KR20170009385A - Natural source based cleaning agent composition for solar wafer - Google Patents
Natural source based cleaning agent composition for solar wafer Download PDFInfo
- Publication number
- KR20170009385A KR20170009385A KR1020150101350A KR20150101350A KR20170009385A KR 20170009385 A KR20170009385 A KR 20170009385A KR 1020150101350 A KR1020150101350 A KR 1020150101350A KR 20150101350 A KR20150101350 A KR 20150101350A KR 20170009385 A KR20170009385 A KR 20170009385A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- cleaning
- wafer
- sodium
- solar
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000012459 cleaning agent Substances 0.000 title abstract description 41
- 238000004140 cleaning Methods 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- -1 hydroxyethyl group Chemical group 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003599 detergent Substances 0.000 claims description 16
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- 150000007529 inorganic bases Chemical class 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 150000007530 organic bases Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000004064 cosurfactant Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 125000006177 alkyl benzyl group Chemical group 0.000 claims description 6
- 229960003330 pentetic acid Drugs 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000006353 oxyethylene group Chemical group 0.000 claims description 3
- 239000010773 plant oil Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 claims description 2
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017454 sodium diacetate Nutrition 0.000 claims description 2
- 229940073490 sodium glutamate Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- XASWYPVFCVEQSU-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;potassium Chemical compound [K].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O XASWYPVFCVEQSU-UHFFFAOYSA-N 0.000 claims 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 abstract description 142
- 238000011109 contamination Methods 0.000 abstract description 29
- 239000000356 contaminant Substances 0.000 abstract description 8
- 238000012805 post-processing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 51
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000010730 cutting oil Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229940074076 glycerol formal Drugs 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 3
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 239000000176 sodium gluconate Substances 0.000 description 3
- 235000012207 sodium gluconate Nutrition 0.000 description 3
- 229940005574 sodium gluconate Drugs 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JZBRFIUYUGTUGG-UHFFFAOYSA-J tetrapotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JZBRFIUYUGTUGG-UHFFFAOYSA-J 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 0 *C1(*)OC(CO)CO1 Chemical compound *C1(*)OC(CO)CO1 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940093956 potassium carbonate Drugs 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- 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
- H01L31/042—PV modules or arrays of single PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
Description
The present invention relates to a natural sunlight wafer cleaner composition, which has excellent detergency against sunlight contamination of a solar photovoltaic wafer and re-adhesion of a contamination source, There is no occurrence of stain, it does not affect the post-process, and it is excellent in human safety and environmental safety.
Due to the regulation of CO 2 emissions to prevent global warming, many petroleum-based chemical materials, materials and products are being converted into substances with low CO 2 emissions such as renewable resources.
Therefore, the use of vegetable and natural raw materials without using petrochemical raw materials is in accordance with domestic and foreign environmental policies regulating CO 2 emissions and total-VOC emissions.
In addition, by solving the contamination defect problem such as dark spot frequently occurred in the production process of silicon wafers with wafer cleaner having superior cleaning power, it is possible to reduce the defective rate of wafers and increase the productivity of wafers by increasing the productivity of wafers.
The wafer can be obtained by cutting a silicon ingot. The ingot is obtained by growing silicon crystals. When the growth process is completed and the silicon ingot is completed, a cutting process is performed to obtain a wafer. After the ingot is cut, it is necessary to carry out a cleaning process to remove the cutting oil and slurry generated in the cutting process.
The pollutants can be largely divided into organic matter and inorganic matter. The organic matter is mostly the cooling agent used in the sawing process and the residual pollution source generated in the cleaning process. The inorganic matter is generated by the abrasive (eg SiC) Polysilicon flakes are dominant, and metals (zinc, iron, copper, etc.) away from the wire and carbon and silicon are also present.
Since the electrical characteristics of the solar photovoltaic wafer are significantly affected by the impurities, the surface of the solar photovoltaic wafer is sufficiently cleaned before each step to remove contamination by impurities. As industrial means thereof, many methods have been proposed in which a treatment solution containing an alkali as a main component or a treatment solution containing an alkaline surfactant, a hydrophilic solvent, hydrogen peroxide solution, and the like is added.
For example, Korean Patent Laid-Open No. 10-2010-0062096 (Jun. 10, 2010) discloses that a wafer cleaner composition composed of a glycol ether compound, an alcohol compound and a surfactant is effective in removing contaminants. However, in the case of glycol compounds, the possibility of re-contamination is very low due to the low emulsification and dispersing power of cutting pollutants after the cleaning is completed. In the case of alcoholol compounds, when the cleaning process temperature is 50 ° C or higher, It may be difficult to repeatedly use the cleaning agent in the process. In addition, since most of the constituents used in the conventional composition are derived from petroleum, they are very disadvantageous in terms of human safety and biodegradability.
In the case of Korean Patent Laid-Open Publication No. 10-2014-0018521 (published on Mar. 23, 2014), a wafer cleaner composition composed of an acrylic copolymer, an amine compound, an inorganic base and an organic base is used for the slurry It is described that the dirt on the surface of the wafer, in particular, the dirt generated by sticking to the surface of the wafer due to the heat generated during the slurry cutting and the process environment, is excellent. However, in the case of the acrylic copolymer, the dispersibility of the slurry source is excellent, but the wettability and penetration of the wafer surface is low, so that the cleaning of the contamination source of the cutting oil and the wafer pieces is not effective in a process in which the distance between the wafer and the wafer is small. In addition, amine compounds are highly toxic to humans and disadvantageous to environmental safety, so it is recommended that they are not used as much as possible.
In the case of WO 2011/154875 A1 (Dec. 15, 2011 international publication), modification of the surface of a silicon substrate to be etched and oxidized by a silicon substrate cleaning composition composed of quaternary ammonium hydroxide, a sulfa anion salt and a phosphoric acid anion salt, It is described as effective for removal of the inert layer produced by doping and glass being silicate, removal of porous silicon produced by wet edge separation, and / or removal of sculpture that repopulates the silicon substrate surface. However, sulfide-based anion salts and phosphate-based anion salts are very bubbles and have low sphericity, resulting in problems in the wastewater treatment process after the process, and the biodegradation is also not favorable, so significant improvement is required to meet the rigorous demand of the present process .
In WO 2004/053045 A1 (international publication 2004, 26 24), a detergent composition consisting of quaternary ammonium hydroxide, ethylene oxide-propylene oxide straight chain or branched alkyl ethers has excellent both degreasing performance and particle removal performance of the wafer surface And also that the etching on the wafer is well controlled. However, ethylene oxide-propylene oxide straight chain or branched alkyl ethers are low in solubility at a high concentration of quaternary ammonium hydroxide, and there is a restriction to add a phase stabilizer. In addition, since ethylene oxide-propylene oxide alone or a branched chain alkyl ether alone is difficult to secure a sufficient dispersing power against a contaminant source of slurry, there is a high risk of reattaching after cleaning, so that occurrence of defective wafers after cleaning may be increased.
SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a solar wafer cleaner composition having excellent cleaning power against flame contamination of a solar wafer, that is, an abrasive (SiC), cutting oil, a metal,
It is another object of the present invention to provide a solar wafer cleaner composition having an anti-reattaching ability against a contamination source in a cleaning process on the surface of a solar wafer.
Another object of the present invention is to provide a solar wafer cleaner composition which is excellent in detergency such as dark spots on the wafer surface after the cleaning process of the solar wafer.
The present invention also provides a solar wafer cleaner composition that does not affect the post-cleaning process of the photovoltaic wafer, i.e., the wafer surface texturing process.
Another object of the present invention is to provide a solar wafer cleaner composition having excellent human safety and environmental safety using a natural raw material.
A natural sunlight wafer cleaner composition according to the present invention comprises: (a) a nonionic surfactant derived from natural origin represented by the following formula (1); (b) a naturally occurring cosurfactant represented by the following formula (2); (c) a glycol additive; (d) at least one compound selected from inorganic bases, organic bases or mixtures thereof; And (e) water.
[Chemical Formula 1]
(Wherein R 1 represents a plant oil, a fatty acid having a hydroxyl group (OH), a fatty alcohol derived from a vegetable oil, EO represents an oxyethylene group, PO And x and y each independently represent an integer of 0 to 50, and the addition of EO, PO, or EO and PO from R 1 proceeds from a hydroxyl group or a carboxyl group (-COOH).
(2)
(Wherein R 2 represents hydrogen (H) or a methyl group (-CH 3 ).)
The above-mentioned (c) glycol additive contained in the natural sunlight wafer cleaner composition according to the present invention may be a compound represented by the following general formula (3).
(3)
Wherein R 3 is selected from the group consisting of hydrogen (-H), an alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, a benzyl group or an alkylbenzyl group ( represents an alkyl benzyl group), n is an integer of from 1 to 100, R 4 denotes a hydroxyl group (-OH), or -CH 2 oR 5, R 5 is hydrogen (-H), an ethyl group (-CH 2 CH 3), hydroxyethyl group (-CH 2 CH 2 OH), hydroxy-ethoxy-hydroxyethyl group (-CH 2 CH 2 OCH 2 CH 2 OH), propyl group (-CH 2 CH 2 CH 3) , isopropyl group (-CH (CH 3) 2) , 2- hydroxy-Pro-2-hydroxy-propyl (-CH 2 CH (OCH 2 CH (OH) CH 3) CH 3), carboxy group (-CH 2 COOH) , Or a sodium carboxymethyl group (-CH 2 COONa).
The inorganic base contained in the natural sunlight wafer cleaner composition according to the present invention may be selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium silicate, potassium phosphate, sodium phosphate, potassium pyrophosphate, sodium pyrophosphate and ammonium sulfate At least one inorganic base; Examples of the organic base include tetramethylammonium hydroxide, tetraethylammonium hydroxide, potassium carbonate, sodium carbonate, sodium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, sodium glutamate, sodium diacetate, diethylenetriaminepentaacetic acid sodium salt , And diethylene triamine pentaacetic acid potassium salt.
The naturally occurring nonionic surfactant represented by the above formula (1) used in the natural sunlight wafer cleaner composition of the present invention is used in an amount of 0.001 to 30% by weight, preferably 0.01 to 20% by weight, May be included in the range of 0.1 to 10% by weight.
The naturally occurring cosurfactant represented by the above formula (2) used in the natural sunlight wafer cleaner composition of the present invention is used in an amount of 0.001 to 30% by weight, preferably 0.01 to 20% by weight, 0.1 to 10% by weight.
The sugar additive represented by the general formula (3) used in the natural sunlight wafer cleaner composition of the present invention is added in an amount of 0.001 to 30% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight ≪ / RTI >
The inorganic base used in the natural sunlight wafer cleaner composition of the present invention may be contained in the range of 0.001 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight based on the total amount of the detergent composition .
The organic base used in the natural sunlight wafer cleaner composition of the present invention may be contained in an amount of 0.001 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the whole amount of the detergent composition .
The natural sunlight wafer cleaner composition according to the present invention has excellent detergency against flame contamination of a solar wafer, that is, abrasive (SiC), cutting oil, metals, etc., The present invention relates to a process for cleaning a wafer surface after a cleaning process of a photovoltaic wafer, that is, a cleaning process of a wafer surface, It does not affect the process and has the advantages of excellent human safety and environmental safety because it uses natural raw materials.
FIGS. 1A to 1D are photographs of a wire-sawing mono-solar wafer obtained by observing the cleaning power of Examples 1 and 2 and Comparative Examples 4 and 5 with an image analyzer (x100).
FIGS. 2A to 2D are photographs of a wire-sawing mono-solar wafer obtained by observing the cleaning power of Examples 1 and 2 and Comparative Examples 4 and 5 with a phase contrast microscope (x400).
FIGS. 3A to 3D are photographs respectively showing observations of cleaning powers of Examples 1 and 2 and Comparative Examples 4 and 5 for a slurry-growing mono-solar wafer with an image analyzer (x100).
FIGS. 4A to 4D are photographs showing the evaluation of detergency of Examples 1 and 2 and Comparative Examples 4 and 5 for a slurry-growing mono-solar wafer, respectively, with a phase contrast microscope (x400).
5A to 5D are photographs respectively showing observations of cleaning powers of Examples 1 and 2 and Comparative Examples 4 and 5 with respect to a slurry-sawing multi-solar wafer with an image analyzer (x100).
6A to 6D are photographs showing the evaluation of cleaning performance of the slurry multi-solar wafers of Examples 1 and 2 and Comparative Examples 4 and 5 with a phase contrast microscope (x400).
7A and 7B are front and rear photographs of the multi-solar wafer before cleaning and after cleaning with the cleaning agent of Example 1, respectively.
8A-8D are electron micrographs at different magnifications for the surface of the solar wafer before cleaning, respectively.
9 is an EDX analysis chart for the surface of a solar wafer before cleaning.
10A to 10D are electron micrographs at different magnifications on the surface of the solar wafer after cleaning with the cleaning agent of Comparative Example 5, respectively.
11 is an EDX analysis chart of the surface of the solar wafer after cleaning with the cleaning agent of Comparative Example 5. Fig.
12A to 12D are electron micrographs at different magnifications on the surface of the solar wafer after cleaning with the cleaning agent of Example 1. Fig.
13 is an EDX analysis chart of the surface of a solar wafer after cleaning with the cleaning agent of Example 1. Fig.
Hereinafter, the present invention will be described in detail.
A natural sunlight wafer cleaner composition according to the present invention comprises: (a) a nonionic surfactant derived from natural origin represented by the following formula (1); (b) a naturally occurring cosurfactant represented by the following formula (2); (c) a glycol additive; (d) at least one compound selected from inorganic bases, organic bases or mixtures thereof; And (e) water.
[Chemical Formula 1]
(Wherein R 1 represents a plant oil, a fatty acid having a hydroxyl group (OH), a fatty alcohol derived from a vegetable oil, EO represents an oxyethylene group, PO And x and y each independently represent an integer of 0 to 50, and the addition of EO, PO, or EO and PO from R 1 proceeds from a hydroxyl group or a carboxyl group (-COOH).
(2)
(Wherein R 2 represents hydrogen (H) or a methyl group (-CH 3 ).)
The naturally occurring nonionic surfactant represented by the above formula (1) used in the photovoltaic wafer cleaner composition of the present invention has excellent degreasing performance and particle removal performance on the wafer surface, Thereby preventing the contamination source from reattaching.
The naturally occurring nonionic surfactant represented by the formula (1) may be contained in an amount of 0.001 to 30% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the whole amount of the detergent composition.
The naturally occurring cosurfactant represented by the above formula (2) used in the photovoltaic wafer cleaner composition of the present invention is excellent in solubility in an oil pollution source such as cutting oil and is a natural nonionic surfactant represented by the above formula When they disperse pollutants, they work together to form stable micelles, which increases pollutant dispersion.
The naturally occurring cosurfactant represented by Formula 2 may be contained in an amount of 0.001 to 30% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight based on the whole amount of the detergent composition.
The above-mentioned (c) glycol additive contained in the natural sunlight wafer cleaner composition according to the present invention is a compound represented by the following formula (3).
(3)
Wherein R 3 is selected from the group consisting of hydrogen (-H), an alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, a benzyl group or an alkylbenzyl group ( represents an alkyl benzyl group), n is an integer of from 1 to 100, R 4 denotes a hydroxyl group (-OH), or -CH 2 oR 5, R 5 is hydrogen (-H), an ethyl group (-CH 2 CH 3), hydroxyethyl group (-CH 2 CH 2 OH), hydroxy-ethoxy-hydroxyethyl group (-CH 2 CH 2 OCH 2 CH 2 OH), propyl group (-CH 2 CH 2 CH 3) , isopropyl group (-CH (CH 3) 2) , 2- hydroxy-Pro-2-hydroxy-propyl (-CH 2 CH (OCH 2 CH (OH) CH 3) CH 3), carboxy group (-CH 2 COOH) , Or a sodium carboxymethyl group (-CH 2 COONa).
In the present invention, the natural-derived sugar additive represented by Formula 3 increases the chelating effect on metal contaminants generated during wafer cleaning and the dispersing power against particle contamination. In addition, phase stability can be imparted at a high pH concentration, and wafer cleaning agent of high concentration can be produced.
The sugar additive represented by the general formula (3) used in the natural sunlight wafer cleaner composition of the present invention is added in an amount of 0.001 to 30% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight ≪ / RTI >
The inorganic base contained in the natural sunlight wafer cleaner composition according to the present invention may be selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium silicate, potassium phosphate, sodium phosphate, potassium pyrophosphate, sodium pyrophosphate and ammonium sulfate At least one inorganic base.
The inorganic base used in the natural sunlight wafer cleaner composition of the present invention may be contained in the range of 0.001 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight based on the total amount of the detergent composition .
As the organic base contained in the natural sunlight wafer cleaner composition according to the present invention, tetramethylammonium hydroxide, tetraethylammonium hydroxide, potassium carbonate, sodium carbonate, ethylenediaminetetraacetate sodium salt, ethylenediaminetetraacetate potassium salt, sodium glutamate salt , Diacetic acid sodium salt, diethylenetriaminepentaacetic acid sodium salt, and diethylenetriaminepentaacetic acid potassium salt.
The organic base used in the natural sunlight wafer cleaner composition of the present invention may be contained in an amount of 0.001 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the whole amount of the detergent composition .
In the present invention, the inorganic base and the organic base provide an etching effect on a contamination source attached to the surface of the wafer, in particular, a metal contamination source, thereby removing or preventing stains on the wafer surface, sealing the metal ions in the contamination source, prevent.
In addition, the natural sunlight wafer cleaner composition of the present invention may further include conventional additives in addition to the above-described components. These additives are components commonly used in the field of detergent manufacturing, and the present invention does not limit the selection of these additives. These additives can improve the cleaning performance, dispersibility, penetration and wettability, which are the main performance of the cleaning, as an auxiliary role, and can function as prevention of reattachment and sealing of metal ions.
These additives may be at least one selected from the group consisting of citric acid, salicylic acid, malonic acid, succinic acid, glutaric acid, sorbitol, etc., derived from natural sources, considering that the feature of the present invention is a natural detergent.
The additive may be added in the range of 0.001 to 10% by weight, preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight in the photovoltaic wafer cleaner composition of the present invention. However, The blending amount can be changed accordingly.
INDUSTRIAL APPLICABILITY The photovoltaic wafer cleaner composition of the present invention exhibits excellent cleaning effect at room temperature and exhibits excellent cleaning power under heating.
The photovoltaic wafer cleaner composition of the present invention can be applied to various cleaning processes such as simple deposition, ultrasonic, spray, vibration, bubbling cleaning. Further, it can be applied to optimum cleaning conditions by adjusting cleaning time, cleaning temperature, rinsing time, rinsing temperature, drying time, drying temperature, drying conditions and the like.
Further, the solar photovoltaic wafer cleaner composition of the present invention exhibits excellent cleaning power for cleaning precision parts requiring high cleanliness such as semiconductor wafers, sapphire wafers, various kinds of electronics related glass substrates, prisms and lenses, in addition to solar wafer cleaning.
Hereinafter, the present invention will be described in detail by way of Examples, Comparative Examples and Experimental Examples, but it is not intended to limit the present invention, but merely to illustrate the present invention.
Examples and Comparative Examples
1. Preparation of contaminated water and pollutants
In the case of cleaned materials, solar mono silicon wafers (LG Siltron, Korea) and photovoltaic multi-silicon wafers (Inrisa, China) were supplied from solar wafer manufacturers and used as cleaning materials. In case of contamination source, contamination source of wafer slurry used in ingot cutting availability of domestic company A was obtained and used as a pollution source. The object to be cleaned was used as a test specimen after drying for 25 to 24 hours after application of the contaminant source.
2. Preparation of wafer cleaner composition
One
2
3
4
5
Surfactants
6
7
8
9
10
Surfactants
1) a natural oil containing X = 15 to 30, Y = 1 to 5 and R1 = hydroxyl group in R 1 -O- (EO) X (PO) Y H of formula
2) the general formula (I) of R 1 -O- (EO) X ( PO) from the Y H X = 5 ~ 15, Y = 1 ~ 5, R1 = nature fatty acid (fatty acid)
3) Solketal: A compound represented by the formula (2) wherein R < 2 >
4) glycerol formal: a compound represented by the formula (2) wherein R < 2 > is hydrogen
5) In the formula (3), CMC (carboxymethyl cellulose) is R 3 = -H, R 4 = -CH 2 OR 5 , R 5 = sodium carboxymethyl group (-CH 2 COONa), and n = 10-20.
(6) In the formula (3), alkyl polyglucoside is a compound wherein R 3 is a straight chain alkyl group having 4 to 10 carbon atoms, R 4 is a hydroxyl group (-OH), and n is 1 to 2.
7) TMAH = tetramethyl ammonium hydroxide
One
2
3
4
5
Surfactants
8) NP-9 = nonyl phenol ethoxylate (9 moles) (derived from petroleum)
9) BDG = butyl diglycol (derived from petroleum)
10) Acrylic acid polymer = poly acrylic acid (repeating unit of acrylic acid, average molecular weight 4,500)
3. Evaluation of cleaning power (cleansing property, rinsing property and anti-redeposition ability) of the wafer cleaner composition
Table 4 below shows the cleaning process for evaluating the cleaning performance of the silicon wafer, the cleaning agent concentration, the cleaning temperature, the cleaning condition, the rinsing temperature, the rinsing condition, the drying temperature and the drying condition.
Time: 3 minutes
Concentration: 25 times dilution
Ultrasound: 40kHz
Time: 3 minutes
Concentration: 25 times dilution
Ultrasound: 40kHz
Time: 3 minutes
Time
Spray rinse
Time: 3 minutes
Distilled water
Dipping rinse
Temperature: 80 degrees
Time: 3 minutes
The performance evaluation of the above wafer cleaner compositions was carried out according to the following stability, cleaning and foaming performance criteria in Table 5 below.
Instability: phase separation or opaque liquid
Typical: There is no contamination residue on the wafer surface, but there is staining.
Poor: Contaminant residues and stains on the wafer surface.
Typical: bubble disappears within 10 minutes
Poor: air bubbles remain after 10 minutes
The performance of the evaluation items for the wafer cleaner compositions of the examples and comparative examples in the above cleaning process is shown in Tables 6, 7 and 8 below.
4. Cleaning performance (cleaning property, rinsing property and anti-redeposition ability) of wafer cleaning composition after surface evaluation
Next, using the wafer cleaner compositions of Example 1, Example 2, Comparative Example 4, and Comparative Example 5, the surface of the wafer specimen after cleaning in the cleaning process was observed with an image analyzer and a phase contrast microscope, The residue was observed.
1) Evaluation of cleaning power (cleanability and rinsing) for wire-sawing mono-solar wafers
1-1) Observation of the washed specimen Image Analyzer (100 times) Observation: There was no wafer surface residue after cleaning according to Example 1 and Example 2, but a spot on the wafer surface after cleaning according to Comparative Example 4 and Comparative Example 5, And residues remained.
(Cleaning agent of Example 1), Fig. 1B (cleaning agent of Example 2), Fig. 1C (cleaning agent of Comparative Example 4), and cleaning agent of wire-sawing mono-solar wafer were observed with an image analyzer ) And FIG. 1D (the cleaning agent of Comparative Example 5), respectively.
1-2) Cleaning Sample Phase Contrast Microscope (400X) Observation: There was no wafer surface residue after cleaning according to Examples 1 and 2, but after cleaning according to Comparative Example 4 and Comparative Example 5, ) And residues remained.
The results are shown in FIG. 2A (cleaning agent of Example 1), FIG. 2B (cleaning agent of Example 2), and FIG. 2C (cleaning agent of Comparative Example 4), and the cleaning power of the wire-sawing mono-solar wafer was observed with a phase difference microscope ) And FIG. 2d (the cleaning agent of Comparative Example 5), respectively.
2) Evaluation of cleaning power (cleaning and rinsing) for slurry-fired mono-solar wafers
2-1) Observation of a washed specimen Image Analyzer (100 times) Observation: There was no wafer surface residue after cleaning according to Examples 1 and 2. However, after cleaning according to Comparative Example 4 and Comparative Example 5, And residues remained.
(Cleaning agent of Example 1), Fig. 3B (cleaning agent of Example 2), Fig. 3C (cleaning agent of Comparative Example 4), cleaning agent for the slurry sawing mono-solar wafer was observed with an image analyzer ) And Fig. 3d (cleaning agent of Comparative Example 5), respectively.
2-2) Cleaning Sample Phase Contrast Microscope (400X) Observation: There was no wafer surface residue after cleaning according to Examples 1 and 2. However, after cleaning according to Comparative Example 4 and Comparative Example 5, ) And residues remained.
4A (cleaning agent of Example 1), FIG. 4B (cleaning agent of Example 2), FIG. 4C (cleaning agent of Comparative Example 4), and cleaning agent for a slurry-growing mono-solar wafer were observed with a phase difference microscope ) And FIG. 4D (the cleaning agent of Comparative Example 5), respectively.
3) Evaluation of cleaning power (cleansing and rinsing) for slurry sawing multi-solar wafers
3-1) Observation of the washed specimen Image Analyzer (100 times): There was no wafer surface residue after cleaning according to Examples 1 and 2. However, after cleaning according to Comparative Example 4 and Comparative Example 5, And residues remained.
5A (the cleaning agent of Example 1), FIG. 5B (the cleaning agent of Example 2), and FIG. 5C (the cleaning agent of Comparative Example 4), and the cleaning agent for the slurry-forming multi- ) And FIG. 5D (the cleaning agent of Comparative Example 5), respectively.
3-2) Cleaning Sample Phase Contrast Microscope (400X) Observation: There was no wafer surface residue after cleaning according to Examples 1 and 2. However, after cleaning according to Comparative Example 4 and Comparative Example 5, ) And residues remained.
6A (the cleaning agent of Example 1), FIG. 6B (the cleaning agent of Example 2), and FIG. 6C (the cleaning agent of Comparative Example 4), and the cleaning power of the slurry- ) And FIG. 6D (the cleaning agent of Comparative Example 5), respectively.
5. Surface observation of the surface of wafer after cleaning according to Example 1 and Comparative Example 5 by electron microscope and EDX before cleaning of multi-solar wafer
The following results were obtained by observing the surfaces of the wafers before and after cleaning of the contaminated multi-solar wafers with the electron microscope and the EDX. Figs. 7A and 7B show photographs before cleaning the multi-solar wafer and after cleaning according to the first embodiment, respectively.
1) Analysis of contamination source by electron microscope and EDX on the surface of multi-solar wafer before cleaning
1-1) Next, the surface of the solar wafer was observed using an electron microscope before cleaning. The surface of the solar wafer mainly consists of contamination sources such as wafer ring processing slurry and cutting oil.
8A to 8D are electron microscopic photographs of x200, x1,000, x5,000, and x10,000 magnification, respectively.
1-2) Next, the surface of the solar wafer was observed before cleaning using EDX. Carbon and oxygen are mainly derived from diethylene glycol (DEG) and proplyene glycol (PG), which are the coolant components used in wafer processing. The iron (Fe) component is a source of contamination caused by the high-temperature cutting of the wire-sawing process of the solar wafer. When the wafer is not cleaned properly, the Fe component adsorbs on the wafer surface and remains as a block spot after drying .
An EDX analysis chart for the above results is shown in Fig.
2) Analysis of contamination source by electron microscope and EDX on the surface of multi-solar wafer after cleaning according to Comparative Example 5
2-1) Next, the surface of the multi-solar wafer was observed after cleaning according to Comparative Example 5 using an electron microscope. The surface of the solar wafer remained contamination sources and unevenness such as machining slurry and cutting oil.
The results are shown in Figs. 10a to 10d, which are electron micrographs x200, x1,000, x5,000, and x10,000 magnification, respectively.
2-2) Next, the surface of the multi-solar wafer was observed after cleaning according to Comparative Example 5 using EDX. Carbon and oxygen content remained in the slurry contamination source, and iron (Fe) contamination generated by hot cutting in the wire-sawing process of the solar wafer remained.
An EDX analysis chart for the above results is shown in Fig.
3) Analysis of contamination source by electron microscope and EDX on the surface of multi-solar wafer after cleaning according to Example 1
3-1) Next, the surface of the multi-solar wafer was observed after cleaning according to Example 1 using an electron microscope. The surface of the solar wafer was free of contaminant residues and unevenness such as processing slurry and cutting oil.
The results are shown in Figs. 12A to 12D, which are electron micrographs x200, x1,000, x5,000, and x10,000 magnification, respectively.
3-2) Next, the surface of the multi-solar wafer was observed after cleaning according to Example 1 using EDX. There was no carbon and oxygen content in the slurry contamination source from the cutting oil residue, and the iron (Fe) contamination generated by the hot cutting in the wire-sawing process of the solar wafer remained.
An EDX analysis chart for the above results is shown in Fig.
Test example: Evaluation of biodegradability
The biodegradability of the detergent compositions of Examples 1 and 2 was evaluated by measuring the percentage of dissolved organic matter (%) by KS M 2714, which was more than the expected value, and the results are shown in Tables 39 and 40, respectively.
As a result, the compositions of Examples 1 to 10 as the wafer cleaner compositions of the present invention all showed excellent phase stability, cleaning power, defoaming property and biodegradability. As a result of observing the surfaces of the solar wafers of Example 1 and Example 2 after cleaning, it was confirmed that no contaminant residues remained, and it was confirmed that the biodegradability was also excellent.
Claims (9)
A natural solar wafer cleaner composition.
[Chemical Formula 1]
(Wherein R 1 represents a plant oil, a fatty acid having a hydroxyl group (OH), a fatty alcohol derived from a vegetable oil, EO represents an oxyethylene group, PO And x and y each independently represent an integer of 0 to 50, and the addition of EO, PO, or EO and PO from R 1 proceeds from a hydroxyl group or a carboxyl group (-COOH).
(2)
(Wherein R 2 represents hydrogen (H) or methyl (-CH 3 ).) (A) a naturally occurring nonionic surfactant represented by the following general formula (1); (b) a naturally occurring cosurfactant represented by the following formula (2); (c) a glycol additive; (d) at least one selected from inorganic bases, organic bases or mixtures thereof; And (e) water.
(3)
Wherein R 3 is selected from the group consisting of hydrogen (-H), an alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, a benzyl group or an alkylbenzyl group ( represents an alkyl benzyl group), n is an integer of from 1 to 100, R 4 denotes a hydroxyl group (-OH), or -CH 2 oR 5, R 5 is hydrogen (-H), an ethyl group (-CH 2 CH 3), hydroxyethyl group (-CH 2 CH 2 OH), hydroxy-ethoxy-hydroxyethyl group (-CH 2 CH 2 OCH 2 CH 2 OH), propyl group (-CH 2 CH 2 CH 3) , isopropyl group (-CH (CH 3) 2) , 2- hydroxy-Pro-2-hydroxy-propyl (-CH 2 CH (OCH 2 CH (OH) CH 3) CH 3), carboxy group (-CH 2 COOH) , Or a sodium carboxymethyl group (-CH 2 COONa).
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| CN108485829A (en) * | 2018-04-03 | 2018-09-04 | 湖州五石科技有限公司 | A kind of silicon slice detergent |
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| WO2004053045A1 (en) | 2002-12-12 | 2004-06-24 | Showa Denko K.K. | Cleaning agent composition, cleaning and production methods for semiconductor wafer, and semiconductor wafer |
| KR20100062096A (en) | 2008-12-01 | 2010-06-10 | 주식회사 엘지생활건강 | Solar cell wafer detergent composition |
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| US20160122696A1 (en) * | 2013-05-17 | 2016-05-05 | Advanced Technology Materials, Inc. | Compositions and methods for removing ceria particles from a surface |
| KR101499611B1 (en) * | 2013-11-25 | 2015-03-09 | 주식회사 위즈켐 | Environmental Friendly Metal-free Cleaning Composition |
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| WO2004053045A1 (en) | 2002-12-12 | 2004-06-24 | Showa Denko K.K. | Cleaning agent composition, cleaning and production methods for semiconductor wafer, and semiconductor wafer |
| KR20100062096A (en) | 2008-12-01 | 2010-06-10 | 주식회사 엘지생활건강 | Solar cell wafer detergent composition |
| WO2011154875A1 (en) | 2010-06-09 | 2011-12-15 | Basf Se | Aqueous alkaline etching and cleaning composition and method for treating the surface of silicon substrates |
| KR20140018521A (en) | 2012-08-02 | 2014-02-13 | 동우 화인켐 주식회사 | Wafer cleaning composition used in process of ingot cutting |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108485829A (en) * | 2018-04-03 | 2018-09-04 | 湖州五石科技有限公司 | A kind of silicon slice detergent |
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| KR101765212B1 (en) | 2017-08-04 |
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