Cu+In+Ga+Se+Na)=0.05~5%含有時，Na具有促進Cuy(InxGa1-x)Se2結晶形成，且減低Se缺損之效果，故於第1及第2實施形態之混合粉末製作時，係設為混合Na化合物例如NaF、Na2S及Na2Se、Na2SeO3之至少1種化合物之粉末。 The third embodiment is a case where the Na compound powder is further added to the mixing of the first and second embodiments. As described above, this is because Na is used as a compound in the sputtering target raw material formed of Cu, Ga, In, and Se, and the Na content is Na/(Cu+In+Ga+Se+Na) in atomic ratio. When it is contained in the range of 0.05 to 5%, Na has an effect of promoting the formation of Cu y (In x Ga 1-x )Se 2 crystal and reducing the Se defect. Therefore, when the mixed powder of the first and second embodiments is produced, it is designed. A powder of at least one compound of a Na compound such as NaF, Na 2 S, Na 2 Se, and Na 2 SeO 3 is mixed.
因此，作為第一至第五原料粉末係準備具有表9所示成分組成之各原料粉末。第五原料粉末中，作為Na化合物粉末係準備NaF、Na2S、Na2Se、Na2SeO3之各粉末，且純度3N，一次平均粒徑0.2μm者。該等Na化合物粉末係在真空乾燥機中於真空環境中進行80℃、3小時以上之乾燥。Na化合物粉末係與第一至第四原料粉末一起秤量後，饋入聚乙烯缽中，加入直徑：5mm之ZrO2球，以球磨機混合指定之時間。此處，製作實施例20~24之混合粉末。 Therefore, each of the raw material powders having the composition shown in Table 9 was prepared as the first to fifth raw material powders. In the fifth raw material powder, each of NaF, Na 2 S, Na 2 Se, and Na 2 SeO 3 powders was prepared as a Na compound powder, and the purity was 3 N, and the primary average particle diameter was 0.2 μm. These Na compound powders were dried in a vacuum oven at 80 ° C for 3 hours or more in a vacuum atmosphere. The Na compound powder was weighed together with the first to fourth raw material powders, fed into a polyethylene crucible, and added to a ZrO 2 sphere having a diameter of 5 mm, and mixed in a ball mill for a specified period of time. Here, the mixed powder of Examples 20 to 24 was produced.
此外，為與實施例比較，製作使作為第一原料粉末之Cu-In合金粉末、作為第二原料粉末之Se粉末、作為第三原料粉末之Cu金屬粉末、作為第四原料粉末之Cu-In-Ga合金粉末、與作為第五原料粉末之NaF化合物粉混合之情況的比較例7之混合粉末。比較例7之混合粉末的粉末調配量示於表9。又，為參考用，表9中記載第一實施形態時所示之比較例3、4。 Further, in comparison with the examples, Cu-In alloy powder as the first raw material powder, Se powder as the second raw material powder, Cu metal powder as the third raw material powder, and Cu-In as the fourth raw material powder were produced. a mixed powder of Comparative Example 7 in the case where -Ga alloy powder was mixed with the NaF compound powder as the fifth raw material powder. The powder blending amount of the mixed powder of Comparative Example 7 is shown in Table 9. Further, for reference, Tables 9 show Comparative Examples 3 and 4 shown in the first embodiment.
接著，以表10所示之壓力、溫度、保持時間之條件燒結如表9所示般調配之實施例20~24及比較例7之混合粉末。 Next, the mixed powders of Examples 20 to 24 and Comparative Example 7 prepared as shown in Table 9 were sintered under the conditions of pressure, temperature and holding time shown in Table 10.
對於實施例20~24及比較例7之混合粉末，採用熱加壓法(HP法，表10表示為HP)，將混合粉末填充於鐵製模具中，在Ar氛圍中進行HP處理。 The mixed powders of Examples 20 to 24 and Comparative Example 7 were subjected to a hot press method (HP method, shown as HP in Table 10), and the mixed powder was filled in an iron mold, and HP treatment was performed in an Ar atmosphere.
接著，藉由乾式切削將該燒結後之燒結體加工成直徑125(mm)×厚度5(mm)之大小，製作實施例20~24及比較例7之濺鍍靶。又，加工後之濺鍍靶以In作為焊料，接合於無氧銅製之背襯板上，供於濺鍍裝置。 Next, the sintered body after sintering was processed into a diameter of 125 (mm) × a thickness of 5 (mm) by dry cutting to prepare sputtering targets of Examples 20 to 24 and Comparative Example 7. Further, the processed sputtering target was bonded to an anti-oxidation copper backing plate using In as a solder for use in a sputtering apparatus.
此處，針對製作之上述實施例20~24及比較例7之濺鍍靶，與上述第一實施形態之情況同樣，進行組成分析。該組成分析之結果示於表11。又，針對表7中 之靶組成測定結果，亦藉第一實施形態之情況中使用之式計算，而且基於計算所得之各金屬元素之原子比，計算Cu相對於In及Ga之比。 Here, the composition analysis of the sputter targets of the above-described Examples 20 to 24 and Comparative Example 7 was carried out in the same manner as in the case of the first embodiment described above. The results of this composition analysis are shown in Table 11. Also, for Table 7 The measurement result of the target composition is also calculated by the formula used in the case of the first embodiment, and the ratio of Cu to In and Ga is calculated based on the calculated atomic ratio of each metal element.
且，針對作為Na化合物的NaF、Na2S、Na2SeO3添加時隨附摻雜於濺鍍靶中之F、S、Se元素，確認幾乎以如與Na之化學計量比含於靶中。 Further, when the Na, Na 2 S, and Na 2 SeO 3 as Na compounds are added, the F, S, and Se elements doped in the sputtering target are added to the target in a stoichiometric ratio such as Na. .
接著，針對使用實施例20~24及比較例7之濺鍍靶濺鍍所得之成膜之樣品，在真空度為5×10-3Pa以下之真空度進行30分鐘之紅外線熱處理後，針對成膜於矽晶圓上之樣品，自基板剝離膜後，進行金屬元素定量分析(ICP法)。所得膜中之各金屬元素(包含Se)之含量示於表8。此處，表12中之膜組成測定結果之各金屬元素的各原子比(%)係藉第一實施形態之情況所使用之式計 算。 Next, the film-formed samples obtained by sputtering using the sputtering targets of Examples 20 to 24 and Comparative Example 7 were subjected to infrared heat treatment for 30 minutes under a vacuum of 5 × 10 -3 Pa or less, and then subjected to infrared heat treatment for 30 minutes. After the film is deposited on the wafer, the metal element is quantitatively analyzed (ICP method) after the film is peeled off from the substrate. The content of each metal element (including Se) in the obtained film is shown in Table 8. Here, the atomic ratio (%) of each metal element of the film composition measurement result in Table 12 is calculated by the formula used in the case of the first embodiment.
又，對以所得實施例20~24及比較例7之濺鍍靶濺鍍之膜之結晶構造解析，係使用X射線繞射裝置(XRD)，分析於成膜有Mo膜之玻璃基板上成膜之CIGS膜。 Further, the crystal structures of the films sputtered by the sputtering targets of Examples 20 to 24 and Comparative Example 7 were analyzed by X-ray diffraction apparatus (XRD) and analyzed on a glass substrate on which a Mo film was formed. Film CIGS film.
膜之剖面觀察係將於附Mo膜之玻璃基板上成膜之CIGS膜浸漬於液態氮後，附膜之玻璃基板破裂，以電解發射型電子顯微鏡(FE-SEM)對其剖面進行觀察。以實施例1之情況作為評價基準，確認並比較CIGS膜之結晶成長狀況。 The cross-section of the film was observed after the CIGS film formed on the glass substrate with the Mo film was immersed in liquid nitrogen, and the glass substrate of the film was broken, and the cross section was observed by an electron emission electron microscope (FE-SEM). Based on the case of Example 1, the crystal growth state of the CIGS film was confirmed and compared.
因此，針對基板加熱成膜或熱處理後之膜，以XRD進行結晶解析，確認其膜為單一相或為二相以上。 Therefore, the film after heating or forming a film on the substrate was subjected to crystal analysis by XRD, and it was confirmed that the film was a single phase or two or more phases.
該等結果示於表12。 These results are shown in Table 12.
由以上之結果判知，以由實施例20~24之Cu-In-Ga-Se-Na五元系元素所成之濺鍍靶進行濺鍍，獲得添加有Na之具有Cu0.95~1.05(In1-xGax)Se1.95~2.05Na之組成之膜，確認係成為目的組成之良好Cu-In-Ga-Se-Na五元系膜，所有實施例之情況均係結晶粒徑均勻。因此，確認藉由添加Na，獲得Cuy(InxGa1-x)Se2結晶中之Se缺損之抑制效果。相對於此，以比較例7之濺鍍靶進行濺鍍所得之膜中，由於Na之含量較多，故Na容易集中在CIGS膜與Mo膜之界面處，不僅結晶粒徑不均，且發生膜剝離。 From the above results, it was found that sputtering was carried out by the sputtering target formed of the Cu-In-Ga-Se-Na pentad elements of Examples 20 to 24, and Cu was added with Cu 0.95 to 1.05 (In 1-x Ga x) film composition of the Se 1.95 ~ 2.05 Na confirmed to be a good system Cu-In-Ga-Se- Na object composed of five elements of the film, the case of all embodiments were all uniform crystal grain size. Therefore, it was confirmed that the effect of suppressing the Se defect in the Cu y (In x Ga 1-x )Se 2 crystal was obtained by adding Na. On the other hand, in the film obtained by sputtering using the sputtering target of Comparative Example 7, since Na is contained in a large amount, Na tends to concentrate at the interface between the CIGS film and the Mo film, and not only the crystal grain size is uneven, but also occurs. The film is peeled off.
又，本發明之技術範圍並不限於上述實施形態及上述實施例，在不脫離本發明主旨之範圍內可進行各種變更。 Further, the technical scope of the present invention is not limited to the above-described embodiments and the above-described embodiments, and various modifications can be made without departing from the spirit and scope of the invention.
依據本發明可無Se缺損地形成用以形成具有高的光電轉換效率之太陽能電池的光吸收層所需之CIGS膜。 According to the present invention, a CIGS film required for forming a light absorbing layer of a solar cell having high photoelectric conversion efficiency can be formed without Se defect.
Claims (11)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012243471 | 2012-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201425620A true TW201425620A (en) | 2014-07-01 |
Family
ID=50627544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102139946A TW201425620A (en) | 2012-11-05 | 2013-11-04 | Sputtering target and method of producing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2014069652A1 (en) |
| CN (1) | CN104903487A (en) |
| TW (1) | TW201425620A (en) |
| WO (1) | WO2014069652A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104404457A (en) * | 2014-11-21 | 2015-03-11 | 北京四方继保自动化股份有限公司 | Na doping method for CIGS (copper indium gallium selenide) quaternary target |
| CN104925760B (en) * | 2015-07-02 | 2017-02-08 | 成都先锋材料有限公司 | Na doping method of CIGS (copper, indium, gallium and selenium) and manufacturing method of Na-doped CIGS sputtering target material |
| CN105118878B (en) * | 2015-07-28 | 2017-09-19 | 成都先锋材料有限公司 | CIGS antimonial doping method |
| CN105070791B (en) * | 2015-08-25 | 2017-07-25 | 成都先锋材料有限公司 | The CIGS and its doping method of doping bismuth compound |
| JP6692724B2 (en) * | 2016-09-02 | 2020-05-13 | Ｊｘ金属株式会社 | Non-magnetic material dispersed Fe-Pt based sputtering target |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI382095B (en) * | 2009-03-04 | 2013-01-11 | Jun Wen Chung | Method for manufacturing multi-element metal chalcogenide synthesis |
| CN101661971B (en) * | 2009-09-10 | 2011-01-05 | 中国科学院电工研究所 | Method for preparing light absorption layer of CuInSe2 (CIS) based thin film solar cell |
| JP5378534B2 (en) * | 2009-10-27 | 2013-12-25 | キヤノンアネルバ株式会社 | Method for producing chalcopyrite type compound thin film and method for producing thin film solar cell using the same |
| WO2011083646A1 (en) * | 2010-01-07 | 2011-07-14 | Jx日鉱日石金属株式会社 | Sputtering target, compound semiconductor thin film, solar cell having compound semiconductor thin film, and method for manufacturing compound semiconductor thin film |
| 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 |
| US9273389B2 (en) * | 2010-09-27 | 2016-03-01 | Jx Nippon Mining & Metals Corporation | Cu—In—Ga—Se quaternary alloy sputtering target |
| JP5919738B2 (en) * | 2011-11-10 | 2016-05-18 | 三菱マテリアル株式会社 | Sputtering target and manufacturing method thereof |
-
2013
- 2013-11-04 TW TW102139946A patent/TW201425620A/en unknown
- 2013-11-05 CN CN201380054636.8A patent/CN104903487A/en active Pending
- 2013-11-05 WO PCT/JP2013/079841 patent/WO2014069652A1/en active Application Filing
- 2013-11-05 JP JP2014544620A patent/JPWO2014069652A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2014069652A1 (en) | 2016-09-08 |
| CN104903487A (en) | 2015-09-09 |
| WO2014069652A1 (en) | 2014-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9660127B2 (en) | Sputtering target and method for producing same | |
| JP5923569B2 (en) | Cu-Ga sputtering target | |
| US8968491B2 (en) | Sputtering target and method for producing same | |
| JP5730788B2 (en) | Sputtering target and manufacturing method of sputtering target | |
| TWI553139B (en) | Sputtering target and its manufacturing method | |
| US8871143B2 (en) | Amalgam method for forming a sputter target useful in the manufacture of thin-film solar photovoltaic cells | |
| US10017850B2 (en) | Cu—Ga alloy sputtering target, and method for producing same | |
| TW201425620A (en) | Sputtering target and method of producing the same | |
| CN104835869B (en) | Copper-indium-galliun-selenium film solar cell and preparation method thereof | |
| JP2010245238A (en) | Photoelectric conversion device and method of manufacturing the same, as well as method of manufacturing sulfide sintered compact target | |
| US9273389B2 (en) | Cu—In—Ga—Se quaternary alloy sputtering target | |
| Cheng et al. | Chalcogenide solar cells fabricated by co-sputtering of quaternary CuIn0. 75Ga0. 25Se2 and In targets: Another promising sputtering route for mass production | |
| JP5153911B2 (en) | Sputtering target and manufacturing method thereof | |
| JP2012246574A (en) | Sputtering target and method for producing the same | |
| JP2012092438A (en) | Mo-based sputtering target and method of manufacturing the same, and cigs-based thin-film solar cell using the same | |
| JP2016082120A (en) | Light absorption layer for solar cell, manufacturing method of the same, and solar cell including the light absorption layer for solar cell |