TWI510680B - 銅電鍍溶液及其製備與使用方法 - Google Patents
銅電鍍溶液及其製備與使用方法 Download PDFInfo
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- TWI510680B TWI510680B TW103108542A TW103108542A TWI510680B TW I510680 B TWI510680 B TW I510680B TW 103108542 A TW103108542 A TW 103108542A TW 103108542 A TW103108542 A TW 103108542A TW I510680 B TWI510680 B TW I510680B
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- Prior art keywords
- copper
- copper plating
- group
- solution
- plating solution
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- 238000007747 plating Methods 0.000 title claims description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 64
- 229910052802 copper Inorganic materials 0.000 title claims description 64
- 239000010949 copper Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000003839 salts Chemical class 0.000 claims description 28
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 24
- 229910001431 copper ion Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 12
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 238000009713 electroplating Methods 0.000 claims description 8
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 claims description 6
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims description 6
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 claims description 6
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 claims description 6
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 150000007979 thiazole derivatives Chemical class 0.000 claims description 6
- OKBJVIVEFXPEOU-UHFFFAOYSA-N 1,2,3-trichloro-4-(2,3,6-trichlorophenyl)benzene Chemical compound ClC1=C(Cl)C(Cl)=CC=C1C1=C(Cl)C=CC(Cl)=C1Cl OKBJVIVEFXPEOU-UHFFFAOYSA-N 0.000 claims description 5
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 4
- PUVGEOXYMWPVPG-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-propylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CCC[N+](C)(C)CCO PUVGEOXYMWPVPG-UHFFFAOYSA-N 0.000 claims 2
- 239000000243 solution Substances 0.000 description 56
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 14
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- 235000012431 wafers Nutrition 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- 229910052732 germanium Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- ZMPAPJBFYQSNFM-UHFFFAOYSA-N 1-sulfanylimidazole Chemical class SN1C=CN=C1 ZMPAPJBFYQSNFM-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- KIQXPRRNZKQBOR-UHFFFAOYSA-O 2-(1,3-benzothiazol-3-ium-3-yl)acetic acid Chemical compound C1=CC=C2[N+](CC(=O)O)=CSC2=C1 KIQXPRRNZKQBOR-UHFFFAOYSA-O 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- -1 thioimidazole compound Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
- C25D7/126—Semiconductors first coated with a seed layer or a conductive layer for solar cells
-
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/011—Electroplating using electromagnetic wave irradiation
-
- 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
- Y02E10/547—Monocrystalline silicon PV cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Sustainable Energy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrodes Of Semiconductors (AREA)
- Photovoltaic Devices (AREA)
Description
[不適用]
概言之，本發明技術係關於銅電鍍溶液及製備與使用該等溶液之方法。具體而言，本發明技術包括包含銅離子源及導電性鹽之銅電鍍溶液，其中銅電鍍溶液具有介於1.7與3.5間之pH，且基本上不含氯離子。本發明技術亦係關於使用該等銅電鍍溶液之方法。此技術可用於製造印刷電路板及太陽能矽晶圓。
本申請案係關於銅電鍍。銅電鍍可用於許多技術領域，例如用於印刷電路之領域。銅可電鍍至許多基材(例如印刷電路板(PCB)、太陽能電池及積體電路(IC)基材)上。
印刷電路板係指形成自位於絕緣材料(通常玻璃纖維強化之環氧樹脂)之相對側之導電材料(通常為銅或電鍍有焊料或金之銅)的固體電路。若印刷電路板具有兩個位於單一絕緣層之相對側之導電表面，則所得電路板係稱為「雙面電路板」。為在單一板上容納甚至更多之電路，將若干銅層夾於絕緣材料之板間以產生多層電路板。
積體電路或單片積體電路(亦稱為IC、晶片或微晶片)係一組在一個半導體材料(通常為矽)之小板(「晶片」)上之電子電路。此可經製
得比自獨立組件製得之離散電路小得多。積體電路現今用於大量電子設備中。電腦、行動電話及其他數位家用器具均利用積體電路。
太陽能電池(亦稱為光伏打(PV)電池)係藉由光伏打效應將光能轉換成電之電裝置。其係光電電池之一種形式(此乃因當光入射於其上時，其電特徵--例如電流、電壓或電阻--有所不同)，其在暴露於光下時可在不附接至任何外部電壓源之情況下生成並支撐電流。典型矽PV電池係由薄晶圓構成，該薄晶圓係由在硼摻雜之(P型)矽之較厚層頂部之磷摻雜之(N型)矽之超薄層組成。在該兩種材料接觸之電池頂部表面(稱為P-N接面)附近產生電場。當日光撞擊PV電池之表面，此電場向光刺激之電子提供動量及方向，從而當將太陽能電池連接至電負載時產生電流流動。
製造習用單晶及多晶矽PV電池之製程以極純之半導體級多晶矽-自石英處理且遍及電子行業廣泛使用之材料開始。然後將多晶矽加熱至熔融溫度，且將痕量之硼添加至熔體中以產生P型半導體材料。接著，通常使用兩種方法中之一者形成矽之錠或塊：1)藉由自熔融多晶矽拔拉之種晶生長純結晶矽晶錠或2)藉由澆鑄熔融多晶矽成塊形式，從而產生多晶矽材料。然後使用線鋸自晶錠切割個別晶圓，且然後使其經受表面蝕刻製程。在清潔晶圓後，將其置於磷擴散爐中，從而在電池之整個外表面周圍產生薄N型半導體層。接著，將抗反射塗層施加至電池之頂部表面。
將鍍鋁導電材料沈積於每一電池之後(正)表面上，從而藉由置換經擴散磷層來恢復後表面之P型性質。有時藉由絲網印刷金屬膏(鋁膏)來施加鍍鋁導電材料。
亦將電觸點壓印在電池之頂部(負)表面。通常將由精細「指狀物」及較大「匯流排」構成之格柵樣金屬觸點絲網印刷至頂部表面上。此通常係使用銀膏實現。然而，銀膏極為昂貴。減少PV電池之
成本之一步驟為藉由利用各種成本較低之電鍍塗層(例如鎳、銅、錫及每一者之各種組合)進行頂塗來印刷較精細銀格柵並改良其導電性。銀膏之電鍍係容易藉由將經絲網印刷並經燒製之晶圓浸漬至施加直流電之電鍍溶液中或LIP電鍍來達成。然後將金屬直接沈積至銀膏上，且由於高導電性及銀粒子上之極薄氧化物而不需要任何預處理。
常見銅電鍍溶液包括明亮酸銅電鍍溶液、含有螯合化合物之銅電鍍溶液、鹼性銅電鍍溶液及含有氰化物之銅電鍍溶液。含有螯合化合物之銅電鍍溶液不總是合意的，此乃因螯合銅溶液之廢物處理比非螯合銅溶液成本更高。鹼性銅電鍍溶液不總是合意的，此乃因鹼性溶液需要螯合劑或強錯合劑(如氰化物)。氰化物有毒且存在健康風險。
一特定銅電鍍方法係明亮酸銅電鍍。明亮酸銅電鍍涉及高數量之硫酸或其他酸。明亮酸銅電鍍亦需要氯離子以製造平滑沈積物。
申請人確定氯離子及含有酸之電鍍溶液不適於某些電鍍應用。例如，該等溶液不適於在矽太陽能電池晶圓上之金屬晶種層上電鍍。該酸將造成晶種層之脫層，此意味著矽晶圓之導電晶種層(通常銀膏或無電鎳晶種層)將損失與矽晶圓表面之黏著且將容易剝離。氯離子將不利地影響太陽能電池晶圓之背側上之材料，例如藉由使鋁膏溶解至銅電鍍溶液中來影響鋁膏。由此，期望研發不產生該等不利效應之新銅電鍍溶液。
概言之，本發明技術係關於銅電鍍溶液及製備與使用該等溶液之方法。具體而言，本發明技術包括包含銅離子源及導電性鹽之銅電鍍溶液，其中銅電鍍溶液具有介於1.7與3.5間之pH，且基本上不含氯離子。本發明技術亦係關於使用該等銅電鍍溶液之方法。此技術可用於製造印刷電路板及太陽能矽晶圓。
將銅電鍍至基材上之本發明方法之實施例包含提供基材並使基
材與包含銅離子源及導電性鹽之銅電鍍溶液接觸，其中該銅電鍍溶液具有介於約1.7與約3.5間之pH，且基本上不含氯離子。
基材可為在矽太陽能電池晶圓上之金屬晶種層。銅離子源可為硫酸銅。導電性鹽可為硫酸鋰。pH可介於約2.3與約3.0間。添加劑選自咪唑及咪唑衍生物、噻唑及噻唑衍生物、含有四級氮原子之化合物(例如噻唑鎓化合物)及聚合四級化合物之群。例如，添加劑可為2巰基咪唑、2巰基噻唑、溴化3-(羧基甲基)苯并噻唑鎓、2巰基-1-甲基咪唑、2胺基噻唑或Cyastat SN。
本發明銅電鍍溶液之實施例包含銅離子源及導電性鹽，其中該銅電鍍溶液具有介於約1.7與約3.5間之pH，且基本上不含氯離子。
基材可為在矽太陽能電池晶圓上之金屬晶種層。銅離子源可為硫酸銅。導電性鹽可為硫酸鋰。pH可介於約2.3與約3.0間。添加劑選自咪唑及咪唑衍生物、噻唑及噻唑衍生物、含有四級氮原子之化合物(例如噻唑鎓化合物)及聚合四級化合物之群。例如，添加劑可為2巰基咪唑、2巰基噻唑、溴化3-(羧基甲基)苯并噻唑鎓、2巰基-1-甲基咪唑、2胺基噻唑或Cyastat SN。
概言之，本發明技術係關於銅電鍍溶液及製備與使用該等溶液之方法。具體而言，本發明技術包括包含銅離子源及導電性鹽之銅電鍍溶液，其中銅電鍍溶液具有介於1.7與3.5間之pH，且基本上不含氯離子。本發明技術亦係關於使用該等銅電鍍溶液之方法。此技術可用於製造印刷電路板及太陽能矽晶圓。本文中所揭示之實施例易於為闡釋性的，且應瞭解本發明不限於該等實施例，此乃因熟習此項技術者可在不背離本發明範疇之情況下進行修改。
在一實施例中，本發明銅電鍍溶液包含銅離子源及導電性鹽。在一實施例之，銅電鍍溶液具有介於1.7與3.5間之pH。在一實施例之，銅電鍍溶液基本上不含氯離子。
本發明銅電鍍溶液可用於許多應用。例如，本發明銅電鍍溶液可用於製造印刷電路板、太陽能細胞及IC基材。
銅離子源可為本技術領域內已知之將提供銅離子源。銅離子之可能來源之實例包括硫酸銅、乙酸銅、碳酸銅及氧化銅。較佳銅離子源係硫酸銅。銅離子源可以以下量10g/L至68g/L之銅離子添加。
導電性鹽可為本技術領域內已知之將增加溶液之導電性之導電性鹽。導電性鹽之可能來源之實例包括硫酸鋰、硫酸鈉、硫酸鉀、乙酸鈉及乙酸鉀。較佳導電性鹽係硫酸鋰。導電性鹽可以以下量1.0g/L直至高達該鹽在溶液中之飽和點添加，以使得達到該鹽之最大濃度且其他添加物將自溶液沈澱出。申請人已發現本發明電鍍溶液係藉由添加導電性鹽(尤其硫酸鋰)來增強。導電性鹽通常且硫酸鋰尤其增強電鍍分佈且高度可溶於電鍍溶液中。在無導電性鹽之情況下，電鍍分佈較差，此歸因於本發明電鍍溶液中缺乏強酸。
在其他實施例中，亦可添加將不會使銅電鍍溶液受損之可選組份。此一可選組份之實例係選自咪唑及咪唑衍生物、噻唑及噻唑衍生物、含有四級氮原子之化合物(例如噻唑鎓化合物)及聚合四級化合物之添加劑。該等添加劑之實例包括2巰基咪唑、2巰基噻唑、溴化3-(羧基甲基)苯并噻唑鎓、2巰基-1-甲基咪唑、2胺基噻唑、Cyastat SN、硫咪唑衍生物及染料(例如健那斯綠B(Janis green B))。已顯示該等添加劑增強沈積物亮度/平滑度/外觀，儘管事實上該浴均不含明亮酸銅電鍍通常需要之氯離子。
在其他實施例中，亦可添加將不會使銅電鍍溶液受損之可選組份。該等可選組份之實例係表面活性劑及聚合物(例如聚乙二醇、壬
基苯酚乙氧基化物、非離子型、陰離子型及陽離子型表面活性劑)及用於維持期望pH之緩衝液。
在一實施例中，本發明方法包括提供基材並使基材與包含銅離子及導電性鹽之銅電鍍溶液接觸。在一實施例中，銅電鍍溶液具有介於1.7與3.5間之pH。在一實施例中，銅電鍍溶液基本上不含氯離子。
在本申請案之一些實施例中，基材可為印刷電路板、太陽能電池或IC基材。若基材係太陽能電池，則其更具體而言可為在矽太陽能電池晶圓上之金屬晶種層。可能金屬晶種層之實例包括銀膏、無電鎳、電鍍鎳及鋁。如上文所論述，典型酸性銅電鍍溶液將藉由使晶種層損失與矽晶圓基材之黏著來負面地影響金屬晶種層。
本發明方法可用於太陽能電池或其他基材(例如電路板)之直接接觸電鍍，其中與所電鍍之表面進行直接電接觸。本發明方法亦可用於太陽能電池之光誘導電鍍，其中與太陽能電池之背側進行電接觸且將光照射至太陽能電池上以使得電鍍將發生至太陽能電池之前側上。
銅離子源可為本技術領域內已知之將提供銅離子源。銅離子之可能來源之實例包括硫酸銅、乙酸銅、碳酸銅及氧化銅。較佳銅離子源係硫酸銅。銅離子源可以以下量10g/L至68g/L之銅金屬添加。
導電性鹽可為本技術領域內已知之將增加溶液之導電性之導電性鹽。導電性鹽之可能來源之實例包括硫酸鋰、硫酸鈉、硫酸鉀、乙酸鈉及乙酸鉀。較佳導電性鹽係硫酸鋰。導電性鹽可以以下量1.0g/L直至高達該鹽在溶液中之飽和點添加，以使得達到該鹽之最大濃度且其他添加物將自溶液沈澱出。
在其他實施例中，亦可添加將不會使銅電鍍溶液受損之可選組份。此一可選組份之實例係選自咪唑及咪唑衍生物、噻唑及噻唑衍生物、含有四級氮原子之化合物(例如噻唑鎓化合物)及聚合四級化合物之添加劑。該等添加劑之實例包括2巰基咪唑、2巰基噻唑、溴化3-
(羧基甲基)苯并噻唑鎓、2巰基-1-甲基咪唑、2胺基噻唑、Cyastat SN、硫咪唑衍生物及染料(例如健那斯綠B)。
在其他實施例中，亦可添加將不會使銅電鍍溶液受損之可選組份。該等可選組份之實例係表面活性劑及聚合物(例如聚乙二醇、壬基苯酚乙氧基化物、非離子型、陰離子型及陽離子型表面活性劑)及用於維持期望pH之緩衝液。
本發明接觸步驟可發生在適於獲得明亮、平滑、均勻分佈之銅電鍍之pH下。例如，可在約1.7至約3.5、更佳約2.3至約3.0之pH下達成期望結果。
本發明接觸步驟可發生在適於獲得明亮、平滑、均勻分佈之銅電鍍之溫度下。例如，可在高達80℃之環境溫度下達成期望結果。
本發明接觸步驟可發生適於獲得明亮、平滑、均勻分佈之銅電鍍之持續時間。例如，可在1分鐘至20分鐘內達成期望結果。
亦可添加額外可選步驟。例如，步驟可包括沖洗、中和、乾燥、後續電鍍及烘焙。
熟習此項技術者應瞭解上文所闡述之條件可有所不同且經調整以達成期望金屬化。
在一非限制性實施例中，將效率為18%之太陽能電池在含有80g/L硫酸銅五水合物、100g/L硫酸鋰之溶液中電鍍，利用硫酸或氫氧化鈉將pH調整至2.3。在50 ASF下電鍍具有含鋁背側之含有銀膏之太陽能電池並持續2分鐘。在銀膏晶種層上獲得無光澤銅沈積物。在電鍍後太陽能電池之效率增加至19%，太陽能電池之鋁背襯仍未受電鍍溶液影響。銀膏晶種層與矽晶圓之黏著未受損。
在一非限制性實施例中，將效率為18%之太陽能電池在含有80
g/L硫酸銅五水合物、100g/L硫酸鋰、0.2g/L之硫咪唑化合物之溶液中電鍍，利用硫酸或氫氧化鈉將pH調整至2.3。在50 ASF下光誘導電鍍具有鋁背之含有銀膏之太陽能電池並持續2分鐘。在銀膏晶種層上獲得明亮銅沈積物。在電鍍後太陽能電池之效率增加至19.2%，太陽能電池之鋁背襯仍未受電鍍溶液影響。銀膏晶種層與矽晶圓之黏著未受損。
儘管已顯示並闡述特定元件、實施例及應用，但當然應瞭解，本發明不限於其，此乃因熟習此項技術者可在不背離本發明之範疇之情況下、尤其根據前述教示進行修改。
Claims (11)
- 一種將銅電鍍至基材上之方法，其包含：提供基材；及使該基材與包含銅離子源及硫酸鋰導電性鹽之銅電鍍溶液接觸，其中該銅電鍍溶液具有介於約1.7與約3.5間之pH，且基本上不含氯離子。
- 如請求項1之方法，其中該基材係在矽太陽能電池晶圓上之金屬晶種層。
- 如請求項1之方法，其中該銅離子源係硫酸銅。
- 如請求項1之方法，其中該pH係介於約2.3與約3.0之間。
- 如請求項1之方法，其進一步包含選自咪唑及咪唑衍生物、噻唑及噻唑衍生物、諸如噻唑鎓化合物之含有四級氮原子之化合物及聚合四級化合物之群之添加劑。
- 如請求項5之方法，其中該添加劑係選自2巰基咪唑、2巰基噻唑、溴化3-(羧基甲基)苯并噻唑鎓、2巰基-1-甲基咪唑、2胺基噻唑及硬脂醯胺丙基二甲基-2-羥基乙基硝酸銨之群。
- 一種銅電鍍溶液，其包含：銅離子源；及硫酸鋰導電性鹽，其中該銅電鍍溶液具有介於約1.7與約3.5間之pH，且基本上不含氯離子。
- 如請求項7之溶液，其中該銅離子源係硫酸銅。
- 如請求項7之溶液，其中該pH係介於約2.3與約3.0之間。
- 如請求項7之溶液，其進一步包含選自咪唑及咪唑衍生物、噻唑及噻唑衍生物、諸如噻唑鎓化合物之含有四級氮原子之化合物 及聚合四級化合物之群之添加劑。
- 如請求項10之溶液，其中該添加劑係選自2巰基咪唑、2巰基噻唑、溴化3-(羧基甲基)苯并噻唑鎓、2巰基-1-甲基咪唑、2胺基噻唑及硬脂醯胺丙基二甲基-2-羥基乙基硝酸銨之群。
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| US20130264214A1 (en) * | 2012-04-04 | 2013-10-10 | Rohm And Haas Electronic Materials Llc | Metal plating for ph sensitive applications |
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2014
- 2014-03-12 TW TW103108542A patent/TWI510680B/zh not_active IP Right Cessation
- 2014-03-14 US US14/211,670 patent/US20140299480A1/en not_active Abandoned
- 2014-03-14 ES ES14159998T patent/ES2731904T3/es active Active
- 2014-03-14 CN CN201410097867.3A patent/CN104047036B/zh not_active Expired - Fee Related
- 2014-03-14 EP EP14159998.5A patent/EP2778262B1/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201127999A (en) * | 2009-09-28 | 2011-08-16 | Basf Se | Copper electroplating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201504482A (zh) | 2015-02-01 |
| EP2778262A1 (en) | 2014-09-17 |
| EP2778262B1 (en) | 2019-05-08 |
| CN104047036A (zh) | 2014-09-17 |
| US20140299480A1 (en) | 2014-10-09 |
| CN104047036B (zh) | 2018-11-02 |
| ES2731904T3 (es) | 2019-11-19 |
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