CN102047438A - 用于11(ib)族-13(iiia)族-16(via)族元素的金属、二元、三元、四元或五元合金沉积的电镀添加剂 - Google Patents
用于11(ib)族-13(iiia)族-16(via)族元素的金属、二元、三元、四元或五元合金沉积的电镀添加剂 Download PDFInfo
- Publication number
- CN102047438A CN102047438A CN2009801194459A CN200980119445A CN102047438A CN 102047438 A CN102047438 A CN 102047438A CN 2009801194459 A CN2009801194459 A CN 2009801194459A CN 200980119445 A CN200980119445 A CN 200980119445A CN 102047438 A CN102047438 A CN 102047438A
- Authority
- CN
- China
- Prior art keywords
- plating
- copper
- family
- indium
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 239000000654 additive Substances 0.000 title claims abstract description 40
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 26
- 239000000956 alloy Substances 0.000 title claims abstract description 26
- 230000000996 additive effect Effects 0.000 title claims description 37
- 238000009713 electroplating Methods 0.000 title abstract description 20
- 230000008021 deposition Effects 0.000 title abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 239000010409 thin film Substances 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract 2
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract 2
- 238000007747 plating Methods 0.000 claims description 92
- 239000010949 copper Substances 0.000 claims description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 41
- 229910052802 copper Inorganic materials 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 33
- 229910052738 indium Inorganic materials 0.000 claims description 29
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 29
- 239000011669 selenium Substances 0.000 claims description 20
- 229910052711 selenium Inorganic materials 0.000 claims description 19
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 150000002540 isothiocyanates Chemical class 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- CHSWXGQEJAPIRC-UHFFFAOYSA-N [In].S(N)(O)(=O)=O Chemical compound [In].S(N)(O)(=O)=O CHSWXGQEJAPIRC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- HPAXFNMMMBLYJU-UHFFFAOYSA-N copper sulfamic acid Chemical compound [Cu].S(N)(O)(=O)=O HPAXFNMMMBLYJU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000005493 quinolyl group Chemical group 0.000 claims description 3
- YBBCLCIGCUBVIR-UHFFFAOYSA-L S(N)([O-])(=O)=O.CN[In+2].S(N)([O-])(=O)=O Chemical compound S(N)([O-])(=O)=O.CN[In+2].S(N)([O-])(=O)=O YBBCLCIGCUBVIR-UHFFFAOYSA-L 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 8
- 125000000732 arylene group Chemical group 0.000 abstract 2
- 125000005549 heteroarylene group Chemical group 0.000 abstract 2
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 239000002585 base Substances 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- -1 benzal Chemical class 0.000 description 16
- 239000012530 fluid Substances 0.000 description 15
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 13
- 239000005329 float glass Substances 0.000 description 13
- 229910052750 molybdenum Inorganic materials 0.000 description 13
- 239000011733 molybdenum Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 229910001370 Se alloy Inorganic materials 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910000846 In alloy Inorganic materials 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 229940044174 4-phenylenediamine Drugs 0.000 description 1
- GDRVFDDBLLKWRI-UHFFFAOYSA-N 4H-quinolizine Chemical compound C1=CC=CN2CC=CC=C21 GDRVFDDBLLKWRI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 0 C*(C*(C)NC(Nc(cc1)ccc1*#C)=S)NC(Nc1ccc(*)cc1)=S Chemical compound C*(C*(C)NC(Nc(cc1)ccc1*#C)=S)NC(Nc1ccc(*)cc1)=S 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 229910018666 Mn—K Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- YDOJKPAHXXTPON-UHFFFAOYSA-N [Cu].CNS(O)(=O)=O Chemical compound [Cu].CNS(O)(=O)=O YDOJKPAHXXTPON-UHFFFAOYSA-N 0.000 description 1
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000005584 chrysenylene group Chemical group 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RMNHNKPSBYTKPO-UHFFFAOYSA-L copper N-methylsulfamate Chemical class CNS(=O)(=O)[O-].[Cu+2].CNS(=O)(=O)[O-] RMNHNKPSBYTKPO-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019524 disodium tartrate Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- LJJQENSFXLXPIV-UHFFFAOYSA-N fluorenylidene Chemical group C1=CC=C2[C]C3=CC=CC=C3C2=C1 LJJQENSFXLXPIV-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- YBKGERLDRMINOV-UHFFFAOYSA-N oxathiine Chemical compound O1SC=CC=C1 YBKGERLDRMINOV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005327 perimidinyl group Chemical group N1C(=NC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- ZFBGNQYKWSPQDQ-UHFFFAOYSA-N piperazine;sodium Chemical compound [Na].C1CNCCN1 ZFBGNQYKWSPQDQ-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003214 pyranose derivatives Chemical class 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical group C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
-
- 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electrochemistry (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Photovoltaic Devices (AREA)
Abstract
本发明涉及用于11(IB)族金属/二元或三元11(IB)族-13(IIIA)族/三元、四元或五元11(IB)族-13(IIIA)族-16(VIA)族合金在薄膜太阳能电池用基材上沉积的电镀添加剂。该添加剂具有通式(A),其中X1和X2可以相同或不同,且选自亚芳基和亚杂芳基;FG1和FG2可以相同或不同,或者选自-S(O)2OH、-S(O)OH、-COOH、-P(O)2OH和伯胺、仲胺和叔胺基团及其盐和酯;R选自亚烷基、亚芳基或亚杂芳基,且n和m为1-5的整数。
Description
发明领域
本发明涉及用于IB族金属/二元或三元IB族-IIIA族/三元、四元或五元IB族-IIIA族-VIA族合金在薄膜太阳能电池用基材上沉积的电镀添加剂。此外,本发明还涉及这些添加剂的制备方法和它们在金属电镀组合物中的用途。
发明背景
人们越来越认识到太阳能光电转换必须尽快成为未来世界能源供应的一个主要来源。
光伏产业将成为生产以平方千米为参考面积单位的太阳能电池组件的主要行业。所有成熟技术,无论是基于硅还是薄膜(a-Si、μc-Si、CIGS或CdTe),均旨在实现这一目标。对于这一点,关键是开发低组件生产成本的大面积加工方法,同时维持或更好地提高转换效率。基于Cu(In,Ga,Al)(S,Se)2黄铜矿吸收层的结已经显示出高的转换效率以及与以工业化之前水平进行高效组件的大面积生产的相容性(D.Lincot等,Solar Energy 77(2004)725-737)。
根据WO 00/62347,太阳能电池具有排列在柔性和带状支撑体上的吸收层。该吸收层至少部分具有铜成分,并具有选自铟和镓的至少一种元素和选自硒和硫的至少一种元素,且至少部分表现为p型。该吸收层至少部分以电镀方式沉积在支撑体上。该吸收层的成分彼此以化学计量比的关系存在。沉积在支撑体上之后,将该吸收层进行热处理。
美国专利7,026,258 B2涉及一种制造薄膜CIGS的方法,其包括:在基材上电化学沉积化学计量接近CuInSe2的层;然后将所述层从具有足够功率脉冲的光源快速退火以使CIS重结晶。电沉积元素被预混合。因此,沉积步骤后,形成均匀基质,它可以支持快速退火过程中温度的突然升高。
所有这些方法涉及IB-IIIA-VIA族金属合金的制备,尤其是包含铜、铟和硒的合金的制备。
通过电化学方法镀金属薄层是现如今公知且经常使用的技术,尤其是用于沉积铜。这种金属的无电沉积以及电沉积已经被开发用于装饰行业、防腐蚀和用于电子行业,并已达到成熟阶段。
然而,沉积上述元素所用的现有技术方法存在沉积的铜与铟的比例在整个基材表面上不恒定的缺陷。尤其是,Cu-In原子比变化得太大,以致于不能在例如10×10cm2大的基材上制造工作的太阳能电池组件。
发明目的
因此,本发明的一个目的是提供金属电镀组合物,其可用于均匀沉积IB族金属/二元或三元IB族-IIIA族/三元、四元或五元IB族-IIIA族-VIA族合金,其中IB族金属/IIIA族金属原子比仅以小标准偏差变化。尤其是,金属电镀组合物的使用应避免由流体动力学、电镀配置的电势和电流密度条件导致的上述金属比例和总平方质量分布(overall square mass distribution)的不均匀性。
发明概述
通过将一种新的添加剂加入金属电镀组合物来实现这些目的,其中添加剂具有以下通式(A):
式(A)
其中X1和X2可以相同或不同,且选自亚芳基和亚杂芳基;
FG1和FG2可以相同或不同,且选自-S(O)2OH、-S(O)OH、-COOH、-P(O)2OH和伯胺、仲胺和叔胺基团及其盐和酯;
R选自亚烷基、亚芳基或亚杂芳基;且
n和m为1-5的整数。
附图简述
图1显示了实施例2(不是根据本发明)描述的从现有技术电解液得到的金属镀层的Cu/In原子比的XRF表面扫描和图。
Cu/In原子比以接近16%的标准偏差变化。在15×15cm2的镀钼浮法玻璃材料上进行沉积(居中画出测量面积10×10cm2)。Cu/In原子比的变化太大,以致于不能在15×15cm2的基材尺寸上生产工作的太阳能电池。
图2显示了实施例2(不是根据本发明)得到的总层厚的XRF表面扫描和图。
合金沉积的总层厚以超过8%的标准偏差变化。由流体动力学、电势和电流密度下降所造成的不均匀性清晰可见。在15×15cm2的镀钼浮法玻璃材料上进行沉积(居中画出测量面积10×10cm2)。
图3显示了根据本发明的实施例1得到的总层厚的XRF表面扫描和图。
总层厚以小于7%的标准偏差变化。在15×15cm2的镀钼浮法玻璃材料上进行沉积(居中画出测量面积10×10cm2)。只有由流体动力学造成的轻微不均匀性是可见的。
图4显示了本发明的实施例1得到的Cu/In原子比的XRF表面扫描和图。
Cu/In原子比以小于3%的标准偏差变化。这种原子比的变化对于太阳能电池的工业化生产是适宜的。在15×15cm2的镀钼浮法玻璃材料上进行沉积(居中画出测量面积10×10cm2)。
图5显示了Mo旋转圆盘电极(RDE)(虚线/方块——现有技术电解液:依赖于来自流体动力学的化学计量[Cu/In比];实线/三角形——根据本发明的电解液:独立于来自流体动力学的化学计量[Cu/In比];电势-1.1V vs.Ag/AgCl;化学计量[Cu/In比]可在灰色区域内通过适当调整溶液pH值来改变)在Levich坐标(R.G.Compton,C.E.Banks,Understanding Voltammetry;World Scientific Publishing Co.Pte.Ltd(2007))中的图。图5中,ω表示旋转阳极的旋转频率,它是电镀槽中流体动力学条件的度量。根据Levich方程,ω的平方根与RDE的电流密度直接相关,RDE是根据法拉第定律对沉积物质的度量。
图6a显示了与外加总电流密度有关的局部电化学势对镀钼浮法玻璃上距电接触的距离的依赖性。
图6b显示了与外加总电流密度有关的局部电流密度对镀钼浮法玻璃上距电接触的距离的依赖性。
图7a和7b显示了根据本发明(实施例1)的电沉积CISe前躯体的化学计量(Cu/In比)与镀钼浮法玻璃上a)施加的电势和b)施加的电流密度以及电解液特性的关系。两条曲线的水平部分显示了使用本发明添加剂可得到均匀合金组合物的范围。
发明详述
在本发明的电镀组合物中使用通式(A)的添加剂,使合金组成的调整变得很容易,原因在于所述添加剂显著影响合金组成。该添加剂可优选用于合金电镀组合物中,也可有利地用于制备单分子层的那些电镀组合物中,所述单分子层一起形成夹层。
该添加剂优选自如下:
式I
式II
式III
其中Ar1、Ar2、Het1、Het2、R、m和n与本文前面的定义相同。
本文所用的术语“亚芳基”是指单-或多芳环二价基团,如亚苯基、亚苄基、亚萘基、亚蒽基、亚金刚烷基、亚菲基(phenantracylene)、亚荧蒽基、亚基(chrysenylene)、亚芘基、亚联苯基(biphenylylene),亚苉基(picenylene)等,包括稠合的苯并碳C5-8亚环烷基,例如亚2,3-二氢化茚基、亚1,2,3,4-四氢萘基、亚芴基等。
优选地,Ar1和Ar2表示亚苯基或亚萘基。
本文所用的术语“杂芳基”是指包含一个或多个各自独立地选自氮、氧、硫和磷的杂原子的单-或多杂芳环二价基团,例如亚吡啶基、亚吡嗪基、亚嘧啶基、亚哒嗪基,亚三嗪基、亚三唑基、亚咪唑基、亚吡唑基、亚噻唑基、亚异噻唑基、亚唑基、亚吡咯基、亚呋喃基、亚噻吩基、亚吲哚基、亚吲唑基、亚苯并呋喃基、亚苯并噻吩基、亚喹啉基、亚喹唑啉基、亚喹喔啉基、亚咔唑基、亚吩嗪基、亚吩噻嗪基、亚呫吨基、亚嘌啉基、亚苯并噻吩基、亚萘并噻吩基、亚噻蒽基、亚吡喃基、亚异苯并呋喃基、亚苯并吡喃基、亚吩氧硫杂环己二烯基(phenoxathiinylene)、亚中氮茚基、亚喹嗪基、亚异喹啉基、亚酞嗪基、亚萘啶基(naphthiridinylene)、亚邻二氮杂萘基、亚蝶啶基、亚咔啉基、亚吖啶基、亚萘嵌间二氮杂苯基、亚菲咯啉基(phenanthrolinylene)、亚吩嗪基、亚吩噻嗪基、亚咪唑啉基、亚咪唑烷基,亚吡唑啉基,亚吡唑烷基、亚吡咯啉基、亚吡咯烷基等,其中包括所有可能的异构体形式。
优选地,Het1和Het2选自含氮的单-和多杂环,包括亚吡啶基和亚喹啉基。
基团FG1和FG2为Ar1、Ar2、Het1和Het2基团的取代基,且选自-S(O)2OH、-S(O)OH、-COOH、-P(O)2OH和伯胺、仲胺和叔胺基团及其盐和酯。
所述盐包括碱金属盐和碱土金属盐,如钠盐、钾盐和钙盐。
合适的酯为烷基酯,尤其是C1-6烷基酯,其中C1-6烷基是指具有1-6个碳原子的直链和支链饱和烃单价基团,如甲基、乙基、丙基、正丁基、1-甲基乙基、2-甲基丙基、1,1-二甲基乙基、2-甲基丁基、正戊基、二甲基丙基、正己基、2-甲基戊基、3-甲基戊基等。
合适的铵盐包括铵(NH4 +)和四正烷基铵,如四正丁基铵盐或四正甲基铵盐。
R表示如上所述定义的亚芳基或亚杂芳基。此外,R可以选自线性或支化亚烷基。该亚烷基具有1-20个碳原子,包括衍生自上述C1-6烷基的亚烷基。术语“C1-20亚烷基”也包括具有7-20个碳原子的其高级同系物,例如亚庚基、乙基亚己基、亚辛基、亚壬基、亚癸基、亚十二烷基、亚十八烷基等。
本发明特别优选的添加剂如下所示:
其中n’为2-12,优选2-8。
一个特别优选的添加剂为:
式IV
根据本发明的通式(A)的添加剂可通过包括如下步骤的方法制备:
使如下异硫氰酸酯:
其中X1、X2、FG1、FG2、m和n如本文前面所定义,与式H2N-R-NH2的二胺化合物反应,其中R如本文前面所定义,
或者使如下胺化合物:
其中Ar1、Ar2、FG1、FG2、m和n如本文前面所定义,与式SCN-R-NCS的二异氰酸酯化合物反应,其中R如本文前面所定义。
同样,根据本发明包含在电镀槽中的通式I-III的添加剂可通过相应的异硫氰酸酯与二胺反应得到,或者通过二异硫氰酸酯与相应的胺反应得到。该反应可由下述示例的反应示意图表示:
该制备方法可在室温或更高温度下,在水、醇或氯卤化介质中进行。
根据本发明的一个实施方案,金属电镀组合物包含IB族镀种和IIIA族镀种和任选的VIA族镀种。
IB族镀种优选包括铜,IIIA族镀种包括镓和铟,VIA族镀种包括硒和硫。
根据本发明的另一个实施方案,金属电镀组合物包含铜作为IB族镀种,镓和/或铟作为IIIA族镀种,和硒和/或硫作为VIA族镀种。
优选地,铜、铟和硒镀种以铜∶铟∶硒摩尔比=1∶0.1-50∶0.01-40,最优选1∶1-5∶0.05-2包含于组合物中。
根据本发明,如下镀种为特别优选的用于金属电镀组合物的镀种:
(i)铜镀种,
(ii)铜和铟镀种,
(iii)铜、铟和镓镀种,
(iv)铜、铟和硒镀种,
(v)铜、铟和硫镀种,
(vi)铜、铟、镓和硒镀种,
(vii)铜、铟、镓和硫镀种,和
(viii)铜、铟、镓、硒和硫镀种。
总的来说,根据本发明的金属电镀组合物包含IB族镀种,尤其是铜,用量为0.5-200毫摩尔/升,优选为1-100毫摩尔/升,最优选3-20毫摩尔/升(不论单独使用,还是与IIIA族镀种和任选的VIA族镀种组合使用)。
IIIA族和VIA族镀种合适的用量可通过前面以举例方式针对镀种铜、铟和硒给出的摩尔比计算。
优选地,铜镀种是硫酸铜,氨基磺酸铜或甲基氨基磺酸铜(copper methanesulfamates),铟镀种是氨基磺酸铟或甲基氨基磺酸铟。在本发明进一步优选的实施方案中,硒镀种包括亚硒酸。
根据本发明的金属电镀组合物优选包含一种或多种络合剂,包括但不限于柠檬酸盐和酒石酸盐络合剂。
所含络合剂用量为0.001-2摩尔/升、优选0.005-1摩尔/升,最优选0.02-0.5摩尔/升。
优选该组合物进一步包含缓冲体系。
所含缓冲体系用量是使该组合物的pH值优选为约1-6、更优选约1.8-5、最优选约2.5-4的量。
甚至更优选该组合物进一步包含至少一种润湿剂。
为了沉积所需合金如铜-铟-硒合金,基材优选与金属电镀组合物在约15-80℃、优选约20-35℃的温度下接触,以形成这种合金。
为了制备根据本发明的镀层,接收这些镀层的基材表面在金属化之前通常将经过预清洗工艺。电镀之前,可以将基材用申请人开发的湿化学工艺或任何其他清洁化学品进行处理,以从表面除去任何油脂、污垢、灰尘或氧化物。一个标准预清洗工艺如表1所述。
表1:标准预清洗工艺
*)Atotech Deutschland GmbH,DE的商标
将基材清洗后,可将所需合金如铜-铟-硒合金沉积在基材上。
优选工作条件如下:
温度:20-35℃
pH值:2.5-3.8
电流密度:0.3-2A/dm2
流体动力学/电解液流量:0-10m3/h
沉积速率:1-20min
沉积层厚度:0.2-3μm
可通过直流电镀或以两个阴极电势(恒电势区)的脉冲电镀进行沉积。通常,如下电势可用于脉冲电镀:-0.5至-2V(所测电势vs.Ag/AgCl电极),脉冲时间从几十分之一毫秒至几秒钟。作为阳极,可使用惰性阳极如Uniplate型惰性阳极。
添加剂浓度为1-500ppm,优选5-100ppm,最优选10-50ppm。
在根据本发明的金属电镀组合物中使用这种添加剂能够制备其中IB族金属/IIIA族金属原子比仅以小标准偏差变化的镀层基材。因此,通过XRF表面图得到的IB族金属与IIIA族金属比例以小于4%,优选小于2%的标准偏差变化。
通过下述实施例进一步描述本发明:
本发明添加剂的一般合成程序1
将0.2mol的异硫氰酸酯、0.1mol的二胺和300mL甲醇加入反应烧瓶中,允许反应在65℃进行24小时直至反应完成。然后将反应液冷却至0℃,将产生的固体过滤,并用甲醇洗涤。
将残留物从甲醇中重结晶,得到白色固体。
编号 | 异硫氰酸酯 | 二胺 | 产率 |
1 | 4-异硫氰酸基-苯基-磺酸钠盐 | 1,6-己二胺 | 74.2% |
2 | 4-异硫氰酸基-苯基-磺酸钠盐 | 1,4-丁二胺 | 58.17% |
3 | 4-异硫氰酸基-苯基-磺酸钠盐 | 1,8-辛二胺 | 58.8% |
4 | 4-异硫氰酸基-苯基-磺酸钠盐 | 乙二胺 | 89.8% |
5 | 4-异硫氰酸基-苯基-磺酸钠盐 | N,N-二甲基-1,6-己二胺 | 73.5% |
6 | 4-异硫氰酸基-苯基-磺酸钠盐 | 哌嗪 | 82.8% |
7 | 4-异硫氰酸基-苯基-磺酸钠盐 | 1,4-苯二胺 | 81.1% |
8 | 6-异硫氰酸基-萘基-2-磺酸钠盐 | 1,6-己二胺 | 69.35% |
9 | 3-异硫氰酸基-吡啶 | 乙二胺 | 45.3% |
本发明添加剂的一般合成程序2
将0.2mol的胺、0.1mol的二异硫氰酸酯和300mL甲醇加入反应烧瓶中,允许反应在65℃进行24小时直至反应完成。然后将反应液冷却至0℃,将产生的固体过滤,并用甲醇洗涤。
将残留物从甲醇中重结晶,得到白色固体。
编号 | 二异硫氰酸酯 | 胺 | 产率 |
1 | 2,6-二异硫氰酸基-吡啶 | 对氨基苯磺酸钠盐 | 49.6% |
2 | 1,6-二异硫氰酸基-己烷 | 对氨基苯磺酸钠盐 | 35.2% |
3 | 1,2-二异硫氰酸基-乙烷 | 对氨基苯磺酸钠盐 | 52.8% |
实施例1
将15×15cm2镀钼浮法玻璃材料使用表1所列的处理方式进行预清洗。
然后,制备金属电镀液,其组成如下:
1M氨基磺酸
1M氢氧化钠
0.3M酒石酸二钠
1mM二氧化硒(IV)
20mM氨基磺酸铟
9mM氨基磺酸铜
40mg/L式IV的添加剂
20μl/l Lutensit TC-CS40(表面活性剂)
将上述基材浸入该金属电镀液中,采用如下工作条件将Cu/In/Se合金电沉积在基材上:
温度:25℃
pH值:~3.2
DC电流:电流密度为1.3A/dm2
高流体动力学/电解液流量达到10m3/h,孔喷嘴阵列——要求的高沉积速率为1.5μm太阳能电池吸收层需~3分钟
惰性阳极(Uniplate型惰性阳极)
实施例2(不是根据本发明)
将15×15cm2镀钼浮法玻璃材料以上述实施例1相同的方式进行预清洗。
然后,制备金属电镀液,其组成如下:
1M氨基磺酸
1M氢氧化钠
16mM柠檬酸三钠
12mM二氧化硒(IV)
50mM氨基磺酸铟
3mM氨基磺酸铜
20μl/l Lutensit TC-CS40(表面活性剂)
将上述基材浸入该金属电镀液中,采用如下工作条件将Cu/In/Se合金沉积在基材上:
温度:25℃
pH值:~2.3
用两个阴极电势(恒电势区)的脉冲电镀:-0.75V、0.9秒/-1.1V、0.1秒(所测电势vs.Ag/AgCl电极)
流体动力学/电解液流量达到600L/h,孔喷嘴阵列
速率为1.5μm太阳能电池吸收层需~15分钟
惰性阳极(Uniplate型惰性阳极)
实施例3
将15×15cm2镀钼浮法玻璃材料以上述实施例1相同的方式进行预清洗。
然后,制备金属电镀液,其组成如下:
1M甲基磺酸
1M氢氧化钠
13.6mM柠檬酸三钠
6mM二氧化硒(IV)
50mM氢氧化铟
50mM氢氧化镓(或为硫酸盐或氯化物)
3mM氧化铜
40mg/l式IV的添加剂
20μl/l CUD 50(表面活性剂)
将上述基材浸入该金属电镀液中,采用如下工作条件将Cu/In/Se合金沉积在基材上:
温度:25℃
pH值:~1.5
用两个阴极电势(恒电势区)的脉冲电镀:-0.75V、0.9秒/-1.1V、0.1秒(所测电势vs.Ag/AgCl电极)
流体动力学/电解液流量达到600L/h,孔喷嘴阵列
速率为1.5μm太阳能电池吸收层需~15分钟
惰性阳极(Uniplate型惰性阳极)
结果与评价
对实施例1-2得到的合金进行XRF表面扫描。
XRF(X射线荧光)分析是一种非破坏性方法。所用设备(来自Thermo-Fisher-Scientific,USA的MicroXR 1200SV)具有30×30cm2的x-y表。它装配有钨管,加速电压为47keV,装配有多毛细管硅漂移探测器(SDD)的分辨率为163.3eV(Mn-Kα的FWHM),并用Peltier热电致冷器冷却。将样品暴露于空气中,但由于特殊几何构造、抽真空的射束管和检察管,有可能测量元素下限至铝。
分析沉积在400nm镀钼浮法玻璃上的薄合金膜(1-2μm)是一项复杂任务。以纯元素标样进行校正是不够的。自制二元、三元、四元或五元标样是必要的。通过ICP-OES/ICP-MS对他们进行交叉分析。
结果,Cu/In原子比和总平方质量分布可在整个基材表面上进行测定,实施例1和2所得合金相应的图如图1和4所示。图1显示了实施例2所得合金的Cu/In原子比,其中金属电镀槽中不含本发明添加剂。从图1看出,Cu/In原子比以接近16%的标准偏差变化。Cu/In原子比的这种变化太大,以致于不能在10×10cm2的基材尺寸上生产工作的太阳能电池(居中切除15×15cm2基材——避免因电接触时直接产生的不均匀性的影响)。
图4显示了根据本发明的实施例1所得合金的XRF表面扫描测得的Cu/In原子比的相应图。从图4看出,Cu/In原子比以小于3%的标准偏差变化。
这种Cu/In原子比的变化对于在10×10cm2的基材尺寸上生产工作的太阳能电池组件是可接受的。
基于XRF表面扫描,对实施例1和2所得合金的总平方质量(以mg/cm2)作图,如图2(对于实施例2)和图3(对于实施例1)所示。
从图2看出,实施例2所得合金的总层厚(其中不含本发明添加剂)以超过8%的标准偏差变化。
另一方面,实施例1(根据本发明)所得合金的总层厚以小于7%的标准偏差变化。流体动力学条件和Mo基材内电势下降造成的不均匀性远远小于实施例2的合金。
图5显示了使用根据实施例1和2的金属电镀槽所得合金的Cu/In原子比随所用旋转圆盘电极的旋转频率的变化。尤其是,旋转频率(ω)的平方根是电镀槽中流体动力学条件的度量。图5表明,当使用的电镀槽包含本发明添加剂时(实施例1),Cu/In比不依赖于流体动力学条件。另一方面,如果不存在这种添加剂(如实施例2中),Cu/In比依赖于旋转频率,因而依赖于电镀槽中的流体动力学条件。
图5还表明,通过改变电镀槽的pH值,可以调节实施例1(包含本发明添加剂)所得的Cu/In比。较低的pH值对应于较低的Cu/In比,较高的pH值对应于较高的Cu/In比。
图6a和6b显示了a)局部电化学势和b)局部电流密度随外加总电流密度的变化。这些值直接在镀钼浮法玻璃基材上距电接触不同距离处测量。图6a和6b所示曲线解释了当现有技术电镀槽用于沉积Cu-In-Se合金时,为什么Cu/In比随着距电接触的距离的增加而大大增加(参见图1和3)。与Cu相比,由于较低的电势,较少量的In(其不如Cu贵)被沉积。本发明添加剂能够补偿这种效应(参见图3和4),并平衡流体动力学条件中的不规则性(参见图5)。
图6a和6b所示曲线对于本申请所用基材是典型的。相应地,对于工业规模所用基材尺寸,将发生同样效果。
最后,图7a和7b显示了根据本发明(实施例1)的电沉积CISe前躯体的化学计量(铜Cu/In比)独立于镀钼浮法玻璃上a)施加的电势和b)施加的电流密度以及电解液特性。两条曲线的水平部分显示了使用本发明添加剂可得到恒定合金组分的操作范围。
实施例4
根据式IV的本发明添加剂用于以如下组成在低酸性铜浴中沉积铜:
35g/l硫酸
35g/l五水硫酸铜
100ppm氯化物
100ppm丙二醇
20mg/l式IV的添加剂
将黄铜基材在总电流1.5A的薄膜电池中镀铜。沉积时间是300秒。
使用式IV的添加剂得到了均匀且明亮的铜沉积层。
Claims (18)
3.根据权利要求2所述的添加剂,其中Ar1和Ar2表示亚苯基或亚萘基。
4.根据权利要求1所述的添加剂,其中Het1和Het2表示亚吡啶基或亚喹啉基。
7.一种金属电镀组合物,包含权利要求1-6任一项所述的添加剂和IB族镀种。
8.根据权利要求7所述的金属电镀组合物,进一步包含IIIA族镀种。
9.根据权利要求8所述的金属电镀组合物,进一步包含VIA族镀种。
10.根据权利要求7-9任一项所述的金属电镀组合物,其中IB族镀种包括铜,其中IIIA族镀种包括镓和/或铟,其中VIA族镀种包括硒和/或硫。
11.根据权利要求10所述的金属电镀组合物,包含选自如下的镀种:
(i)铜镀种,
(ii)铜和铟镀种,
(iii)铜、铟和镓镀种,
(iv)铜、铟和硒镀种,
(v)铜、铟和硫镀种,
(vi)铜、铟、镓和硒镀种,
(vii)铜、铟、镓和硫镀种,和
(viii)铜、铟、镓、硒和硫镀种。
12.根据权利要求11所述的金属电镀组合物,其中铜和铟镀种以铜∶铟摩尔比为1∶0.1-50包含于组合物中,其中铜和硒镀种以铜∶硒摩尔比为1∶0.01-40包含于组合物中。
13.根据权利要求12所述的金属电镀组合物,其中铜和铟镀种以铜∶铟摩尔比为1∶1-5包含于组合物中,其中铜和硒镀种以铜∶硒摩尔比为1∶0.05-2包含于组合物中。
14.根据权利要求10或11所述的金属电镀组合物,其中铜镀种选自硫酸铜、氨基磺酸铜和甲基磺酸铜,其中铟镀种选自氨基磺酸铟和甲基氨基磺酸铟。
15.一种用IB族金属/二元或三元IB族-IIIA族/三元、四元或五元IB族-IIIA族-VIA族合金镀覆基材的方法,包括如下步骤:
(i)预清洗待镀覆的基材;和
(ii)使预清洗的基材与权利要求7-20任一项所述的金属电镀组合物在约15-80℃的温度下接触以得到镀有IB族金属/二元或三元IB族-IIIA族/三元、四元或五元IB族-IIIA族-VIA族合金的基材。
16.一种根据权利要求15所述方法得到的镀层基材。
17.根据权利要求16所述的镀层基材,其中通过XRF表面图获得的IB族金属与IIIA族金属的比例以小于4%的标准偏差变化。
18.一种包含权利要求16或17所述基材的薄膜太阳能电池。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08009979.9A EP2128903B1 (en) | 2008-05-30 | 2008-05-30 | Electroplating additive for the deposition of a metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (IB)-group 13 (IIIA)-group 16 (VIA) |
EP08009979.9 | 2008-05-30 | ||
PCT/EP2009/003885 WO2009144036A1 (en) | 2008-05-30 | 2009-05-29 | Electroplating additive for the deposition of metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (ib)-group 13 (iiia) -group 16 (via) |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102047438A true CN102047438A (zh) | 2011-05-04 |
CN102047438B CN102047438B (zh) | 2013-10-09 |
Family
ID=39869699
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2009801194459A Expired - Fee Related CN102047438B (zh) | 2008-05-30 | 2009-05-29 | 用于11(ib)族-13(iiia)族-16(via)族元素的金属、二元、三元、四元或五元合金沉积的电镀添加剂 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8828278B2 (zh) |
EP (1) | EP2128903B1 (zh) |
JP (1) | JP5286410B2 (zh) |
CN (1) | CN102047438B (zh) |
ES (1) | ES2624637T3 (zh) |
WO (1) | WO2009144036A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103924268A (zh) * | 2013-12-26 | 2014-07-16 | 苏州昕皓新材料科技有限公司 | 一种酸铜整平剂的应用 |
CN103924269A (zh) * | 2013-12-26 | 2014-07-16 | 苏州昕皓新材料科技有限公司 | 一种非染料系整平剂的应用 |
CN105696035A (zh) * | 2016-04-18 | 2016-06-22 | 程敏敏 | 一种高性能填孔镀铜溶液 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110108115A1 (en) * | 2009-11-11 | 2011-05-12 | International Business Machines Corporation | Forming a Photovoltaic Device |
US8304272B2 (en) | 2010-07-02 | 2012-11-06 | International Business Machines Corporation | Germanium photodetector |
US20120055612A1 (en) * | 2010-09-02 | 2012-03-08 | International Business Machines Corporation | Electrodeposition methods of gallium and gallium alloy films and related photovoltaic structures |
US8545689B2 (en) * | 2010-09-02 | 2013-10-01 | International Business Machines Corporation | Gallium electrodeposition processes and chemistries |
US8840770B2 (en) * | 2010-09-09 | 2014-09-23 | International Business Machines Corporation | Method and chemistry for selenium electrodeposition |
JP5552042B2 (ja) | 2010-12-27 | 2014-07-16 | インターナショナル・ビジネス・マシーンズ・コーポレーション | プログラム解析の方法、システムおよびプログラム |
US20130327652A1 (en) * | 2012-06-07 | 2013-12-12 | International Business Machines Corporation | Plating baths and methods for electroplating selenium and selenium alloys |
US9495989B2 (en) | 2013-02-06 | 2016-11-15 | International Business Machines Corporation | Laminating magnetic cores for on-chip magnetic devices |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL217034A (zh) * | 1956-06-15 | |||
NL134137C (zh) * | 1961-02-02 | |||
NL281922A (zh) * | 1961-08-10 | |||
DE2334355A1 (de) * | 1973-07-06 | 1975-01-16 | Hoechst Ag | Diphenylharnstoffderivate und ihre herstellung |
JPS5865439A (ja) * | 1981-10-15 | 1983-04-19 | Fuji Photo Film Co Ltd | 光導電性組成物およびそれを用いた電子写真感光材料 |
US6875864B2 (en) * | 1991-08-01 | 2005-04-05 | Bracco International B.V. | Aminocarboxylate ligands having substituted aromatic amide moieties |
WO1993002652A2 (en) * | 1991-08-01 | 1993-02-18 | Hybritech Incorporated | Modified haptens useful as imaging and therapeutic agents |
US5326856A (en) * | 1992-04-09 | 1994-07-05 | Cytogen Corporation | Bifunctional isothiocyanate derived thiocarbonyls as ligands for metal binding |
US5955053A (en) * | 1996-05-06 | 1999-09-21 | Emory University | Metal chelates as pharmaceutical imaging agents, processes of making such and uses thereof |
DE19917758C2 (de) | 1999-04-10 | 2003-08-28 | Cis Solartechnik Gmbh | Verfahren zur Herstellung einer CuInSe2(CIS)Solarzelle |
JP2001073182A (ja) * | 1999-07-15 | 2001-03-21 | Boc Group Inc:The | 改良された酸性銅電気メッキ用溶液 |
FR2839201B1 (fr) | 2002-04-29 | 2005-04-01 | Electricite De France | Procede de fabrication de semi-conducteurs en couches minces a base de composes i-iii-vi2, pour applications photovoltaiques |
US7507321B2 (en) * | 2006-01-06 | 2009-03-24 | Solopower, Inc. | Efficient gallium thin film electroplating methods and chemistries |
US20090188808A1 (en) * | 2008-01-29 | 2009-07-30 | Jiaxiong Wang | Indium electroplating baths for thin layer deposition |
-
2008
- 2008-05-30 ES ES08009979.9T patent/ES2624637T3/es active Active
- 2008-05-30 EP EP08009979.9A patent/EP2128903B1/en not_active Not-in-force
-
2009
- 2009-05-29 JP JP2011510899A patent/JP5286410B2/ja not_active Expired - Fee Related
- 2009-05-29 US US12/995,078 patent/US8828278B2/en not_active Expired - Fee Related
- 2009-05-29 CN CN2009801194459A patent/CN102047438B/zh not_active Expired - Fee Related
- 2009-05-29 WO PCT/EP2009/003885 patent/WO2009144036A1/en active Application Filing
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103924268A (zh) * | 2013-12-26 | 2014-07-16 | 苏州昕皓新材料科技有限公司 | 一种酸铜整平剂的应用 |
CN103924269A (zh) * | 2013-12-26 | 2014-07-16 | 苏州昕皓新材料科技有限公司 | 一种非染料系整平剂的应用 |
CN103924269B (zh) * | 2013-12-26 | 2016-04-13 | 苏州昕皓新材料科技有限公司 | 一种非染料系整平剂的应用 |
CN103924268B (zh) * | 2013-12-26 | 2016-04-13 | 苏州昕皓新材料科技有限公司 | 一种酸铜整平剂的应用 |
CN105696035A (zh) * | 2016-04-18 | 2016-06-22 | 程敏敏 | 一种高性能填孔镀铜溶液 |
Also Published As
Publication number | Publication date |
---|---|
EP2128903B1 (en) | 2017-02-22 |
JP2011524945A (ja) | 2011-09-08 |
US8828278B2 (en) | 2014-09-09 |
CN102047438B (zh) | 2013-10-09 |
EP2128903A1 (en) | 2009-12-02 |
WO2009144036A1 (en) | 2009-12-03 |
JP5286410B2 (ja) | 2013-09-11 |
US20110094583A1 (en) | 2011-04-28 |
ES2624637T3 (es) | 2017-07-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102047438B (zh) | 用于11(ib)族-13(iiia)族-16(via)族元素的金属、二元、三元、四元或五元合金沉积的电镀添加剂 | |
US9263609B2 (en) | Metal plating composition and method for the deposition of copper—zinc—tin suitable for manufacturing thin film solar cell | |
Sarswat et al. | CZTS thin films on transparent conducting electrodes by electrochemical technique | |
CN103959483B (zh) | 用于制备薄膜型太阳能电池的组合式连续电沉积设备 | |
CN1922343B (zh) | 用于电镀锌-镍三元的和更高的合金的电镀液,系统和方法及其电镀产品 | |
US20070272558A1 (en) | Efficient Gallium Thin Film Electroplating Methods and Chemistries | |
Ueno et al. | Electrodeposition of CuInSe2 films from a sulphate bath | |
CN107723712A (zh) | 用于光生阴极保护的ZnIn2S4/TiO2纳米管复合膜光阳极的制备方法 | |
Aksu et al. | Recent advances in electroplating based CIGS solar cell fabrication | |
Valdes et al. | Electrodeposited Cu2ZnSnS4 thin films | |
CN102021613A (zh) | 电解质组合物 | |
Mandati et al. | Two-dimensional CuIn1− xGaxSe2 nano-flakes by pulse electrodeposition for photovoltaic applications | |
US20090188808A1 (en) | Indium electroplating baths for thin layer deposition | |
CN103779438B (zh) | 一种电化学沉积制备铜铟镓硒预制层的方法 | |
CN103540975B (zh) | 一种在铜表面电镀金属锰的方法 | |
US20110132462A1 (en) | Modified copper-zinc-tin semiconductor films, uses thereof and related methods | |
Oda et al. | Electrodeposition of crack-free CuGaSe2 thin films from single bath | |
Chandran et al. | Composition Tuning of Single Step Electrodeposited CuInSe2 Thin Films Using Sodium Dodecyl Sulfate as Additive | |
Lee et al. | Electrochemical behavior of CIGS electrodeposition for applications to photovoltaic cells | |
TWI488312B (zh) | Structure and Process of Thin - film Solar Cell Buffer Layer | |
Chandran et al. | An attempt to co-deposit photovoltaic quality CuInSe 2 thin films: effect of surfactant and deposition potential | |
Chandran et al. | An attempt to co‑deposit photovoltaic quality CuInSe | |
Farooq | STUDY OF ELECTRODEPOSITION OF COPPER-INDIUM MATERIAL FOR FABRICATION OF CIS THIN-FILM SOLAR CELLS | |
Marsen et al. | Copper gallium diselenide photocathodes for solar photoelectrolysis | |
Arai et al. | Galvanic contact deposition of CdTe from ammoniacal basic electrolytes at elevated temperatures using an autoclave-type electrolysis vessel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131009 Termination date: 20180529 |
|
CF01 | Termination of patent right due to non-payment of annual fee |