TW201835941A - 含矽油的導電膏 - Google Patents
含矽油的導電膏 Download PDFInfo
- Publication number
- TW201835941A TW201835941A TW106106142A TW106106142A TW201835941A TW 201835941 A TW201835941 A TW 201835941A TW 106106142 A TW106106142 A TW 106106142A TW 106106142 A TW106106142 A TW 106106142A TW 201835941 A TW201835941 A TW 201835941A
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- TW
- Taiwan
- Prior art keywords
- conductive paste
- semiconductor substrate
- conductive
- weight
- eucalyptus oil
- Prior art date
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- 229920002545 silicone oil Polymers 0.000 title abstract 3
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000004065 semiconductor Substances 0.000 claims abstract description 33
- 238000009835 boiling Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 8
- 239000010642 eucalyptus oil Substances 0.000 claims description 55
- 229940044949 eucalyptus oil Drugs 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 38
- 238000007650 screen-printing Methods 0.000 claims description 21
- 238000007639 printing Methods 0.000 claims description 17
- -1 tetradecyl hexaoxane Chemical compound 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010776 emu oil Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000006259 organic additive Substances 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- WLRWTEIAYJHXDW-UHFFFAOYSA-N 2,2,3,3,4,4,4a,5,5,6-decamethyl-6H-cyclopenta[b]pyran Chemical compound CC1C=C2C(C(C(C(O2)(C)C)(C)C)(C)C)(C1(C)C)C WLRWTEIAYJHXDW-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 241000219927 Eucalyptus Species 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
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- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 2
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 2
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 2
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KITANORVVDJFTO-UHFFFAOYSA-N C(CCCCCCCCCCCCC)C1OC=2C(CC1)C=CC2 Chemical compound C(CCCCCCCCCCCCC)C1OC=2C(CC1)C=CC2 KITANORVVDJFTO-UHFFFAOYSA-N 0.000 description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 2
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 2
- QTPKWWJYDWYXOT-UHFFFAOYSA-N [W+4].[O-2].[In+3] Chemical compound [W+4].[O-2].[In+3] QTPKWWJYDWYXOT-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
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- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- MMKRHZKQPFCLLS-UHFFFAOYSA-N ethyl myristate Chemical compound CCCCCCCCCCCCCC(=O)OCC MMKRHZKQPFCLLS-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 2
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- 238000009736 wetting Methods 0.000 description 2
- LDJAOSSRIHBIMJ-MURFETPASA-N (9z,12z)-2-ethyloctadeca-9,12-dienoic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCC(CC)C(O)=O LDJAOSSRIHBIMJ-MURFETPASA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
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- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Chemical class CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H01L21/702—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof of thick-or thin-film circuits or parts thereof
- H01L21/705—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof of thick-or thin-film circuits or parts thereof of thick-film circuits or parts thereof
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E10/00—Energy generation through renewable energy sources
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Abstract
本發明係關於一種導電膏,其包含:各自按該導電膏之總質量計,30至97重量%的導電粒子、0至20重量%的玻璃料、3至70重量%的有機介質及0.1至67重量%的矽油,其中該矽油之沸點或沸點範圍介於180℃與350℃之間的範圍內。本發明進一步關於該導電膏之用途及使用該導電膏在半導體基板上製造電極之方法。
Description
本發明係關於一種導電膏,其包含30至97重量%的導電粒子、3至70重量%的有機介質及0至20重量%的玻璃料。
導電膏或墨水可用於在半導體基板或絕緣材料基板之表面上形成電極(諸如導電柵格線,例如銀柵格線)及匯流排。尤佳用途為在半導體基板上網版印刷電極以製造太陽能電池或光伏打電池,當來自日光之光子將半導體上的電子自價能帶激發至傳導帶時,該等太陽能電池或光伏打電池將太陽能轉化為電能,藉由接觸半導體之金屬電極來彙集流動至傳導帶之電子。
除在半導體基板上印刷電極以製造太陽能電池或光伏打電池以外,導電膏或墨水亦可用於在絕緣基板上印刷柵格線,以製造陶瓷基板上的印刷電子電路板或混合電路。
為了將細線印刷至半導體基板或絕緣基板上,通常使用網版印刷方法來進行具成本效益的大批量製造。然而,產生均勻的窄線而無線中斷對於網版印刷(尤其對於高速網版印刷)而言具有挑戰性,工業印刷速度視應用要求而定,其介於80mm/s至800mm/s範圍內,較佳不慢於150mm/s,例如在太陽能電池印刷中,印刷速度為150mm/s至300mm/s。
藉由稱為網版乳液之聚合物層覆蓋不鏽鋼線之網眼中的所選區域來製造用於網版印刷之網版,在網版印刷製程期間,導電膏僅可流經未由網版乳液覆蓋之網版區域,出於此原因,網版印刷膏必須顯示對不鏽鋼線之表面及對網版乳液之表面的最小黏著性。
當導電膏用於在半導體基板上印刷時,導電膏通常包含:導電粒子,其典型地為金屬粉末;有機介質;以及視情況玻璃料。有機介質典型地包含至少一種有機液體,諸如有機溶劑或有機鹽,或者是在室溫下具有液態形式之其他有機化合物,有機介質視情況包含聚合組分;為了形成金屬接觸,將導電膏印刷至基板上,視材料類型而定,隨後在介於約150℃至約950℃範圍內之溫度下加熱基板,其中有機介質分解,且無機物質形成導電軌及與基板電接觸。
用於在半導體基板上印刷電極(例如用以製造太陽能電池)之糊膏揭示於例如JP-A 2010-087251、KR-A 10-2009-0067992或US-A 2014/0124713中。
然而,為了在網版印刷方法中使用,糊膏必須以定量方式自製成網版之材料的表面釋放,且完全轉移至基板表面;另一方面,該糊膏必須顯示對上面印刷該糊膏之基板表面的足夠黏著性,以獲得具有足夠厚度且不顯示任何中斷之細線。
因此,本發明之目的在於提供一種導電膏,其可藉由網版印刷進行印刷,而不會過牢固地黏著於網版材料上;且其具有足夠黏著性以形成細柵格線,而不會滲漏於上面印刷有導電膏之基板上。
此目的係藉由一種導電膏而達成,該導電膏包含:各自按導電膏之總質量計,30至97重量%的導電粒子、0至20重量%的玻璃料、3至70重量%的有機介質及0.1至67重量%的矽油,其中矽油之沸點或沸點範圍介於180℃與350℃之間的範圍內。
矽油可包含僅一種類別之矽油分子或不同類別之矽油分子。矽油分子含有元素矽、氧、碳以及氫,在矽油分子中,矽原子經由一至四個氧原子與其他矽原子互連,每個矽原子與其他原子形成4個共價鍵,其他原子可為氧原子或甲基。
矽油分子可為環狀、分支或線性的。環狀矽油分子之典型實例為十甲基環五矽氧烷、十二甲基環六矽氧烷或十四甲基環七矽氧烷;線性矽油分子之典型實例為十甲基四矽氧烷、十二甲基五矽氧烷、十四甲基六矽氧烷以及十六甲基七矽氧烷。
若矽油僅含有單一類型之分子,則此矽油在1013毫巴之正常壓力下具有確定的沸點,舉例而言,純六甲基二矽氧烷之沸點為100.0℃;若矽油含有數種不同類型之分子,則此矽油呈現之沸點範圍取決於矽油之化學組成。在沸點範圍之下限處,矽油中最易揮發的組分自矽油之液相變為氣相;在沸點範圍之上限處,矽油中最不易揮發的組分自矽油之液相變為氣相,矽油之沸點範圍的上限可由矽油中最不易揮發的組分界定,該組分的確會蒸發但不會化學分解。
矽油之物理特性視所含矽油分子之化學結構而定。在線性矽油之情況下,分子量提高導致沸點提高、恆溫下的蒸汽壓降低、導電膏調配物中的擴散速度降低、表面張力提高以及黏度提高。
矽油分子與如聚醚之其他化學物質的共聚物通常在如消泡、黏著性控制、分散以及潤濕之各種應用中用作表面活性組分。
舉例而言,矽油與其他化學物質之該等共聚物揭示於KR923741B1、JP2010087251A2以及US2014/0124713A1中。
在高於25℃之溫度及環境壓力下,聚矽氧蒸發或分解。六甲基二矽氧烷之沸點為100℃,其為所有矽油分子之最低沸點;所有其他矽油分子均具有較大分子量,並因此沸點較高且恆溫下的蒸汽壓較低,在將矽油分子自25℃加熱至800℃時,分子是否蒸發或化學分解則視加熱速率及矽油分子之類型而定。
在包含矽油分子之錯合物調配物(如金屬膏)中,矽油分子是否在以確定的加熱速率加熱期間蒸發或化學分解,其亦視調配物之總組成物而定。矽油分子之蒸汽壓及擴散速度將決定矽油分子是否可經由蒸發過程到達導電膏表面及轉換為氣相,或決定矽油分子是否在導電膏燒結期間於導電膏內部進行化學分解。
在自25℃加熱至800℃期間,矽油分子之化學分解包含形成二氧化碳、水以及二氧化矽,在高於100℃之溫度下,二氧化碳及水轉換為氣相,然而,即使在高達800℃之溫度下,二氧化矽仍為固態。此外,二氧化矽為非導電材料,其提高了金屬電極之比電阻,經由網版印刷金屬膏、隨後使導電膏乾燥且在高溫下燒製而形成該等金屬電極,因此,向金屬膏調配物中添加矽油似乎不利於最佳線導電性。
另一方面,在於25℃及環境壓力下進行網版印刷期間,金屬膏中之揮發性液體組分可使導電膏快速乾燥,在網版印刷期間失去液體
膏組分導致導電膏流變性之變化,且對印刷效能產生不利影響,因液體組分快速蒸發所致的導電膏黏度提高可造成網版印刷出間斷電極,其原因在於不充足的導電膏流經網版乳液之窄線開口。
矽油因其獨特的化學及物理特性而得到廣泛使用。矽油分子之低極性僅實現矽油分子與其他化學物質之間的微弱吸引力,因此,矽油分子為用於降低黏著性之塗層部分,且用作橡膠、塑膠以及低熔點金屬之熱模製的脫模劑。
此外,矽油呈現極低表面張力,此為其各種表面獨特潤濕特性的原因。舉例而言,不鏽鋼具有極高表面能。因此,不鏽鋼試圖藉由吸附任何類別之材料來使其表面能降至最低。
出人意料地,已發現包含有機介質及矽油(其沸點範圍介於180℃與350℃之間)的導電膏的確在將導電膏網版印刷至半導體上(例如用於製造太陽能電池)之期間顯著改良印刷品質。因為該等矽油極有效地潤濕不鏽鋼篩目之金屬線,所以其顯著改良導電膏自網版乳液之窄開口的釋放,在網版印刷期間用矽油分子潤濕篩目之不鏽鋼線降低了金屬膏對不鏽鋼線之黏著性,且支持導電膏自不鏽鋼表面的有效釋放。
另一出人意料的結果為兩種導電膏之相同固體含量測量,其中在第二導電膏中,矽油僅已取代第一導電膏之溶劑摻合物。此意謂,沸點範圍介於180℃與350℃之間的矽油不會形成非導電二氧化矽殘餘物,該等殘餘物為乾燥導電膏期間,或者是在高溫下燒製導電膏期間,矽油分子的化學分解產物。
在本發明之一個較佳具體實例中,導電膏含有0.1至50重量%的矽油,其沸點或沸點範圍介於180℃與350℃之間的範圍內,沸點或沸點範圍較佳介於190℃與300℃之間的範圍內,且沸點或沸點範圍尤佳介於200℃與270℃之間的範圍內;導電膏中有機介質之量較佳為3至70重量%,且導電粒子之量較佳為30至97重量%。
在本發明的範疇內,應將術語「沸點範圍介於……之間的範圍內(boiling range in the range between)」理解為沸點範圍之最小值及最大值各自介於限制該範圍之溫度範圍內,但最小值及最大值不必對應於限制沸點範圍所在之溫度。
矽油較佳包含聚二甲基矽氧烷分子。
在本發明之一個具體實例中,矽油含有線性矽油分子,若使用線性矽油分子,則矽油分子較佳選自:十甲基四矽氧烷、十二甲基五矽氧烷、十四甲基六矽氧烷、十六甲基七矽氧烷或其混合物。
在本發明之另一具體實例中,矽油含有環狀矽油分子,若使用環狀矽油分子,則矽油分子較佳選自:十甲基環五矽氧烷、十二甲基環六矽氧烷、十四甲基環七矽氧烷或其混合物。
除使用線性矽油分子、分支矽油分子或環狀矽油分子以外,亦可使用前述類型之矽油分子中的至少兩者。無關乎矽油分子之形式,無論是線性、分支或環狀,或者是其至少兩者之混合,當矽油分子為聚二甲基矽氧烷時為尤佳的。
導電膏中存在之導電粒子可為由任何導電材料構成之任何幾何形狀的粒子。較佳地,導電粒子包含碳、銀、金、鋁、鉑、鈀、錫、鎳、鎘、鎵、銦、銅、鋅、鐵、鉍、鈷、錳、鉬、鉻、釩、鈦、鎢,或者是其混合物、或合金或呈其核殼結構形式,用於導電粒子之較佳材料為銀或鋁,尤其為銀(歸因於其良好導電性及良好抗氧化性)。
導電粒子之平均粒度較佳介於10nm至100μm範圍內,更佳地,平均粒度介於100nm至50μm範圍內,且尤佳地,平均粒度介於500nm至10μm範圍內。導電粒子可具有熟習此項技術者已知的任何所要形式。舉例而言,粒子可呈薄片、棒狀、線狀、團塊、球形或其任何混合之形式,本發明之上下文中的球形粒子亦包含具有偏離理想球形之實際形式的粒子,舉例而言,球形粒子由於製造原因亦可具有液滴形狀或被截短,可用於製造導電膏之適合粒子為熟習此項技術者已知的且可商購,尤佳地,使用球形銀粒子。相比於不規則形狀粒子,球形粒子之優點在於其改良之流變行為。
導電粒子在組成物中之比例介於30至97重量%範圍內,比例較佳介於70至95重量%範圍內,且尤佳介於85至92重量%範圍內,此固體粒子重量百分比經常稱為固體含量。
粒子形狀及尺寸不會改變本發明之性質,所用粒子可以呈不
同形狀及尺寸之混合形式。如熟習此項技術者所知,當呈不同形狀或尺寸之混合的粒子分散於相同有機介質中時,其可導致較高或較低黏度,在該情況下,如熟習此項技術者所知,需要相應地調整有機介質,該調整可為(但不限於)改變固體含量、溶劑含量、聚合物含量、搖變減黏膠含量及/或界面活性劑含量,舉例而言,典型地當使用奈米尺寸的粒子代替微米尺寸的粒子時,必須減少固體含量以避免導電膏黏度之增加,由此導致較高之有機組分含量。
通常在製造過程中用有機添加劑塗佈導電粒子,尤其當其由金屬製成時;在製備用於印刷導體軌之組成物的過程中,典型地不移除表面上的有機添加劑,因此其隨後亦存在於導電膏中。按粒子質量計,用於穩定化之添加劑的比例通常不超過10重量%,用於塗佈導電粒子之添加劑可為例如脂肪胺或脂肪醯胺,例如十二胺,其他適用於使粒子穩定之添加劑為例如辛胺、癸胺以及聚伸乙基亞胺;另一具體實例可為經環氧化或未經環氧化之脂肪酸、脂肪酸酯,例如十二酸、棕櫚酸、油酸、硬脂酸或其鹽,粒子上的塗層不會改變本發明之性質。
在一個具體實例中,導電膏另外包含玻璃料,若玻璃料存在於導電膏中,則可使用熟習此項技術者已知的基於含鉛組成物或無鉛組成物之任何玻璃料。玻璃料不限於任何特定形狀或形式,所用玻璃料粒子之平均粒度介於10nm至100μm範圍內,玻璃料粒子之平均粒度更佳介於100nm至50μm範圍內,且尤佳介於500nm至10μm範圍內,所用粒子可具有熟習此項技術者已知的任何所要形式,舉例而言,粒子可呈薄片、棒狀、線狀、團塊、球形或其任何混合之形式,在此情形中,球形粒子意謂粒子
之實際形式偏離理想球形,舉例而言,球形粒子由於製造原因亦可具有液滴形狀或被截短,可用作玻璃料之適合粒子為熟習此項技術者已知的且為可商購的,尤佳地係使用球形粒子,相比於不規則形狀粒子,球形粒子之優點在於其改良之流變行為。根據本發明,按導電膏之總質量計,玻璃料含量介於0至20重量%、較佳0至10重量%且最佳1至5重量%範圍內。
導電膏中之有機介質可包含至少一種溶劑,在本發明之一個具體實例中,溶劑包含一或多種選自具有至少一個氧原子之液體有機組分的溶劑。具有至少一個氧原子之液體有機組分選自:醇、酯醇、二醇、二醇醚、酮、脂肪酸酯、萜類衍生物以及二元酯,舉例而言,該液體有機組分可為苯甲醇、Texanol、乳酸乙酯、二甘醇乙酸單乙酯、二甘醇單丁醚、二甘醇二丁醚、二甘醇單丁醚乙酸酯、丁賽路蘇(butyl cellosolve)、乙酸丁賽路蘇(butyl cellosolve acetate)、丙二醇單甲醚、丙二醇單甲醚乙酸酯、二丙二醇單甲醚、丙二醇單甲基丙酸酯、乙醚丙酸酯、二甲胺基甲醛、甲基乙基酮、γ-丁內酯、亞麻油酸乙酯、次亞麻油酸乙酯、肉豆蔻酸乙酯、油酸乙酯、肉豆蔻酸甲酯、亞麻油酸甲酯、次亞麻油酸甲酯、油酸甲酯、鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯以及萜品醇。
作為具有至少一個氧原子之液體有機組分的溶劑可在導電膏中用作單一溶劑或溶劑混合物,倘若使用溶劑混合物,則按溶劑混合物之總質量計,溶劑可額外包含5至50wt%的至少一種二元酯,二元酯較佳選自:己二酸、戊二酸、丁二酸之二甲酯或其混合物。
當使用單一溶劑或溶劑混合物時,必要的是,有機黏合劑可以大於2wt%溶解於所選單一或混合溶劑中,因此按有機介質之總質量計,
有機介質包含至少2wt%經溶解的黏合劑。
在本發明之一個具體實例中,導電膏額外包含0.1至20wt%的至少一種添加劑,該添加劑選自:界面活性劑、觸變劑、塑化劑、增溶劑、消泡劑、乾燥劑、交聯劑、抑制劑、錯合劑及/或導電聚合物粒子,添加劑可單獨使用或作為其中之兩者或多於兩者的混合物使用。
當界面活性劑用作添加劑時,可僅使用一種界面活性劑或使用多於一種界面活性劑。原則上,熟習此項技術者已知的,或先前技術中所描述的所有界面活性劑均可為適合的,較佳界面活性劑為單一或複數種化合物,例如陰離子、陽離子、兩性或非離子界面活性劑,然而,亦可使用具有色素近緣(pigment-affinitive)錨基之聚合物,其作為界面活性劑而為熟習此項技術者所知。
倘若導電粒子預塗佈有界面活性劑,則導電膏可不包含額外界面活性劑作為添加劑。
除溶劑及其他有機添加劑以外,導電膏亦可包含介於0.1至20重量%範圍內之有機黏合劑。有機黏合劑可選自天然或合成樹脂及聚合物,如熟習此項技術者所已知,係基於(但不限於)溶劑相容性及化學穩定性來進行選擇,舉例而言,如先前技術中所揭示之常用黏合劑包含:纖維素衍生物、丙烯酸系樹脂、酚系樹脂、脲-甲醛樹脂、醇酸樹脂、脂族石油樹脂、三聚氰胺甲醛樹脂、松香、聚乙烯、聚丙烯、聚苯乙烯、聚醚、聚胺甲酸酯、聚乙酸乙烯酯以及其共聚物。
本發明之導電膏尤其用於網版印刷方法以在基板上製造導電圖案,尤佳地,導電膏用於在半導體上印刷電極以製造太陽能電池。
本發明進一步關於用於在半導體基板上製造電極之方法,其包含以下步驟:(a)在半導體基板上以預定圖案來網版印刷如上文所描述之導電膏,以形成經印刷之半導體基板,(b)在介於100℃至300℃範圍內之溫度下乾燥經印刷之半導體基板,(c)將具有印刷組成物之乾燥經印刷的半導體基板加熱至介於600℃至900℃範圍內之燒結溫度,以燒結導電粒子。
適合半導體基板為例如製造光伏打電池之該等基板,其包含n型區域、p型區域、p-n接面以及導電格線,光伏打電池視情況包含抗反射層於基板表面上,半導體基板可為塗佈有單晶矽、多晶矽、非晶矽之固體基板,或者是表面塗佈有以下各者之基板:多晶或非晶透明導電氧化物(TCO),諸如氧化銦錫(ITO);基於ZnO之透明導電氧化物,諸如氧化銦鎵鋅(IGZO)、氧化銦鋅錫(IZTO)及氧化銦鋅(IZO);氧化銦鎢(IWO)及氧化鎵鋅(GZO),藉由網版印刷方法自導電膏形成導電格線。
以熟習此項技術者已知的任何已知方式進行步驟(a)中之網版印刷,印刷方法尤其可為工業高速網版印刷方法,在該方法中,印刷速度視應用要求而定,其介於80mm/s至800mm/s範圍內,較佳不慢於150mm/s,例如在太陽能電池印刷中,印刷速度為150mm/s至300mm/s。
在將導電膏印刷至半導體基板上之後,在介於100℃至300℃範圍內之溫度下乾燥經印刷之半導體基板,乾燥步驟較佳進行達介於10至50sec範圍內、尤佳介於15至30sec範圍內之持續時間。
在乾燥之後,將乾燥經印刷之半導體基板加熱至介於600℃
至900℃範圍內之燒結溫度,以燒結導電粒子。在加熱步驟中,在5至50sec內、較佳5至35sec內將經印刷之半導體基板自乾燥溫度加熱至燒結溫度,保持燒結溫度達小於5sec,且隨後在3至60sec內、較佳3至30sec內將經印刷之半導體基板冷卻至室溫,整個加熱步驟進行之持續時間介於10至80sec、較佳15至50sec範圍內。
實施例
已使用如表3中所示之網版參數來網版印刷根據表1中之組成的導電膏。
在調配物E2中,溶劑摻合物A已由矽油部分取代,有機添加劑摻合物A含有分散劑、聚合物以及搖變減黏膠之混合物,有機溶劑摻合物A含有Texanol與己二酸二甲酯之混合物。
已使用以下網版參數來進行網版印刷:
調配物E2對具有板-板幾何結構之流變儀的不鏽鋼表面顯示較低黏著性,因此,在調配物E2之情況下,上板在恆定剪應力下顯示較快旋轉速度。
印刷方法之結果顯示於圖1及圖2中。
圖1及圖2顯示在250℃下乾燥、且隨後在800℃下燒結後,導電膏組成物E1及E2之印刷線的顯微鏡圖片。藉由比較圖1及圖2中所示之線,可看出使用本發明之調配物E2所印刷之線顯示較少滲漏。
已使用個別導電膏E1及E2來網版印刷8個多晶晶圓,圖3顯示電池效率測量結果,圖4顯示熱重分析結果。
自圖3可顯而易見的是,包含矽油之根據本發明的導電膏組成物比不含矽油之導電膏組成物具有更高電池效率。
圖4顯示,在加熱步驟期間,兩種導電膏之質量降低幾乎相同,其顯示在加熱步驟期間,矽油未形成將使電池效率降低之二氧化矽。
Claims (12)
- 一種導電膏,其包含:各自按該導電膏之總質量計,30至97重量%的導電粒子、0至20重量%的玻璃料、3至70重量%的有機介質及0.1至67重量%的矽油,其中該矽油之沸點或沸點範圍介於180℃與350℃之間的範圍內。
- 如申請專利範圍第1項之導電膏,其中該矽油含有線性分子、分支分子、環狀分子或其混合物。
- 如申請專利範圍第1項之導電膏,其中該矽油包含聚二甲基矽氧烷。
- 如申請專利範圍第2項之導電膏,其中該線性矽油分子選自由以下組成之群:十甲基四矽氧烷、十二甲基五矽氧烷、十四甲基六矽氧烷、十六甲基七矽氧烷或其混合物。
- 如申請專利範圍第2項之導電膏,其中該環狀矽油分子選自由以下組成之群:十甲基環五矽氧烷、十二甲基環六矽氧烷、十四甲基環七矽氧烷或其混合物。
- 如申請專利範圍第1項之導電膏,其中該等導電粒子包含碳、銀、金、鋁、鉑、鈀、錫、鎳、鎘、鎵、銦、銅、鋅、鐵、鉍、鈷、錳、鉬、鉻、釩、鈦、鎢,或者是其混合物、或合金或呈其核殼結構形式。
- 如申請專利範圍第1項之導電膏,其中該等導電粒子塗佈有有機添加劑。
- 一種如申請專利範圍第1項至第7項中任一項之導電膏的用途,其用於藉由網版印刷將電極印刷至半導體基板上。
- 一種用於在半導體基板上製造電極之方法,其包含以下步驟: (a)在半導體基板上以預定圖案來網版印刷如申請專利範圍第1項至第7項中任一項之導電膏,以形成經印刷之半導體基板,(b)在介於100℃至300℃範圍內之溫度下乾燥該經印刷之半導體基板,(c)將具有該印刷組成物的該乾燥之經印刷半導體基板加熱至介於650℃至900℃範圍內之燒結溫度,以燒結該等導電粒子。
- 如申請專利範圍第9項之方法,其中該乾燥步驟進行之持續時間介於10至50sec範圍內。
- 如申請專利範圍第9項之方法,其中在該加熱步驟中,在5至50sec內將該經印刷之半導體基板自室溫加熱至該燒結溫度,保持該燒結溫度達1至5sec,且隨後在3至60sec內將該經印刷之半導體基板冷卻至室溫。
- 如申請專利範圍第9項之方法,其中該半導體基板為用於太陽能電池之半導體基板。
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TWI721620B (zh) * | 2018-12-21 | 2021-03-11 | 南韓商三星Sdi股份有限公司 | 用於太陽能電池電極的組合物及使用所述組合物製備的太陽能電池電極 |
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KR102149488B1 (ko) * | 2017-12-21 | 2020-08-28 | 엘에스니꼬동제련 주식회사 | 태양전지용 전극용 페이스트 조성물 및 이를 사용하여 제조된 태양전지 |
FR3089061B1 (fr) * | 2018-11-27 | 2020-12-18 | Commissariat Energie Atomique | Procede de fabrication d’un contact electrique pour une cellule photovoltaïque |
CN110248465B (zh) * | 2019-06-20 | 2024-03-19 | 上海铠琪科技有限公司 | 一种厚膜和覆铜一体陶瓷电路板及其制备方法 |
KR102413679B1 (ko) * | 2019-12-31 | 2022-06-24 | 엘에스니꼬동제련 주식회사 | 태양전지 전극용 페이스트 및 이를 사용하여 제조된 태양전지 |
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