CN103098225B - 镓和镓合金膜的电沉积方法以及相关的光伏结构 - Google Patents
镓和镓合金膜的电沉积方法以及相关的光伏结构 Download PDFInfo
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- CN103098225B CN103098225B CN201180042274.1A CN201180042274A CN103098225B CN 103098225 B CN103098225 B CN 103098225B CN 201180042274 A CN201180042274 A CN 201180042274A CN 103098225 B CN103098225 B CN 103098225B
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- gallium
- layer
- indium
- copper
- plating solution
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 93
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910000807 Ga alloy Inorganic materials 0.000 title claims abstract description 30
- 238000004070 electrodeposition Methods 0.000 title description 29
- 238000007747 plating Methods 0.000 claims abstract description 36
- 239000006259 organic additive Substances 0.000 claims abstract description 28
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000009713 electroplating Methods 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 12
- 150000002258 gallium Chemical class 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 7
- 229910052738 indium Inorganic materials 0.000 claims description 36
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 35
- 239000010949 copper Substances 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 239000011669 selenium Substances 0.000 claims description 16
- 229910052711 selenium Inorganic materials 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052752 metalloid Inorganic materials 0.000 claims description 5
- 150000002738 metalloids Chemical class 0.000 claims description 5
- -1 sulphur oxygen-bis-hydroxyl amino molybdenum Chemical compound 0.000 claims description 5
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 claims description 4
- KYPIULIVYSQNNT-UHFFFAOYSA-N prop-2-enylsulfonylbenzene Chemical compound C=CCS(=O)(=O)C1=CC=CC=C1 KYPIULIVYSQNNT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims description 4
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 3
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000003456 sulfonamides Chemical class 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 229910052785 arsenic Inorganic materials 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 229910052787 antimony Inorganic materials 0.000 abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- 238000000151 deposition Methods 0.000 description 23
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 230000008021 deposition Effects 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000003475 lamination Methods 0.000 description 10
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- 150000004706 metal oxides Chemical class 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
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- 229960002594 arsenic trioxide Drugs 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 2
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- 230000003746 surface roughness Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
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- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- BEWAJAMESUGLPZ-UHFFFAOYSA-N carbonic acid;indium Chemical compound [In].OC(O)=O BEWAJAMESUGLPZ-UHFFFAOYSA-N 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
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- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 description 1
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- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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Abstract
光伏器件以及为光伏器件制备p型半导体层的方法一般包括:通过使导电层与不包含络合剂的镀液接触,将镓或镓合金的层电镀到所述导电层上,所述镀液包含镓盐、甲磺酸或硫酸钠、溶剂、以及有机添加剂,所述有机添加剂包含至少一个氮原子和/或至少一个硫原子;将所述溶液的pH调整为小于2.6或大于12.6。所述光伏器件包括:在p型半导体层中的杂质,其选自砷、锑、铋或其混合物。通过以这种方式电镀镓或镓合金,可以形成用于形成CIS、CGS和CIGS?p型半导体结构的各种光伏前体层。还公开了利用电镀方法形成镓或镓合金的热界面的方法。
Description
技术领域
本发明一般地涉及用于薄膜光伏器件制造以及作为热界面材料的镓和镓合金膜(例如包含铜、铟、镓和/或硒的那些)的电沉积方法。
背景技术
对于光伏应用,一般使用具有不同特性的两个半导体材料层,以建立电场和所产生的电流。第一层典型地是n型半导体材料并且一般很薄,以便让光线穿过到达下面的p型半导体层材料层,该p型半导体层材料层通常被称为吸收层。吸收层和n型半导体材料层相结合提供了合适的带隙,以吸收来自光源的光子并产生大电流和改善的电压。对于p型层,二硒化铜铟镓半导体材料(即,CuInGaSe2及其变体,也被称为CIGS)或二硒化铜铟(即,CuInSe2,也被称为CIS)或二硒化铜镓(即,CuGaSe2,也被称为CGS)的薄膜最近几年已在光伏器件应用中产生了显著的兴趣。
举例来说,p型CIGS层典型地与n型CdS层结合,以形成p-n异质结CdS/CIGS器件。可以添加氧化锌和掺杂的氧化锌,来提高透明度。CIGS的直接能隙产生了大的光吸收系数,这转而允许使用1-2μm量级的薄层。举例来说,有报告称,通过用镓部分地取代铟,吸收层带隙从CuInSe2(CIS)半导体材料的1.02电子伏特(eV)提高到1.1-1.2eV,带来了明显的效率提升。
典型地通过真空沉积、化学沉积或电沉积来形成CIGS结构。最常用的基于真空的方法共蒸发(co-evaporate)或共溅射(co-sputter)铜、镓和铟,然后用包含硒或硫的蒸汽对所产生的膜进行退火,以形成最终的CIGS结构。备选方案是将铜、镓、铟和硒直接共蒸发到经加热的基板上。基于非真空的备选方法使前体(precursor)材料的纳米颗粒沉积在基板上,然后对其进行原位烧结。电沉积是施加CIGS层的另一低成本备选者。尽管电沉积是形成镓薄膜的吸引人的选择,特别是对于光伏应用(例如CIGS),但目前的方法一般不是商业上实用的。一般认为,如果在阴极上不产生过量的氢,则镓是难以沉积的金属,这是因为镓的平衡电势相对高。在阴极上的氢产生导致沉积效率低于100%,这是因为部分沉积电流被用于形成氢气而不是在基板或阴极上形成镓膜。由于产生过量氢而带来的低阴极沉积效率导致了差的工艺可重复性,部分地是因为差的阴极效率,且最重要地是因为具有高表面粗糙度和差沉积形貌的差沉积膜质量。
因此,本领域中需要改进的用于沉积镓和镓合金的电沉积方法以及包含具有增加的带隙的该镓和镓合金层以提供增加的光伏电流的新颖光伏器件。
发明内容
本发明一般涉及形成用于光伏器件的p型半导体层的方法。在一方面,该方法包括:将第一层电镀到基板的导电表面上,其中,所述第一层选自铜层和铜镓层;将第二层电镀到所述第一层上,其中,所述第二层选自铟层、镓层、铟镓层、二硒化铜铟层以及二硒化铜镓层;以及可选地,将第三层电镀到所述第二层上,其中,所述第三层选自镓层和铟层;并且可选地,将第四层电镀到所述第三层上,其中,所述第四层选自硒和硫;其中,所述电镀是通过这样的方法来实施的,该方法包括:使(i)基板和(ii)溶液接触,所述溶液包括:前体,其包含选自铜、镓、铟、硒、硫及其组合的元素;可选地,准金属(metalloid)化合物添加剂;进一步可选地,有机添加剂,其至少具有硫原子;以及溶剂,其溶解所述前体;其中,所述溶液不包含络合剂;将所述溶液的pH调整为选自从约0到小于约2.6的pH以及从约12.6到约14的pH的范围,并施加电流以电镀所述基板,以产生所述第一、第二、第三或第四层;以及在存在硒源和/或硫源的条件下,对所述第一层、所述第二层和所述第三层进行退火,以形成所述p型半导体层。
在用于形成热界面(thermalinterface)的方法中,该方法包括:将镓或镓合金的层电镀到发热表面上,所述发热表面被耦合到微处理器,其中,电镀所述镓或镓合金包括使所述发热表面与不包含络合剂的镀液(platingbath)接触,所述镀液包含镓盐、溶剂和可选的有机添加剂,所述有机添加剂包含至少一个硫原子;将所述镀液的pH调整为选自大于约0到小于2.6的pH以及大于约12.6到约14的pH的范围,并施加电流来电镀所述发热表面,以产生所述镓或镓合金的层;以及将散热件(heatsink)或散热器(heatspreader)耦合到所述镓或镓合金的层,以形成所述热界面。
一种光伏器件包括:包含镓或铟或者含镓和铟的合金的至少一个层,其中,所述至少一个层是通过电沉积形成的;以及所述至少一个层中的杂质,其选自砷、锑、铋、硒、硫及其混合物。
通过本发明的技术来实现另外的特征和优点。本发明的其他实施例和方面在这里被详细描述并被视为所要求的发明的一部分。为了更好地理解本发明的优点和特征,参考描述和附图。
附图说明
在说明书结尾处的权利要求书中特别指出并清晰地要求被视为本发明的主题。通过结合附图给出的以下详细描述,本发明的上述和其他目的、特征和优点将显而易见,在附图中:
图1示出了根据本发明的CIGS前体结构的截面图;
图2示出了根据本发明的CIGS前体结构的截面图;
图3示出了根据本发明的CIGS前体结构的截面图;
图4示出了根据本发明的CIGS前体结构的截面图;
图5示出了镓热界面的截面图;
图6示意性地示例出将镓层沉积到基板上的示例性电沉积设备;
图7示出了膜叠层(stack)的截面图的扫描电子显微照片,其中,镓被电沉积到铟层上并随后被退火,以形成富铟的镓低共熔层(eutecticlayer);
图8和9示出了分别在20和30mAcm-2下从添加有硫脲的酸性甲磺酸溶液恒电流地沉积的镓的自顶向下视图的扫描电子显微照片;以及
图10图示出没有添加剂、具有三氧化砷添加剂、以及具有三氧化砷和硫脲作为添加剂的酸性镓镀液的循环伏安图。
参考附图并通过实例,详细的描述解释了本发明的优选实施例以及优点和特征。
具体实施方式
本发明提供了用于形成例如在形成各种光伏器件时所需以及作为热界面的镓和/或镓合金(例如CIGS、CIS、CGS等)的薄层的低成本的电沉积方法。
电沉积方法使用电镀溶液(electroplatingsolution)来以高电镀效率和可重复性沉积在组成上纯净、均匀、基本无缺陷、且光滑的薄膜。该电镀溶液没有络合剂,并且在高pH范围和低pH范围下都可以实施。也可以电镀合金薄膜。所需的镓合金的实例一般依赖于所预期的应用,并可以包括但不限于银、铜、铟、锌、锡、铅、银、铋、金、硒、硫等的二元、三元或更高元合金。可选地,可以通过对膜叠层退火来形成合金,该膜叠层包括电沉积的镓层以及一种或多种合金元素金属层。通过这种方式,实现镓或镓合金薄膜的低成本制造,其中,镓层或镓合金层有均匀的厚度、优良的形貌并且基本无缺陷。
在一个实施例中,电沉积镓以形成CIGS前体结构,该前体结构被配置为控制膜叠层中的镓互扩散。在图1示出的示例性实施例中,导电层14首先被沉积到用作金属背面接触(backcontact)的基板12上。导电层可以包括但不限于钼、钽、钨、钛、其相应的氮化物等。一般通过任何手段以约300nm到约600纳米(nm)的厚度沉积导电层。然后以约10nm到约500nm的厚度将铜层16沉积到导电层14上;在另外的实施例中,铜层的厚度为220nm到260nm;在进一步另外的实施例中,铜层的厚度为约240nm。然后以50nm到500nm的厚度将铟层18沉积到铜层16上;在另外的实施例中,铟层的厚度为375nm到425nm;且在进一步另外的实施例中,铟层的厚度为约420nm。然后以20nm到200nm的厚度将镓层20沉积到铟层18上;在另外的实施例中,镓层的厚度为100nm到150nm;且在进一步另外的实施例中,镓层的厚度为约140nm。镓层是使用根据本公开的电沉积方法来沉积的。其他层可以通过任意沉积技术(例如,真空沉积)来沉积,但一般优选这些层是通过电沉积来沉积的。
图2示例出根据本公开的另一实施例的适于用作前体结构的示例性膜叠层30。在该示例性实施例中,首先以约300nm到约600nm的厚度将导电层34沉积到基板32上。然后以275到330nm(例如310nm)的厚度将铜镓合金层36电沉积到导电层34上。然后以420到500nm(例如490nm)的厚度将铟镓层38电沉积到铜镓层36上。Cu/(In+Ga)的比率可以维持在0.8到0.9,例如0.88;且Ga/(Ga+In)的比率可以维持在0.3到0.33,例如0.31。考虑到本公开很明显,导电层可以通过任意沉积技术来沉积,但一般优选地这些层是通过电沉积来沉积的。镓是熔点非常低的元素。它在约35℃时是液体,因此很容易移动并易于互扩散。具有诸如铜和铟的较高熔点的金属的合金镓不仅减少了电沉积方法的步骤数目,还稳定了微结构并允许前体CIGS材料的更好互混合。这最终导致对CIGSp-吸收材料的更好组成控制。
图3示例出根据本公开的另一实施例的适于用作CIGS前体结构的示例性膜叠层50。在该示例性实施例中,首先将导电层54沉积到基板54上。然后将铜层56沉积到钼层56上。铜层和钼层的厚度如前所述。然后以400nm到500nm且最精确地为490nm的厚度,将铟镓层58电沉积到铜层56上。Cu/(In+Ga)的比率可以维持在0.8到0.9,例如0.88;且Ga/(Ga+In)的比率可以维持在0.3到0.33,例如0.31。导电层和铜层可以通过任意沉积技术来沉积,但一般优选地这些层是通过电沉积来沉积的。InGa合金的沉积提供了对CIGS前体互混合的更好控制以及对CIGS组成的最终控制。
图4示例出根据本公开的另一实施例的适于用作CIGS前体结构的示例性膜叠层60。在该示例性实施例中,首先将导电层64沉积到基板62上。然后以约1微米到2.5微米的厚度将铜铟硒层66电沉积到钼层64上。然后将镓合金层68电沉积到铜硒铟层66上。钼层和镓层的厚度如上所述。考虑到本公开很明显,导电层可以通过任意沉积技术来沉积,但一般优选地这些层是通过电沉积来沉积的。通过该方法,CuInSe2材料中的部分铟被镓取代,在退火后形成CuInGaSe2。
然后使如上关于图1-4所述的包括铜层、镓层和铟层的膜叠层与硒和/或硫反应,以形成CuInGaSe2或CuInGaSe2S或CuInGaS结构。例如,硒层可以被沉积到膜叠层上且随后被退火以形成硒化物。或者,膜叠层例如可以被暴露到硒化氢和/或硫化氢且随后被退火。在硫和/或硒气氛中的退火可以在约400℃到约700℃且优选地550℃的温度下发生。对于本领域技术人员来说很明显,继CIGS形成之后,然后将n型结层(未示出)的沉积物沉积到CIGS层上。如上所述,该层将与CIGS层接触以形成p-n结。要沉积的下一层典型地是ZnO和掺杂的ZnO透明氧化物层(未示出)。此外,很明显,电镀工艺可以被用于形成其他类型的光伏器件的前体层,例如,铜铟硒(CIS)、铜镓硒(CGS)、铜铟硫(CISu)、铜镓硫(CGSu)等。
在上述各个实施例中,所产生的CIGS结构一般具有0.8到约0.9的Cu/(In+Ga)比率和0.3到约0.33的Ga/(Ga+In)比率。
在另一实施例中,镓层或镓合金层被电沉积以形成热界面。镓层或镓合金层可以被电镀为在Zn、Sn、In、Au、Cu、其混合物等的下垫层(underlayer)上的叠层。镓提供了低的抗拉强度以及高的堆积导热率(bulkthermalconductivity)。作为合金,自扩散提供了适于其作为热界面材料的应用的低熔点合金。这样,镓可以与其他元素进行合金化以降低熔点。图5示出了示例性装置,其包括被耦合到散热件的微处理器芯片,以通过吸热并将热耗散到空气中来防止过热。装置100包括基板102,微处理器104形成并安装在该基板102上。将镓或镓合金层106电沉积到微处理器的表面上。然后将散热件108耦合到镓层。表1提供了适于用作热界面的示例性镓合金以及相应的液相线(liquidus)温度和固相线(solidus)温度。
表1
用于形成镓层或镓合金层的电沉积方法一般包括对设置在含水镀液中的基板表面(例如工作电极)进行电镀,该镀液包含镓盐、甲磺酸(MSA)电解质以及溶剂。可以用酸或碱来控制镀液的pH。电解质中的镓离子浓度的范围可以为从约0.000005摩尔(M)M到接近于所使用的电解质和pH的饱和极限的摩尔浓度。可用于镀液的镓源包括可在镀液中溶解的镓盐,所述镓盐包括但不限于氯化镓(GaCl3)、溴化镓(GaBr3)、碘化镓(GaI3)、硝酸镓Ga(NO3)3、硫酸镓Ga(SO4)3、其混合物等。其他合适的镓盐包括硫酸盐、氨基磺酸盐、链烷磺酸盐、芳族磺酸盐、氟硼酸盐、以及强碱,例如氢氧化钠、氢氧化钾、氢氧化锂、氢氧化钙、氢氧化镁等。
作为电解质的诸如MSA的酸的浓度的范围可以为从约0.1M到约2M;在另外的实施例中,酸的范围为约0.1M到1M;且在进一步另外的实施例中,酸的范围为0.5M到1M。如上所述,电解浴液(electrolytebath)没有任何类型的有机或无机络合剂。即,镓盐可溶于电解浴液中。
电解浴液的pH一般小于2.6或大于12.6。申请人已发现,当溶液pH在2.6≤pH≤12.6的范围内时,镀液的外观变为浑浊的,即乳状。尽管不想被理论约束,相信镓的氧化物和/或氢氧化物是在该pH范围内形成的,例如,在水溶液中的氧化镓或氢氧化镓。提供并维持电解浴液的pH的合适的酸或碱不包含络合剂,并可以包括但不限于诸如硫酸的无机酸、有机酸,例如甲磺酸、乙磺酸、丙磺酸、丁磺酸或其他链烷磺酸、以及诸如苯磺酸和甲苯磺酸的芳族磺酸。有利地,发现处于这些pH范围的电沉积方法提供了均匀、薄的保形(conformal)镓层,从而防止独立岛的形成。
合金元素可以被直接添加到镀液。例如,可以通过铜源,例如溶解的铜金属或诸如硫酸铜、氯化铜、醋酸铜、硝酸铜的铜盐等,来提供电解质中的铜。同样地,可以通过铟源,例如氯化铟、硫酸铟、氨基磺酸铟、醋酸铟、碳酸铟、硫酸铟、磷酸铟、氧化铟、高氯酸铟、氢氧化铟等,在电解质中提供铟。
镓电镀液(electroplatingbath)可以进一步包括可选的有机添加剂,该有机添加剂包含至少一个氮原子或至少一个硫原子。该有机添加剂被添加到镀液以有效地增加析氢过电位(hydrogenevolutionoverpotential),并在镓的电镀期间防止或有效地限制氢的共沉积/析出,并通过控制成核和生长来控制沉积的微结构。有利地,在伴随地帮助镓成核的同时,该添加剂还用作光亮剂(brightener)和晶粒细化剂。通过其中同时在表面上形成相同尺寸的岛状物的瞬时成核来形成最薄的层。并且,可以通过其中岛状物的形成为时间的函数的渐进成核来形成薄层。通过这样做,所产生的镓层是均匀的和保形的,从而在沉积期间防止大的三维岛状物的形成。示例性有机添加剂包括但不限于脂族和/或杂环化合物,例如硫脲、噻嗪、磺酸、磺酸、烯丙基苯基砜(allylphenylsulfone)、磺酰胺(sulfamides)、咪唑、胺、异腈、二硫氧-双羟基氨基钼(dithioxo-bishydroxylaminomolybdenum)络合物及其衍生物。
已发现包含至少一个氮原子和/或至少一个硫原子添加剂的有机添加剂出乎意料地在抑制氢析出的同时加速镓电镀。通过这种方式,已发现在与作为电解质的MSA组合使用时,该有机添加剂提供了协同(synergistic)效果。包含至少一个氮原子和/或至少一个硫原子的有机添加剂的浓度范围可以为从约百万分之1(ppm)到约10000ppm,在另外的实施例中,有机添加剂的范围为约10ppm到5000ppm,且在进一步另外的实施例中,有机添加剂的范围为100ppm到1000ppm。
在另外的实施例中,与有机添加剂组合地添加金属氧化物,以抑制(poison)阴极,由此增加氢析出的起始过电位(即,抑制氢生成)并加速镓沉积。无机金属氧化物包括但不限于准金属氧化物,例如砷氧化物(例如As2O3;As2O5、KH2AsO4、K2HAsO4、K3AsO4、K3AsO3、KAsO2、NaH2AsO4、Na2HAsO4、Na3AsO4、Na3AsO3、NaAsO2、Na4As2O7等);锑氧化物(例如Sb2O3、Sb2O5、KH2SbO4、K2HSbO4、K3SbO4、K3SbO3、KSbO2、NaH2SbO4、Na2HSbO4、Na3SbO4、Na3SbO3、NaSbO2、Na4Sb2O7等);以及铋氧化物(例如Bi2O3、K3BiO3、KBiO2、Na3BiO3、NaBiO2等)。
已知镓沉积和氢析出同时发生,由此,现有技术的电镀方法一般呈现出较低的电镀效率以避免氢析出,该氢析出导致了所沉积的膜结构中的多孔性。上述金属氧化物是有效的阴极抑制剂,并有利地增加氢析出的起始过电位,并出乎意料地加速了镓沉积。利用包括金属氧化物以及包含至少一个氮原子和/或至少一个硫原子的有机添加剂的组合的镀镓溶液,已观察到大于90-95%的电镀效率。电解质中的金属氧化物的浓度范围可以为从约百万分之1(ppm)到约10,000ppm,在另外的实施例中,金属氧化物的范围为约100ppm到5,000ppm,且在进一步另外的实施例中,金属氧化物的范围为1,000ppm到3,000ppm。通过在镀液中引入金属氧化物和/或硫,所产生的层将包括相应的金属(例如砷、锑、铋或其混合物)和/或硫作为杂质,该杂质为沉积物中的百万分之几到原子百分之几的量级,这可以用Auger或SIMS分析方法来检测。
在另一实施例中,镀液包含镓盐、硫酸钠(Na2SO4)电解质、包含至少一个氮原子和/或至少一个硫原子的有机添加剂、以及溶剂。镓盐和有机添加剂的浓度如上所述。作为电解质的硫酸钠的浓度的范围可以为从约0.01M到约2M;在另外的实施例中,硫酸钠的范围为约0.1M到1M;且在进一步另外的实施例中,硫酸钠的范围为0.2M到60M。可选地,如上所述的金属氧化物可以被包含在镀液中。如上所述,pH小于2.6或大于12.6。在如上所述的各个实施例中,可在导电或不导电基板上使用电镀化学。合适的导电基板包括但不限于金、钼、铟铜、硒、锌等。合适的不导电基板一般为其上具有金属籽晶层的不导电基板,并包括且不限于玻璃、石英、塑料、聚合物等。例如,不导电基板可以包括籽晶层,例如铜籽晶层。沉积籽晶层的具体方法不受限制,并且被本领域技术人员所公知。例如,可以通过化学气相沉积、等离子体气相沉积或无电沉积来形成籽晶层。
电镀液还可以包含另外的成分。这些成分包括但不限于晶粒细化剂、表面活性剂、掺杂剂、其他金属或非金属元素等。例如,在配方中可以包括其他类型的有机添加剂,例如表面活性剂、抑制剂、匀平剂(leveler)、加速剂等,以细化其晶粒结构和表面粗糙度。有机添加剂包括但不限于聚亚烷基二醇型聚合物、聚链烷磺酸、香豆素、糖精、糠醛、丙烯腈、品红染料、胶、淀粉、葡萄糖等。
尽管在镀液配方中水是优选的溶剂,但应理解,在配方中还可以添加有机溶剂,部分地或全部地替代水。这样的有机溶剂包括但不限于酒精、乙腈、碳酸异丙烯酯、甲酰胺、二甲亚砜、甘油等。
尽管在电沉积方法中可以利用DC电压/电流,但应注意,脉冲或其他可变电压/电流源也可被用于获得高电镀效率和高质量沉积物。电镀液的温度范围可以是5到90℃,这取决于溶剂的性质。基于水的配方的优选镀液温度范围为10到30℃。
现在参考图6,在实施中,背部电接触5被制作到导电基板4,该导电基板4用作工作电极,镓或镓合金层将被沉积在其上。或者,如果基板是不导电的,首先可以沉积导电层和/或籽晶层(未示出),并通过欧姆接触来直接制作到籽晶层或到下面的导电层的电接触。根据本公开的电解质溶液1被放置为与基板表面4接触。导电对电极6,即,阳极或导体被设置在电解质溶液中,并与基板(工作电极)分隔开。尽管基板4被示为具有平面表面,但应理解,基板4上也可以具有某些形貌和/或保形导电层。对于电化学处理,通过电源7和电引线8将电流或电压施加到基板(电极)4和对电极6。如果需要,可以通过引入第三电极(即参考电极)(未示出)来更精确地控制结构/电解质的电化学势,该参考电极具有恒定的电化学势。参考电极的实例包括饱和甘汞电极(SCE)和银-氯化银(Ag/AgCl)参考电极或诸如Cu或Pt的其他金属参考电极。在电沉积期间可以搅拌电解质溶液。
以下实例仅为了示例的目的而给出,且不旨在限制本发明的范围。
实例1
在该实例中,镓被电镀到膜叠层上,且随后被自退火,以形成富铟的铟镓合金。电镀化学在0.5MMSA中包含0.2MGa3+,用0.5MNaOH来急冷(quench),然后使用额外量的MSA来调整到1.21的pH。镓被电镀到360nm的铟层和250nm的铜层上。具有150nm厚度的镓层随后在18-22℃的室温下被自退火持续3天的时间。一旦将镓镀在铟上,互扩散立即开始并逐渐形成In-Ga低共熔合金。
图7示出了膜叠层的截面图的扫描电子显微照片,其中,镓被电沉积到铟层上,且随后被退火,以形成富铟的镓低共熔层。有趣的是,Ga互扩散不会在铟层上停止,并会继续进入铜中,形成CuInGa的合金。
实例2
在该实例中,具有和不具有有机添加剂的各种镓镀液被用于将镓电沉积到玻璃基板上,在该基板上具有钼层,该钼层之前已用铜引晶(seed)。电镀溶液在具有0和500ppm硫脲的0.5MMSA中包含0.25M硫酸镓。电解浴液处于18-20℃,并以0和550rpm被搅拌。使用H2SO4,将pH保持在1.14。
结果表明,与不包含有机添加剂的镀液相比,有机添加剂的存在明显加速了镓电镀。此外,与没有搅拌相比,对电解质的连续搅拌提供了明显更高的电流密度。图8和9分别图形示出了以20mA/cm2和30mA/cm2来恒电流地沉积的镓膜的表面形貌视图。随着电流密度增加,观察到晶粒尺寸的增加。没有观察到多孔,且膜是均匀的并具有优良的形貌。
实例3
在该实例中,镀液在0.5MMSA中包含0.2MGa3+,用0.5MNaOH来急冷,然后通过添加更多的MSA来调整,以获得1.18的pH。在镀液中包含指出的不同量的As2O3。对于不包含As2O3或硫脲的镀液,镀液在0.5MMSA中包含Ga3+,用0.5MNaOH来急冷,使用额外的MSA将pH调整为1.18。包含As2O3和硫脲的组合的镀液所含的As2O3为500-6000ppm且硫脲为100-1000ppm。
图10提供了各种伏安图的叠加并包括As2O3和硫脲的组合的数据。如图所示,As2O3的逐渐增加的量为氢析出过电位的起始提供了负电位漂移,从而有效地抑制了氢生成。此外,硫脲和As2O3的组合加速了镓沉积。
实例4
在该实例中,镀液在0.5MMSA中包含0.25MGa3+,用0.5MNaOH来急冷,并用额外量的MSA来调整为1.18的pH。在没有任何额外的添加剂、具有6000ppm的As2O3、以及具有6000ppm的As2O3和500ppm的硫脲的条件下,进行电镀。图10中提供了这些电镀化学的循环伏安图。在添加了As2O3时,观察到氢析出的抑制和镓沉积的加速,且在As2O3和硫脲的组合的条件下,观察到加速(acceleration)的进一步提高。还示出了As2O3和As2O5的组合对于抑制氢析出也是有效的(其结果在这里未示出)。当这些氧化物二者组合在一起时,效果更为有效,即使是在较低的浓度下也是如此。
这里公开的所有范围包括端点,且端点可以互相组合。
所有被引用的专利、专利申请以及其他参考文献通过引用而将其全部内容并入本文中。
在描述本发明的上下文(特别是在以下权利要求的上下文)中术语“一”、“一个”和“该”以及类似的指示物的使用应被解释为既覆盖单数也覆盖复数,除非本文中另外指明或在上下文中明显抵触。此外,还应注意,术语“第一”、“第二”等在本文中不表示任何顺序、数量或重要性,而是被用于区分一个要素与另一要素。
尽管描述了本发明的优选实施例,但应理解,现在以及在将来,本领域技术人员可以进行落在以下权利要求的范围内的各种改进和提高。这些权利要求将被解释为保持对首次描述的本发明的恰当保护。
Claims (13)
1.一种形成用于光伏器件的p型半导体层的方法,包括:
将第一层电镀到基板的导电表面上,其中,所述第一层选自铜层和铜镓层;
将第二层电镀到所述第一层上,其中,所述第二层选自铟层、镓层、铟镓层、二硒化铜铟层、以及二硒化铜镓层;以及可选地,
将第三层电镀到所述第二层上,其中,所述第三层选自镓层和铟层;以及
可选地,将第四层电镀到所述第三层上,其中,所述第四层选自硒和硫;其中,所述电镀是通过这样的方法来实施的,该方法包括:使(i)基板和(ii)溶液接触,所述溶液包括:前体,其包含选自铜、镓、铟、硒、硫及其组合的元素;准金属的氧化物;在电镀镓层或镓合金层时使用的有机添加剂,其至少具有硫原子和/或氮原子;以及溶剂,用于溶解所述前体;将所述溶液的pH调整为选自从0到小于2.6的pH以及从12.6到14的pH的范围,并施加电流以电镀所述基板,以产生所述第一、第二、第三或第四层;以及
在存在硒源和/或硫源的条件下,对所述第一层、所述第二层和所述第三层进行退火,以形成所述p型半导体层。
2.如权利要求1所述的方法,其中,所述导电表面选自钼、钽、钨、钛、及其相应的氮化物。
3.如权利要求1所述的方法,其中,所述溶液包含浓度为0.01M到2M的硫酸钠。
4.如权利要求1所述的方法,其中,所述准金属的氧化物的量为百万分之1到百万分之10,000。
5.如权利要求1所述的方法,其中,所述有机添加剂选自硫脲、噻嗪、磺酸、烯丙基苯基砜、磺酰胺、二硫氧-双羟基氨基钼络合物及其衍生物。
6.如权利要求1所述的方法,其中,所述溶液包含选自甲磺酸、乙磺酸、丙磺酸和丁磺酸的链烷磺酸,并且其中,所述链烷磺酸的浓度为0.1M到2M。
7.如权利要求1所述的方法,其中,所述p型半导体具有0.8到0.9的Cu/(In+Ga)比率以及0.3到0.33的Ga/(Ga+In)比率。
8.如权利要求1到4、6到7中任一项所述的方法,其中,所述溶液不包含络合剂。
9.一种用于形成热界面的方法,所述方法包括:
将镓或镓合金的层电镀到发热表面上,所述发热表面被耦合到微处理器,其中,电镀所述镓或镓合金包括使所述发热表面与镀液接触,所述镀液包含镓盐、准金属的氧化物、溶剂和有机添加剂,所述有机添加剂至少包含一个硫原子和/或一个氮原子;将所述镀液的pH调整为选自大于0到小于2.6的pH以及大于12.6到14的pH的范围,并施加电流来电镀所述发热表面,以产生所述镓或镓合金的层;以及
将散热件或散热器耦合到所述镓或镓合金的层,以形成所述热界面。
10.如权利要求9所述的方法,其中,所述镀液包含选自甲磺酸、乙磺酸、丙磺酸和丁磺酸的链烷磺酸,并且其中,所述链烷磺酸的浓度为0.1M到2M。
11.如权利要求9所述的方法,其中,所述镀液包含浓度为0.01M到2M的硫酸钠。
12.如权利要求9所述的方法,其中,所述有机添加剂选自硫脲、噻嗪、磺酸、烯丙基苯基砜、磺酰胺、二硫氧-双羟基氨基钼络合物及其衍生物。
13.如权利要求9到11中任一项所述的方法,其中,所述镀液不包含络合剂。
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2011
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- 2011-08-05 JP JP2013526388A patent/JP5827689B2/ja active Active
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JP2013536986A (ja) | 2013-09-26 |
DE112011102300B4 (de) | 2022-11-17 |
GB2498879A (en) | 2013-07-31 |
GB2498879B (en) | 2014-09-24 |
GB201305111D0 (en) | 2013-05-01 |
JP5827689B2 (ja) | 2015-12-02 |
US9401443B2 (en) | 2016-07-26 |
US20120055612A1 (en) | 2012-03-08 |
WO2012028415A1 (en) | 2012-03-08 |
US20130008798A1 (en) | 2013-01-10 |
DE112011102300T5 (de) | 2013-05-16 |
CN103098225A (zh) | 2013-05-08 |
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