JP6369460B2 - Etching composition - Google Patents
Etching composition Download PDFInfo
- Publication number
- JP6369460B2 JP6369460B2 JP2015519634A JP2015519634A JP6369460B2 JP 6369460 B2 JP6369460 B2 JP 6369460B2 JP 2015519634 A JP2015519634 A JP 2015519634A JP 2015519634 A JP2015519634 A JP 2015519634A JP 6369460 B2 JP6369460 B2 JP 6369460B2
- Authority
- JP
- Japan
- Prior art keywords
- etching
- etching composition
- boron
- composition
- mass
- 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.)
- Expired - Fee Related
Links
- 238000005530 etching Methods 0.000 title claims description 110
- 239000000203 mixture Substances 0.000 title claims description 73
- -1 metal complex ion Chemical class 0.000 claims description 110
- 238000000034 method Methods 0.000 claims description 52
- 238000007639 printing Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 23
- 239000002841 Lewis acid Substances 0.000 claims description 16
- 150000007517 lewis acids Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000010419 fine particle Substances 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 150000001639 boron compounds Chemical class 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000004437 phosphorous atom Chemical group 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 229910052736 halogen Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 239000010408 film Substances 0.000 description 37
- 239000002245 particle Substances 0.000 description 32
- 229910052581 Si3N4 Inorganic materials 0.000 description 30
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 30
- 239000010409 thin film Substances 0.000 description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 21
- 229910052710 silicon Inorganic materials 0.000 description 21
- 239000010703 silicon Substances 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- 238000007650 screen-printing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 150000003377 silicon compounds Chemical class 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- VSTBONUOIOMHSE-UHFFFAOYSA-N 3-methyl-4-(4-phenylmethoxyphenyl)-1h-1,2,4-triazole-5-thione Chemical compound CC1=NNC(=S)N1C(C=C1)=CC=C1OCC1=CC=CC=C1 VSTBONUOIOMHSE-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZNOZWUKQPJXOIG-XSBHQQIPSA-L [(2r,3s,4r,5r,6s)-6-[[(1r,3s,4r,5r,8s)-3,4-dihydroxy-2,6-dioxabicyclo[3.2.1]octan-8-yl]oxy]-4-[[(1r,3r,4r,5r,8s)-8-[(2s,3r,4r,5r,6r)-3,4-dihydroxy-6-(hydroxymethyl)-5-sulfonatooxyoxan-2-yl]oxy-4-hydroxy-2,6-dioxabicyclo[3.2.1]octan-3-yl]oxy]-5-hydroxy-2-( Chemical compound O[C@@H]1[C@@H](O)[C@@H](OS([O-])(=O)=O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H]2OC[C@H]1O[C@H](O[C@H]1[C@H]([C@@H](CO)O[C@@H](O[C@@H]3[C@@H]4OC[C@H]3O[C@H](O)[C@@H]4O)[C@@H]1O)OS([O-])(=O)=O)[C@@H]2O ZNOZWUKQPJXOIG-XSBHQQIPSA-L 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- OJOSABWCUVCSTQ-UHFFFAOYSA-N cyclohepta-2,4,6-trienylium Chemical compound C1=CC=C[CH+]=C[CH]1 OJOSABWCUVCSTQ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- IZZVHOPLTANRPW-UHFFFAOYSA-N 2-(2-propan-2-yloxyethoxy)ethyl acetate Chemical compound CC(C)OCCOCCOC(C)=O IZZVHOPLTANRPW-UHFFFAOYSA-N 0.000 description 1
- SGQLKNKVOZVAAY-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethyl acetate Chemical compound CCCCOCCOCCOCCOC(C)=O SGQLKNKVOZVAAY-UHFFFAOYSA-N 0.000 description 1
- NVSCAPMJFRYMFK-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethyl acetate Chemical compound CCOCCOCCOCCOC(C)=O NVSCAPMJFRYMFK-UHFFFAOYSA-N 0.000 description 1
- SDHQGBWMLCBNSM-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl acetate Chemical compound COCCOCCOCCOC(C)=O SDHQGBWMLCBNSM-UHFFFAOYSA-N 0.000 description 1
- WZDMGBHDHARVNN-UHFFFAOYSA-N 2-[2-(2-propan-2-yloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(C)OCCOCCOCCOC(C)=O WZDMGBHDHARVNN-UHFFFAOYSA-N 0.000 description 1
- ONPJEOPZOXVCDK-UHFFFAOYSA-N 2-[2-(2-propoxyethoxy)ethoxy]ethyl acetate Chemical compound CCCOCCOCCOCCOC(C)=O ONPJEOPZOXVCDK-UHFFFAOYSA-N 0.000 description 1
- VNSOQPWJZGNFAW-UHFFFAOYSA-N 2-[2-[(2-methylpropan-2-yl)oxy]ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOC(C)(C)C VNSOQPWJZGNFAW-UHFFFAOYSA-N 0.000 description 1
- GAWXXOYITYGULJ-UHFFFAOYSA-N 2-[2-[2-[(2-methylpropan-2-yl)oxy]ethoxy]ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)(C)C GAWXXOYITYGULJ-UHFFFAOYSA-N 0.000 description 1
- TZIJEHNHNLJSSH-UHFFFAOYSA-N 2-[4-(dimethylamino)phenyl]-1,3-benzoxazol-5-amine Chemical compound C1=CC(N(C)C)=CC=C1C1=NC2=CC(N)=CC=C2O1 TZIJEHNHNLJSSH-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- YWJHQHJWHJRTAB-UHFFFAOYSA-N 4-(2-Methoxypropan-2-yl)-1-methylcyclohex-1-ene Chemical compound COC(C)(C)C1CCC(C)=CC1 YWJHQHJWHJRTAB-UHFFFAOYSA-N 0.000 description 1
- UNDXPKDBFOOQFC-UHFFFAOYSA-N 4-[2-nitro-4-(trifluoromethyl)phenyl]morpholine Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1N1CCOCC1 UNDXPKDBFOOQFC-UHFFFAOYSA-N 0.000 description 1
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- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- HDIWKNXVBQPJCO-UHFFFAOYSA-N ethyl 2-methylsulfanyl-6-oxo-1h-pyrimidine-5-carboxylate Chemical compound CCOC(=O)C1=CN=C(SC)NC1=O HDIWKNXVBQPJCO-UHFFFAOYSA-N 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 229920003049 isoprene rubber Polymers 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000813 microcontact printing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- Photovoltaic Devices (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
Description
本発明は、無機薄膜の除去（エッチング）等に使用される組成物に関する。 The present invention relates to a composition used for removing (etching) an inorganic thin film.
酸化ケイ素や窒化ケイ素等の無機薄膜は、層間絶縁膜、パッシベーション膜、反射防止膜等として、各種半導体素子や太陽電池等で使用されている。
例えば、太陽電池には変換効率を向上するため、受光面側にＳｉＮ膜からなる反射防止膜を形成し、受光面の反対側の面にパッシベーション膜が形成されているものがある。Inorganic thin films such as silicon oxide and silicon nitride are used in various semiconductor elements, solar cells, and the like as interlayer insulating films, passivation films, antireflection films, and the like.
For example, in some solar cells, an antireflection film made of a SiN film is formed on the light receiving surface side and a passivation film is formed on the surface opposite to the light receiving surface in order to improve conversion efficiency.
太陽電池として一般的な結晶シリコン太陽電池セルの製造では、ｐ型シリコンウェハの表層にｎ＋層となるリン拡散層を形成し、下層のｐ層との間にｐｎ接合を形成する。その後、ｎ＋層上に反射防止膜を形成した後、受光面側及び裏面側に電極を形成し、必要に応じてパッシベーション膜を形成する。
太陽電池の製造では、反射防止膜やパッシベーション膜を形成した後で、電極をｎ＋層に接続することが多いため、これら無機薄膜に開口を設ける必要がある。In the manufacture of a crystalline silicon solar battery cell that is generally used as a solar battery, a phosphorus diffusion layer that becomes an n + layer is formed on the surface layer of a p-type silicon wafer, and a pn junction is formed between the lower p layer. Thereafter, after forming an antireflection film on the n + layer, electrodes are formed on the light receiving surface side and the back surface side, and a passivation film is formed as necessary.
In the manufacture of solar cells, electrodes are often connected to the n + layer after the formation of an antireflection film or a passivation film, and thus it is necessary to provide openings in these inorganic thin films.
無機薄膜に開口を設ける方法の１つとして、エッチング法がある。エッチング法としては、フォトレジストを用いた方法が一般的である。例えば、無機薄膜を除去する成分（エッチング成分）として、特許文献１には特定の化学構造式を有する４級アルキルアンモニウム塩及び含窒素塩基性化合物並びに無機酸及び／又は有機酸を含むエッチング液が記載されている。
また、レーザーによって開口を形成する方法がある。しかしながら、加工位置制御が煩雑であり、加工時間を要するため、生産性が十分ではない。また、レーザーによって下部にあるｎ＋層やウェハ等が損傷する可能性がある。One method for providing an opening in an inorganic thin film is an etching method. As an etching method, a method using a photoresist is generally used. For example, as a component for removing an inorganic thin film (etching component), Patent Document 1 discloses an etching solution containing a quaternary alkyl ammonium salt having a specific chemical structural formula, a nitrogen-containing basic compound, and an inorganic acid and / or an organic acid. Have been described.
There is also a method of forming an opening with a laser. However, since the processing position control is complicated and requires processing time, productivity is not sufficient. In addition, there is a possibility that the n + layer, the wafer, and the like below are damaged by the laser.
また、従来、最も一般的な製造方法としては、電極となる金属と、ケイ素酸化物等のガラスを構成する化合物を含有する導電ペーストを塗布し、加熱によってファイヤースルー（焼成貫通）を起こし、無機薄膜に開口部を形成すると同時に電極とｎ＋層を接続する方法がある。しかしながら、本方法では２５０℃以上の高温処理が必要なため、ｎ＋層やウェハがダメージを受け、発電効率の低下を生じる可能性がある。
尚、無機薄膜をはじめからパターン状に形成する方法が考えられるが、工程が煩雑であることから効率的ではなく、また、パターン形成の精度の点で十分ではない。In addition, conventionally, the most common manufacturing method is to apply a conductive paste containing a metal that constitutes an electrode and a compound that constitutes glass such as silicon oxide, and cause fire through (fired penetration) by heating, and inorganic There is a method of forming an opening in a thin film and simultaneously connecting an electrode and an n + layer. However, since this method requires high-temperature treatment at 250 ° C. or higher, the n + layer and the wafer may be damaged and power generation efficiency may be reduced.
In addition, although the method of forming an inorganic thin film in the pattern form from the beginning is considered, it is not efficient because the process is complicated, and it is not sufficient in terms of the accuracy of pattern formation.
一方、エッチングペーストを印刷して無機薄膜上にパターン等を形成し、その後、加熱することにより、エッチングペースト下部に開口を形成する方法が提案されている。
エッチング成分としては、例えば、特許文献２にはリン酸又はリン酸塩を含むエッチング媒体が記載されている。しかしながら、最適なエッチング温度が２５０℃超と高いため、ｎ＋層やウェハ等がダメージを受ける可能性がある。On the other hand, a method has been proposed in which an etching paste is printed to form a pattern or the like on an inorganic thin film, and then heated to form an opening below the etching paste.
As an etching component, for example, Patent Document 2 describes an etching medium containing phosphoric acid or phosphate. However, since the optimum etching temperature is as high as over 250 ° C., the n + layer, the wafer, and the like may be damaged.
また、エッチング成分として、アンモニウム、アルカリ金属、及びアンチモンのフッ化物；アンモニウム、アルカリ金属、及びカルシウムの酸性フッ化物；並びにテトラフルオロホウ酸カリウムの群より選択される少なくとも１種類のフッ素化合物と、任意に、所定の無機鉱酸及び有機酸を含むエッチング媒体を用いる方法が記載されている（特許文献３参照）。しかしながら、フッ素化合物と酸を混合したエッチング媒体は毒性が極めて高いという問題がある。 Further, as an etching component, ammonium, alkali metal, and antimony fluoride; ammonium, alkali metal, and calcium acidic fluoride; and at least one fluorine compound selected from the group of potassium tetrafluoroborate, and any Describes a method using an etching medium containing a predetermined inorganic mineral acid and organic acid (see Patent Document 3). However, an etching medium in which a fluorine compound and an acid are mixed has a problem of extremely high toxicity.
本発明の目的は、無機膜のエッチングに使用できる新規組成物を提供することである。 An object of the present invention is to provide a novel composition that can be used for etching an inorganic film.
本発明によれば、以下のエッチング組成物等が提供される。
１．フッ素原子とリン原子が単結合で結合した構造を有する陰イオンと、陽イオンからなる塩と、溶媒と、を含有するエッチング組成物。
２．前記陽イオンが、金属イオン又は金属錯体イオンである、１に記載のエッチング組成物。
３．前記陽イオンが金属イオンである、１又は２に記載のエッチング組成物。
４．さらに、ホウ素及び該ホウ素と結合したハロゲンとを構造中に含むルイス酸、前記ルイス酸の塩、並びに前記ルイス酸を発生する化合物から選択される少なくとも１つのホウ素化合物を含有する１〜３のいずれかに記載のエッチング組成物。
５．下記一般式（１）で表される、アンモニウムイオンとリン酸イオンの塩である化合物と、溶媒と、を含有するエッチング組成物。
［ＮＲ４］＋・［ＰＸ６］− （１）
（式中、Ｒはそれぞれ独立に、水素原子、脂肪族炭化水素基又はアリールアルキル基であり、Ｘはそれぞれ独立にＦ、Ｃｌ、Ｂｒ又はＩであり、Ｘの少なくとも１つはＦである。）
６．さらに、ホウ素及び該ホウ素と結合したハロゲンとを構造中に含むルイス酸、前記ルイス酸の塩、並びに前記ルイス酸を発生する化合物から選択される少なくとも１つのホウ素化合物を含有する５に記載のエッチング組成物。
７．前記一般式（１）で表される化合物の含有率が、全体の５〜９０質量％である、５又は６に記載のエッチング組成物。
８．前記一般式（１）で表される化合物と前記ホウ素化合物の含有率が、全体の５〜９０質量％である、７に記載のエッチング組成物。
９．さらに、増粘剤及び微粒子の少なくとも一方を含有する１〜８のいずれかに記載のエッチング組成物。
１０．１〜９のいずれかに記載のエッチング組成物を使用して、無機薄膜を除去する工程を有する、無機薄膜の除去方法。
１１．１〜９のいずれかに記載の組成物を、印刷法により無機薄膜上に塗布する工程と、
前記塗布後に加熱することにより、無機薄膜を除去する工程と、を有する、１０に記載の無機薄膜の除去方法。
１２．１０又は１１に記載の方法で得られる基板。
１３．１０又は１１に記載の方法を使用して得られる太陽電池セル。According to the present invention, the following etching composition and the like are provided.
1. An etching composition comprising an anion having a structure in which a fluorine atom and a phosphorus atom are bonded by a single bond, a salt composed of a cation, and a solvent.
2. 2. The etching composition according to 1, wherein the cation is a metal ion or a metal complex ion.
3. 3. The etching composition according to 1 or 2, wherein the cation is a metal ion.
4). Further, any one of 1 to 3 containing at least one boron compound selected from a Lewis acid containing boron and a halogen bonded to the boron in the structure, a salt of the Lewis acid, and a compound generating the Lewis acid An etching composition according to claim 1.
5. An etching composition containing a compound represented by the following general formula (1), which is a salt of ammonium ions and phosphate ions, and a solvent.
[NR 4 ] + · [PX 6 ] − (1)
(In the formula, each R is independently a hydrogen atom, an aliphatic hydrocarbon group, or an arylalkyl group; each X is independently F, Cl, Br, or I; and at least one of X is F. )
6). 6. The etching according to 5, further comprising at least one boron compound selected from a Lewis acid containing boron and a halogen bonded to the boron in the structure, a salt of the Lewis acid, and a compound that generates the Lewis acid. Composition.
7). Etching composition of 5 or 6 whose content rate of the compound represented by the said General formula (1) is 5-90 mass% of the whole.
8). The etching composition of 7 whose content rate of the compound represented by the said General formula (1) and the said boron compound is 5-90 mass% of the whole.
9. Furthermore, the etching composition in any one of 1-8 containing at least one of a thickener and microparticles | fine-particles.
The removal method of an inorganic thin film which has a process of removing an inorganic thin film using the etching composition in any one of 10.1-9.
11. The process of apply | coating the composition in any one of 1-9 on an inorganic thin film with a printing method,
11. The method for removing an inorganic thin film according to 10, comprising a step of removing the inorganic thin film by heating after the application.
12. A substrate obtained by the method according to 10 or 11.
13. A solar cell obtained using the method according to 10 or 11.
本発明によれば、新規なエッチング組成物が提供できる。本発明の組成物を使用することにより、従来よりも低温で無機薄膜を除去できる。 According to the present invention, a novel etching composition can be provided. By using the composition of the present invention, the inorganic thin film can be removed at a lower temperature than before.
本発明のエッチング組成物の第１の態様は、フッ素原子とリン原子が単結合で結合した構造を有する陰イオンと、陽イオンからなる塩（以下、成分（Ａ１））と、溶媒（以下、成分（Ｂ））と、を含有することを特徴とする。
成分（Ａ１）は、無機薄膜を浸食し除去するエッチング成分である。本発明の第１の態様では、エッチング成分は室温（２５℃）で固体であることが好ましい。本発明の組成物の第１の態様は、成分（Ａ１）を含有することにより、従来のエッチング剤に添加されていた有機酸又は無機酸を含有しなくとも、十分なエッチング性を有する。In the first aspect of the etching composition of the present invention, an anion having a structure in which a fluorine atom and a phosphorus atom are bonded by a single bond, a salt composed of a cation (hereinafter, component (A1)), a solvent (hereinafter, Component (B)).
The component (A1) is an etching component that erodes and removes the inorganic thin film. In the first aspect of the present invention, the etching component is preferably solid at room temperature (25 ° C.). The 1st aspect of the composition of this invention has sufficient etching property even if it does not contain the organic acid or inorganic acid which was added to the conventional etching agent by containing a component (A1).
成分（Ａ１）において、フッ素原子とリン原子が単結合で結合した構造を有する陰イオンとしては、例えば、ヘキサフルオロリン酸イオン、フルオリドリン酸イオン等が挙げられる。好ましくは、ヘキサフルオロリン酸イオンである。 In the component (A1), examples of the anion having a structure in which a fluorine atom and a phosphorus atom are bonded by a single bond include hexafluorophosphate ions and fluoride ions. Preferably, it is a hexafluorophosphate ion.
陽イオンとしては、特に限定はないが、金属イオン、金属錯体イオン、ニトロニウムイオン、ニトロソニウムイオン等が好ましい。なかでも金属イオン又は金属錯体イオンが好ましく、特に、金属イオンが好ましい。
金属イオンとしては、ナトリウム、カリウム、銀、コバルト、タリウム等が挙げられる。好ましくは、ナトリウム又はカリウムである。The cation is not particularly limited, but metal ions, metal complex ions, nitronium ions, nitrosonium ions and the like are preferable. Of these, metal ions or metal complex ions are preferable, and metal ions are particularly preferable.
Examples of the metal ion include sodium, potassium, silver, cobalt, thallium and the like. Preferably, it is sodium or potassium.
成分（Ａ１）の具体例としては、ヘキサフルオロリン酸リチウム、ヘキサフルオロリン酸ナトリウム、ヘキサフルオロリン酸カリウム、ヘキサフルオロリン酸銀、ヘキサフルオロリン酸コバルト、ヘキサフルオロリン酸テトラキス（アセトニトリル）銅（Ｉ）、ヘキサフルオロリン酸タリウム（Ｉ）、ヘキサフルオロリン酸（トリシクロヘキシルホスフィン）（１，５−シクロオクタジエン）（ピリジン）イリジウム（Ｉ）、ヘキサフルオロリン酸トリス（アセトニトリル）シクロペンタジエニルルテニウム（ＩＩ）、ヘキサフルオロリン酸トリス（アセトニトリル）シクロペンタジエニルルテニウム（ＩＩ）、ヘキサフルオロリン酸トリス（アセトニトリル）ペンタメチルシクロペンタジエニルルテニウム（ＩＩ）、Ｏ−（７−アザベンゾトリアゾール−１−イル）−Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラメチルウロニウムヘキサフルオロリン酸塩、Ｏ−（ベンゾトリアゾール−１−イル）−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルウロニウムヘキサフルオロリン酸塩、ビス（ペンタメチルシクロペンタジエニル）コバルト（ＩＩＩ）ヘキサフルオロリン酸塩、コバルト塩センヘキサフルオロホスファート、ヘキサフルオロリン酸２−（７−アザ−１Ｈ−ベンゾトリアゾール−１−イル）−１，１，３，３−テトラメチルウロニウム、ヘキサフルオロリン酸（２Ｓ，４Ｓ）−（−）−２，４−ビス（ジフェニルホスフィノ）ペンタン（ノルボルナジエン）ロジウム（Ｉ）、ヘキサフルオロリン酸ビス（ペンタメチルシクロペンタジエニル）コバルト、ヘキサフルオロリン酸３−ジ−ｉ−プロピルホスフィノ−２−（Ｎ，Ｎ−ジメチルアミノ）−１Ｈ−インデン（１，５−シクロオクタジエン）イリジウム（Ｉ）、ヘキサフルオロリン酸３−ジ−ｉ−プロピルホスフィノ−２−（Ｎ，Ｎ−ジメチルアミノ）−１Ｈ−インデン（１，５−シクロオクタジエン）イリジウム（Ｉ）、ヘキサフルオロリン酸フェロセニウム、ヘキサフルオロリン酸ニトロニウム、ヘキサフルオロリン酸ニトロソニウム、ヘキサフルオロリン酸ジフェニルヨードニウム、ヘキサフルオロリン酸テトラブチルホスホニウム、ヘキサフルオロリン酸テトラエチルホスホニウム、ヘキサフルオロリン酸トリヘキシル（テトラデシル）ホスホニウム、ビス（４−メチルフェニル）ヨードニウムヘキサフルオロリン酸、１Ｈ−ベンゾトリアゾール−１−イルオキシトリピロリジノホスホニウムヘキサフルオロリン酸塩、トリアゾール−１−イルオキシトリス（ジメチルアミノ）ホスホニウムヘキサフルオロリン酸塩、ブロモトリ（１−ピロリジニル）ホスホニウムヘキサフルオロリン酸塩、フルオリドリン酸ジナトリウム、フルオリドリン酸ジカリウム、フルオリドリン酸ジリチウム、モノフルオロリン酸カルシウム等が挙げられる。特に、ヘキサフルオロリン酸ナトリウム等が好ましい。 Specific examples of the component (A1) include lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, silver hexafluorophosphate, cobalt hexafluorophosphate, tetrakis (acetonitrile) copper (hexafluorophosphate) ( I), thallium hexafluorophosphate (I), hexafluorophosphoric acid (tricyclohexylphosphine) (1,5-cyclooctadiene) (pyridine) iridium (I), hexafluorophosphoric acid tris (acetonitrile) cyclopentadienyl Ruthenium (II), hexafluorophosphate tris (acetonitrile) cyclopentadienyl ruthenium (II), hexafluorophosphate tris (acetonitrile) pentamethylcyclopentadienyl ruthenium (II), O- (7-azabenzo Riazol-1-yl) -N, N, N ′, N ′,-tetramethyluronium hexafluorophosphate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetra Methyluronium hexafluorophosphate, bis (pentamethylcyclopentadienyl) cobalt (III) hexafluorophosphate, cobalt salt sen hexafluorophosphate, hexafluorophosphate 2- (7-aza-1H-benzo Triazol-1-yl) -1,1,3,3-tetramethyluronium, hexafluorophosphoric acid (2S, 4S)-(−)-2,4-bis (diphenylphosphino) pentane (norbornadiene) rhodium ( I), bis (pentamethylcyclopentadienyl) cobalt hexafluorophosphate, 3-di-i-pro hexafluorophosphate Ruphosphino-2- (N, N-dimethylamino) -1H-indene (1,5-cyclooctadiene) iridium (I), 3-di-i-propylphosphino-2-hexafluorophosphate (N, N -Dimethylamino) -1H-indene (1,5-cyclooctadiene) iridium (I), ferrocenium hexafluorophosphate, nitronium hexafluorophosphate, nitrosonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, hexafluoro Tetrabutylphosphonium phosphate, tetraethylphosphonium hexafluorophosphate, trihexyl (tetradecyl) phosphonium hexafluorophosphate, bis (4-methylphenyl) iodonium hexafluorophosphoric acid, 1H-benzotriazol-1-yloxytripiro Lydinophosphonium hexafluorophosphate, triazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, bromotri (1-pyrrolidinyl) phosphonium hexafluorophosphate, disodium fluoride, dipotassium fluoride , Dilithium fluorophosphate, calcium monofluorophosphate and the like. In particular, sodium hexafluorophosphate and the like are preferable.
本発明のエッチング組成物の第２の態様は、下記一般式（１）で表される、アンモニウムイオンとリン酸イオンの塩（以下、成分（Ａ２））と、溶媒（第１の態様の成分（Ｂ）と同じ）と、を含有する。
［ＮＲ４］＋・［ＰＸ６］− （１）A second aspect of the etching composition of the present invention is a salt of ammonium ion and phosphate ion (hereinafter referred to as component (A2)) represented by the following general formula (1), and a solvent (component of the first aspect). (Same as (B)).
[NR 4 ] + · [PX 6 ] − (1)
尚、本発明の第１の態様及び第２の態様のエッチング組成物を総括して、本発明のエッチング組成物という。また、成分（Ａ１）及び（Ａ２）を総括して、成分（Ａ）という。 The etching compositions of the first and second aspects of the present invention are collectively referred to as the etching composition of the present invention. In addition, components (A1) and (A2) are collectively referred to as component (A).
成分（Ａ２）は、フッ素原子とリン原子が単結合で結合した構造を有するルイス酸と、アンモニウム系イオンの塩である。成分（Ａ２）は、無機薄膜を浸食し除去するエッチング成分である。本発明の第２の態様では、エッチング成分は室温（２５℃）で固体であることが好ましい。本発明の組成物の第２の態様は、成分（Ａ２）を含有することにより、従来のエッチング剤に添加されていた有機酸又は無機酸を含有しなくとも、十分なエッチング性を有する。
式（１）において、４つのＲはそれぞれ独立に、水素原子、脂肪族炭化水素基又はアリールアルキル基である。
脂肪族炭化水素基としては、炭素数が１〜１０の直鎖状アルキル基、炭素数が３〜１２のシクロアルキル基、炭素数が１〜１０の分岐状アルキル基が挙げられる。好ましくは、炭素数が１〜７の直鎖状アルキル基であり、特に好ましくは、炭素数が１〜４の直鎖状アルキル基である。
アリールアルキル（アラルキル）基としては、アルキル鎖の炭素数が１〜４であり、アリール基の炭素数が６〜１０であるものが好ましい。好ましくはベンジル基である。
Ｒはそれぞれ独立に、水素原子、又は、炭素数が１〜４の直鎖状アルキル基であることが好ましく、特に、Ｒがすべて水素原子である場合が好ましい。The component (A2) is a salt of a Lewis acid having a structure in which a fluorine atom and a phosphorus atom are bonded by a single bond, and an ammonium ion. The component (A2) is an etching component that erodes and removes the inorganic thin film. In the second aspect of the present invention, the etching component is preferably solid at room temperature (25 ° C.). The 2nd aspect of the composition of this invention has sufficient etching property even if it does not contain the organic acid or inorganic acid which was added to the conventional etching agent by containing a component (A2).
In the formula (1), four Rs are each independently a hydrogen atom, an aliphatic hydrocarbon group, or an arylalkyl group.
Examples of the aliphatic hydrocarbon group include a linear alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a branched alkyl group having 1 to 10 carbon atoms. Preferably, it is a C1-C7 linear alkyl group, Most preferably, it is a C1-C4 linear alkyl group.
As the arylalkyl (aralkyl) group, an alkyl chain having 1 to 4 carbon atoms and an aryl group having 6 to 10 carbon atoms is preferable. A benzyl group is preferred.
Each R is preferably independently a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and particularly preferably all R are hydrogen atoms.
Ｘはそれぞれ独立にＦ、Ｃｌ、Ｂｒ又はＩであり、Ｘの少なくとも１つはＦである。ＸはすべてＦであること、即ち、［ＰＸ６］−はヘキサフルオロリン酸イオン［ＰＦ６］−であることが好ましい。X is independently F, Cl, Br or I, and at least one of X is F. X is preferably all F, that is, [PX 6 ] − is preferably a hexafluorophosphate ion [PF 6 ] − .
成分（Ａ２）の具体例としては、ヘキサフルオロリン酸アンモニウム、ヘキサフルオロリン酸テトラメチルアンモニウム、ヘキサフルオロリン酸テトラエチルアンモニウム、ヘキサフルオロリン酸テトラ−ｎ−ブチルアンモニウム、ヘキサフルオロリン酸ベンジルトリメチルアンモニウム等が挙げられる。本発明の第２の態様では、特に、ヘキサフルオロリン酸アンモニウムが好ましい。 Specific examples of the component (A2) include ammonium hexafluorophosphate, tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, tetra-n-butylammonium hexafluorophosphate, benzyltrimethylammonium hexafluorophosphate, and the like. Is mentioned. In the second aspect of the present invention, ammonium hexafluorophosphate is particularly preferable.
成分（Ａ）の含有率は、使用時における組成物の性状を考慮して適宜調整すればよい。エッチング成分である成分（Ａ）の含有率は高い方が好ましいが、印刷法にて組成物を塗布することを考慮すると、組成物の粘度やペースト性状の調整が重要となる。エッチング成分（Ａ）の含有率は、組成物全体に対して５〜９０質量％であることが好ましく、７．５〜７５質量％であることがより好ましく、さらに、８〜４０質量％であることが好ましく、特に、１０〜３０質量％であることが特に好ましい。 What is necessary is just to adjust the content rate of a component (A) suitably in consideration of the property of the composition at the time of use. Although it is preferable that the content of the component (A) as an etching component is high, adjustment of the viscosity and paste properties of the composition is important in consideration of applying the composition by a printing method. The content of the etching component (A) is preferably 5 to 90% by mass, more preferably 7.5 to 75% by mass, and further 8 to 40% by mass with respect to the entire composition. It is particularly preferable that the content is 10 to 30% by mass.
成分（Ｂ）である溶媒は、上述した成分（Ａ）を分散できればよく、特に、制限はない。本発明の組成物をスクリーン印刷で印刷する場合には、印刷中に溶媒の揮発により粘度が変化すると印刷性が変化してしまうことから，２５℃における蒸気圧が１．３４×１０３Ｐａ未満、好ましくは、１．０×１０３Ｐａ・ｓ未満であることが好ましい。The solvent which is a component (B) should just disperse | distribute the component (A) mentioned above, and there is no restriction | limiting in particular. When printing the composition of the present invention by screen printing, if the viscosity changes due to volatilization of the solvent during printing, the printability changes, so the vapor pressure at 25 ° C. is less than 1.34 × 10 3 Pa. Preferably, it is less than 1.0 × 10 3 Pa · s.
溶媒の例としては、ノナン、デカン、ドデカン、テトラデカン等の脂肪族炭化水素系溶媒；エチルベンゼン、アニソール、メシチレン、ナフタレン、シクロヘキシルベンゼン、ジエチルベンゼン、フェニルアセトニトリル、フェニルシクロヘキサン、ベンゾニトリル、メシチレン等の芳香族炭化水素系溶媒；酢酸イソブチル、プロピオン酸メチル、プロピオン酸エチル、γ−ブチロラクトン、グリコールスルファイト、乳酸エチル、乳酸エチル等のエステル系溶媒；メタノール、エタノール、１−ブタノール、シクロヘキサノール、グリセリン等のアルコ−ル系溶媒；テルピネオール、ターピネオールＣ、ジヒドロターピネオール、ジヒドロターピニルアセテート、テルソルブＤＴＯ−２１０、テルソルブＴＨＡ−９０、テルソルブＴＨＡ−７０、テルソルブＴＯＥ−１００、ジヒドロキシターピニルオキシエタノール、ターピニルメチルエーテル、ジヒドロターピニルメチルエーテル、テルソルブＭＴＰＨ等のテルペン系溶媒；シクロヘキサノン、２−ヘキサノン、２−ヘプタノン、２−オクタノン、１，３−ジオキソラン−２−オン、１，５，５−トリメチルシクロヘキセン−３−オン等のケトン系溶媒；ジエチレングリコールエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテート、ジエチレングリコールプロピルエーテルアセテート、ジエチレングリコールイソプロピルエーテルアセテート、ジエチレングリコールブチルエーテルアセテート、ジエチレングリコール−ｔ−ブチルエーテルアセテート、トリエチレングリコールメチルエーテルアセテート、トリエチレングリコールエチルエーテルアセテート、トリエチレングリコールプロピルエーテルアセテート、トリエチレングリコールイソプロピルエーテルアセテート、トリエチレングリコールブチルエーテルアセテート、トリエチレングリコール−ｔ−ブチルエーテルアセテート、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノブチルエーテル、ポリエチレングリコール、ポリプロピレングリコール等のアルキレングリコール系溶媒；ジヘキシルエーテル、ブチルフェニルエーテル、ペンチルフェニルエーテル、メトキシトルエン、ベンジルエチルエーテル等のエーテル系溶媒；プロピレンカーボネート、エチレンカーボネート等のカーボネート系溶媒；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド系溶媒；ジメチルスルホキシド等のスルホキシド系溶媒；マロノニトリル等のニトリル系溶媒；水が例示できる。
なかでも、テルピネオール、テルソルブＭＴＰＨ，γ−ブチロラクトン、Ｎ−メチルピロリドン、グリコールスルファイト、プロピレンカーボネート、水が好ましい。
これらの溶媒は、１種を単独で又は２種以上を組み合わせて使用することができる。Examples of solvents include aliphatic hydrocarbon solvents such as nonane, decane, dodecane, and tetradecane; aromatic carbonization such as ethylbenzene, anisole, mesitylene, naphthalene, cyclohexylbenzene, diethylbenzene, phenylacetonitrile, phenylcyclohexane, benzonitrile, and mesitylene Hydrogen solvents: ester solvents such as isobutyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, glycol sulfite, ethyl lactate and ethyl lactate; alcohols such as methanol, ethanol, 1-butanol, cyclohexanol and glycerin Terpineol, terpineol C, dihydroterpineol, dihydroterpinel acetate, tersolve DTO-210, tersolve THA-90, tersolve THA- Terpene solvents such as 0, tersolve TOE-100, dihydroxyterpinyloxyethanol, terpinylmethyl ether, dihydroterpinylmethyl ether, tersolve MTPH; cyclohexanone, 2-hexanone, 2-heptanone, 2-octanone, 1 Ketone solvents such as 1,3-dioxolan-2-one and 1,5,5-trimethylcyclohexen-3-one; diethylene glycol ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, diethylene glycol ethyl ether acetate, die Tylene glycol propyl ether acetate, diethylene glycol isopropyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol-t-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate, Alkylene glycol solvents such as triethylene glycol butyl ether acetate, triethylene glycol-t-butyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether, polyethylene glycol, polypropylene glycol; Ether solvents such as ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether; carbonate solvents such as propylene carbonate and ethylene carbonate; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Examples include amide solvents such as pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as malononitrile; water.
Of these, terpineol, tersolve MTPH, γ-butyrolactone, N-methylpyrrolidone, glycol sulfite, propylene carbonate, and water are preferable.
These solvents can be used alone or in combination of two or more.
成分（Ｂ）の含有率は、使用時における組成物の性状を考慮して適宜調整すればよい。通常、組成物全体に対して、１０〜９５質量％が好ましく、１５〜７０質量％であることがより好ましく、２５〜５５質量％であることが特に好ましい。 What is necessary is just to adjust the content rate of a component (B) suitably considering the property of the composition at the time of use. Usually, 10-95 mass% is preferable with respect to the whole composition, it is more preferable that it is 15-70 mass%, and it is especially preferable that it is 25-55 mass%.
本発明の組成物は、上述した成分（Ａ）及び（Ｂ）の他に、ホウ素及び該ホウ素と結合したハロゲンとを構造中に含むルイス酸、前記ルイス酸の塩、並びに前記ルイス酸を発生する化合物から選択される少なくとも１つのホウ素化合物（以下、成分（Ｃ））を含有することが好ましい。成分（Ａ）及び成分（Ｃ）を含有する場合、低温によるエッチング性が向上し、また、エッチング速度も向上する。 In addition to the components (A) and (B) described above, the composition of the present invention generates a Lewis acid containing boron and a halogen bonded to the boron in the structure, a salt of the Lewis acid, and the Lewis acid. It is preferable to contain at least one boron compound (hereinafter referred to as component (C)) selected from the compounds to be prepared. When the component (A) and the component (C) are contained, the etching property at a low temperature is improved and the etching rate is also improved.
成分（Ｃ）の具体例としては、
テトラフルオロホウ酸トリフェニルカルベニウム、Ｎ−フルオロ−Ｎ’−クロロメチルトリエチレンジアミンビス（テトラフルオロホウ酸）、テトラフルオロホウ酸１−（クロロ−１−ピロリジニルメチレン）ピロリジニウム、テトラフルオロホウ酸トロピリウム、テトラフルオロホウ酸ジ−ｎ−ブチルアンモニウム、テトラフルオロホウ酸テトラエチルアンモニウム、テトラフルオロホウ酸テトラブチルアンモニウム、テトラフルオロホウ酸テトラメチルアンモニウム、テトラフルオロホウ酸トリメチルオキソニウム、テトラフルオロホウ酸トリエチルオキソニウム、１，３−ビス（２，４，６−トリメチルフェニル）−４，５−ジヒドロイミダゾリウムテトラフルオロホウ酸塩、１−ブチル−３−メチルイミダゾリウムテトラフルオロホウ酸塩、１−ヘキシル−３−メチルイミダゾリウムテトラフルオロホウ酸塩、１−エチル−３−メチルイミダゾリウムテトラフルオロホウ酸塩、１−エチル−２，３−ジメチルイミダゾリウムテトラフルオロホウ酸塩、１−ヘキシル−３−メチルイミダゾリウムテトラフルオロホウ酸塩、１−メチル−３−オクチルイミダゾリウムテトラフルオロホウ酸塩、１−ブチル−２，３−ジメチルイミダゾリウムテトラフルオロホウ酸塩、１，３−ジ−ｔｅｒｔ−ブチルイミダゾリニウムテトラフルオロホウ酸塩、１−ブチル−１−メチルピペリジニウムテトラフルオロホウ酸、１−ブチル−３−メチルピリジニウムテトラフルオロホウ酸塩、１−ブチルピリジニウムテトラフルオロホウ酸塩、テトラフルオロホウ酸２，４，６−トリメチルピリジニウム、１−ブチル−１−メチルピロリジニウムテトラフルオロホウ酸塩、１−エチル−１−メチルピロリジニウムテトラフルオロホウ酸塩、１−エチル−１−メチルピペリジニウムテトラフルオロホウ酸塩、トリシクロペンチルフォスフィンテトラフルオロホウ酸、等のテトラフルオロホウ酸有機塩基塩；
テトラフルオロホウ酸リチウム等のテトラフルオロホウ酸ハロゲン塩；
テトラフルオロホウ酸銅、テトラフルオロホウ酸亜鉛等のテトラフルオロホウ酸金属塩；
メチルトリフルオロホウ酸カリウム、（モルホリン−４−イル）メチルトリフルオロホウ酸カリウム、（３，３−ジメチルブチル）トリフルオロホウ酸カリウム、４−ヨードフェニルトリフルオロホウ酸カリウム、４−フルオロフェニルトリフルオロホウ酸カリウム、フェニルトリフルオロホウ酸カリウム、ピリジン−３−トリフルオロホウ酸カリウム、ビニルトリフルオロホウ酸カリウム、メチルトリフルオロホウ酸塩、［（Ｎ−ｔｅｒｔ−ブチルアンモニオ）メチル］トリフルオロホウ酸等のアルキルトリフルオロホウ酸塩；
三フッ化ホウ素モノエチルアミン錯体、三フッ化ホウ素−酢酸錯体、三フッ化ホウ素テトラヒドロフラン錯体、三フッ化ホウ素フェノール錯体、三フッ化ホウ素ジエチルエーテル錯体、三フッ化ホウ素アセトニトリル錯体や三フッ化ホウ素メタノール錯体等の三フッ化ホウ素錯体化合物；
テトラフルオロホウ酸ニトロニウム、三よう化ホウ素、トリス（ペンタフルオロフェニル）ボラン、テトラキス（ペンタフルオロフェニル）ホウ酸塩エチルエーテル錯体などが挙げられる。Specific examples of component (C) include
Triphenylcarbenium tetrafluoroborate, N-fluoro-N′-chloromethyltriethylenediaminebis (tetrafluoroboric acid), 1- (chloro-1-pyrrolidinylmethylene) pyrrolidinium tetrafluoroborate, tetrafluoroboric acid Tropylium, di-n-butylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, trimethyloxonium tetrafluoroborate, triethyloxotetrafluoroborate 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate Acid salt, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-octylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1,3 -Di-tert-butylimidazolinium tetrafluoroborate, 1-butyl-1-methylpiperidinium tetrafluoroborate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butylpyridinium tetrafluoro Borate, 2,4,6-trimethylpyridinium tetrafluoroborate 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, 1-ethyl-1-methylpiperidinium tetrafluoroborate, tri Tetrafluoroboric acid organic base salts such as cyclopentylphosphine tetrafluoroboric acid;
Tetrafluoroborate halogen salts such as lithium tetrafluoroborate;
Tetrafluoroborate metal salts such as copper tetrafluoroborate and zinc tetrafluoroborate;
Potassium methyltrifluoroborate, potassium (morpholin-4-yl) methyltrifluoroborate, potassium (3,3-dimethylbutyl) trifluoroborate, potassium 4-iodophenyltrifluoroborate, 4-fluorophenyltri Potassium fluoroborate, potassium phenyltrifluoroborate, potassium pyridine-3-trifluoroborate, potassium vinyltrifluoroborate, methyl trifluoroborate, [(N-tert-butylammonio) methyl] trifluoro Alkyl trifluoroborate salts such as boric acid;
Boron trifluoride monoethylamine complex, boron trifluoride-acetic acid complex, boron trifluoride tetrahydrofuran complex, boron trifluoride phenol complex, boron trifluoride diethyl ether complex, boron trifluoride acetonitrile complex and boron trifluoride methanol Boron trifluoride complex compounds such as complexes;
Examples thereof include nitronium tetrafluoroborate, boron triiodide, tris (pentafluorophenyl) borane, and tetrakis (pentafluorophenyl) borate ethyl ether complex.
上記のエッチング成分のうち、テトラフルオロホウ酸トリフェニルカルベニウム、テトラフルオロホウ酸トロピリウム、テトラフルオロホウ酸ジ−ｎ−ブチルアンモニウム、テトラフルオロホウ酸テトラブチルアンモニウム、テトラフルオロホウ酸トリメチルオキソニウム、テトラフルオロホウ酸トリエチルオキソニウム、１−エチル−２，３−ジメチルイミダゾリウムテトラフルオロホウ酸塩、１−ブチル−１−メチルピロリジニウムテトラフルオロホウ酸塩、メチルトリフルオロホウ酸カリウム、４−ヨードフェニルトリフルオロホウ酸カリウム、（４−メチル−１−ピペラジニル）メチルトリフルオロホウ酸カリウム、トリシクロペンチルフォスフィンテトラフルオロホウ酸、三フッ化ホウ素モノエチルアミン錯体、ピリジン−３−トリフルオロホウ酸カリウム、テトラフルオロホウ酸ニトロニウム、三よう化ホウ素、トリス（ペンタフルオロフェニル）ボラン、テトラキス（ペンタフルオロフェニル）ホウ酸リチウム エチルエーテル錯体が好ましい。特に、テトラフルオロホウ酸ジ−ｎ−ブチルアンモニウム、テトラフルオロホウ酸テトラブチルアンモニウム、三フッ化ホウ素モノエチルアミン錯体が好ましい。 Among the above etching components, triphenylcarbenium tetrafluoroborate, tropylium tetrafluoroborate, di-n-butylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, trimethyloxonium tetrafluoroborate, tetra Triethyloxonium fluoroborate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-1-methylpyrrolidinium tetrafluoroborate, potassium methyltrifluoroborate, 4-iodo Potassium phenyltrifluoroborate, potassium (4-methyl-1-piperazinyl) methyltrifluoroborate, tricyclopentylphosphine tetrafluoroborate, boron trifluoride monoethylamine complex, pyridine-3-to Potassium fluoroborate, nitronium tetrafluoroborate, triiodide, boron, tris (pentafluorophenyl) borane, lithium tetrakis (pentafluorophenyl) ethyl ether complex borate is preferred. In particular, di-n-butylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, and boron trifluoride monoethylamine complex are preferable.
成分（Ｃ）の含有率は、使用時における組成物の性状を考慮して適宜調整すればよい。例えば、組成物全体に対して１〜４０質量％であることが好ましく、さらに、２〜３０質量％であることが好ましく、特に、２．５〜１５質量％であることが好ましい。
尚、上述した成分（Ａ）と成分（Ｃ）の合計量は、組成物全体に対して５〜９０質量％であることが好ましく、さらに、７．５〜７５質量％であることが好ましく、特に、１５〜３５質量％であることが特に好ましい。What is necessary is just to adjust the content rate of a component (C) suitably considering the property of the composition at the time of use. For example, it is preferable that it is 1-40 mass% with respect to the whole composition, Furthermore, it is preferable that it is 2-30 mass%, and it is especially preferable that it is 2.5-15 mass%.
In addition, the total amount of the component (A) and the component (C) described above is preferably 5 to 90% by mass, more preferably 7.5 to 75% by mass with respect to the entire composition, Particularly preferred is 15 to 35% by mass.
本発明の組成物には、必要に応じて増粘剤及び微粒子（以下、成分（Ｄ））の少なくとも一方を添加してもよい。印刷法によっては、細線描画性のために組成物にチキソ性を付与することが好ましい。チキソ性を付与する方法としては、増粘剤（チキソ性付与剤）を使用する方法や、微粒子を分散する方法が挙げられる。これらの方法は、併用してもよい。 If necessary, at least one of a thickener and fine particles (hereinafter referred to as component (D)) may be added to the composition of the present invention. Depending on the printing method, it is preferable to impart thixotropy to the composition for fine line drawing. Examples of the method for imparting thixotropy include a method using a thickener (thixotropic agent) and a method for dispersing fine particles. These methods may be used in combination.
増粘剤は、エッチング成分等が溶媒に溶解又は分散した際に、水素結合等によりゆるい疑凝集を形成することによりチキソ性を付与する添加剤である。
増粘剤としては、エチルセルロース、κ−カラギナン、ステアリン酸アミド、カルボキシメチルセルロースアンモニウム、カルボキシメチルセルロースナトリウム、ＢＹＫ−４０５、４１０、４１１、４１５、４２０、４２５、４２０、４３０、４３１等（ビック・ケミー株式会社）、Ｄｉｓｐａｒｌｏｎチクソトロピック剤シリーズ（楠本化成）等の市販されているものが挙げられる。尚、チキソ性付与剤は、使用する溶媒と目的のチキソ性を得られれば、特に限定はない。
また、ポリシロキサン、ポリアクリル、ポリアミド、ポリビニルアルコール、アルキル変性セルロース、ペプチド、ポリペプチド、及びこれらのうち２つ以上の構造を有する共重合体も好ましい。A thickener is an additive that imparts thixotropy by forming loose aggregates due to hydrogen bonding or the like when an etching component or the like is dissolved or dispersed in a solvent.
Examples of thickeners include ethyl cellulose, κ-carrageenan, stearamide, carboxymethyl cellulose ammonium, sodium carboxymethyl cellulose, BYK-405, 410, 411, 415, 420, 425, 420, 430, 431, etc. (Bic Chemie Co., Ltd.) ) And Disparlon thixotropic agent series (Enomoto Kasei) and the like. The thixotropic agent is not particularly limited as long as the solvent to be used and the desired thixotropy can be obtained.
In addition, polysiloxane, polyacryl, polyamide, polyvinyl alcohol, alkyl-modified cellulose, peptide, polypeptide, and a copolymer having two or more of these structures are also preferable.
微粒子としては、有機微粒子や、金属酸化物粒子等の無機微粒子が挙げられる。微粒子を添加することで、粘度やチキソ性を適宜調整でき、印刷性（例えば、細線描画性や形状保持性）やエッチング性を制御することができる。また、無機薄膜のエッチング温度まで加熱すると、エッチング成分の一部は液状になるが、粒子により流動性が抑制され、印刷された組成物の形状が変形することを防ぐ。 Examples of the fine particles include organic fine particles and inorganic fine particles such as metal oxide particles. By adding fine particles, viscosity and thixotropy can be appropriately adjusted, and printability (for example, fine line drawing property and shape retention) and etching property can be controlled. When heated to the etching temperature of the inorganic thin film, some of the etching components become liquid, but the fluidity is suppressed by the particles, and the shape of the printed composition is prevented from being deformed.
有機微粒子としては例えば、ポリスチレンビーズ、ポリエチレン粒子、アクリル粒子、ポリシロキサン樹脂粒子、イソプレンゴム粒子、ポリアミド粒子、フルオロポリマー粒子を例示することができる。
無機微粒子としては、酸化銅、水酸化銅、酸化鉄、アルミナ、酸化亜鉛、酸化鉛、マグネシア、酸化スズ等の金属酸化物粒子、炭酸カルシウム、カーボン、シリカ、マイカ、スメクタイトを例示することができる。
また、表面が電気的に引き合う粒子であれば液状組成物中で疑凝集を形成することから、同様の効果が期待できる。Examples of the organic fine particles include polystyrene beads, polyethylene particles, acrylic particles, polysiloxane resin particles, isoprene rubber particles, polyamide particles, and fluoropolymer particles.
Examples of the inorganic fine particles include metal oxide particles such as copper oxide, copper hydroxide, iron oxide, alumina, zinc oxide, lead oxide, magnesia, tin oxide, calcium carbonate, carbon, silica, mica, and smectite. .
Further, if the surface is an electrically attracting particle, a similar effect can be expected because a pseudo-aggregation is formed in the liquid composition.
微粒子の一次粒子形状は、概球状、針状、板状、米粒状等から選択できる。特に、チキソ性付与を目的とする場合は、針状、板状、米粒状、数珠状の形状が好ましい。
尚、微粒子の分散のため、目的の機能を損なわない範囲で、分散助剤や分散安定剤を添加することができる。
微粒子の長径（長辺）は１０ｎｍ〜１０μｍが好ましい。
尚、微粒子の長径（長辺）はエッチング成分の粒径をＳＥＭ観察像から求める方法と同様の方法で求められる。The primary particle shape of the fine particles can be selected from a substantially spherical shape, a needle shape, a plate shape, a rice grain shape, and the like. In particular, for the purpose of imparting thixotropy, a needle shape, a plate shape, a rice grain shape, or a bead shape is preferable.
For dispersion of the fine particles, a dispersion aid or a dispersion stabilizer can be added as long as the target function is not impaired.
The major axis (long side) of the fine particles is preferably 10 nm to 10 μm.
The major axis (long side) of the fine particles is obtained by a method similar to the method for obtaining the particle size of the etching component from the SEM observation image.
成分（Ｄ）の含有率は、組成物全体に対して０．１〜８０質量％であることが好ましい。０．１質量％未満ではチキソ性の発現に十分な効果が得られない場合がある。一方、８０質量％を超えると粘度が高くなりすぎる場合がある。
成分（Ｄ）の含有率は、１０〜７０質量％であることが好ましく、特に、１５〜５０質量％であることが好ましい。It is preferable that the content rate of a component (D) is 0.1-80 mass% with respect to the whole composition. If it is less than 0.1% by mass, a sufficient effect for thixotropic expression may not be obtained. On the other hand, when it exceeds 80 mass%, a viscosity may become high too much.
The content of the component (D) is preferably 10 to 70% by mass, and particularly preferably 15 to 50% by mass.
本発明のエッチング組成物には、上述した各成分の他に、必要に応じて任意に、基板への濡れ性調整剤、粒子分散剤、脱泡剤、柚子肌等を防止するための外観向上剤（レベリング剤）、均一乾燥促進のための添加剤等の添加剤や、ドーピング剤、ｐＨ調整剤等を添加することができる。 In addition to the components described above, the etching composition of the present invention optionally improves the appearance to prevent wettability adjusting agents, particle dispersants, defoaming agents, cocoon skin, etc., as necessary. An additive (leveling agent), an additive such as an additive for promoting uniform drying, a doping agent, a pH adjusting agent, and the like can be added.
成分（Ａ）及び成分（Ｃ）は、印刷性向上のため、混合前の粒径が粒径１００μｍ以下であることが好ましい。
尚、ここでの粒径は数平均粒子径であり、ＳＥＭ観察像における重複せずランダムに選んだ１００個の平均値として求められる。具体的には、ＳＥＭの試料台上にカーボン粘着テープを貼り付け、その上にエッチング成分を振り掛ける。試料台上のエッチング成分のうち、粘着していないものをエアガンで吹き飛ばす。このエッチング成分の付着したＳＥＭ試料台に対し，真空スパッタ装置（例えばＩＯＮ ＳＰＵＴＴＥＲ、日立ハイテク製）を用いＰｔを１０〜２０ｎｍの厚みでスパッタしてＳＥＭ用サンプルとする。このＳＥＭ用サンプルをＳＥＭ装置（例えばＥＳＥＭ ＸＬ３０、Ｐｈｉｌｉｐｓ製）により、接着剤組成物硬化物の断面を印過電圧１０ｋＶで観察する。倍率は，平均的な導電性粒子の直径が視野の１割程度を占めように選ぶ。観察された粒子像の中から重なって外形の確認できないエッチング成分を除いた中からランダムに１００個選び、それぞれのエッチング成分像対し外接する並行二直線のうち最大距離となるように選んだ並行二直線間距離を計測する。これら１００個の値に対して平均値を求め数平均粒子径とする。尚、１視野の中から１００個の粒子が選べない場合には複数視野から計測する。The component (A) and the component (C) preferably have a particle size of 100 μm or less before mixing in order to improve printability.
In addition, the particle size here is a number average particle size, and is obtained as an average value of 100 randomly selected without overlapping in the SEM observation image. Specifically, a carbon adhesive tape is affixed on the SEM sample stage, and an etching component is sprinkled thereon. Of the etching components on the sample stage, those that are not adhered are blown off with an air gun. Using a vacuum sputtering apparatus (for example, ION SPUTTER, manufactured by Hitachi High-Tech), Pt is sputtered with a thickness of 10 to 20 nm on the SEM sample stage to which the etching component is adhered to obtain a sample for SEM. The cross section of the cured adhesive composition is observed with an overvoltage of 10 kV using a SEM apparatus (for example, ESEM XL30, manufactured by Philips). The magnification is selected so that the average conductive particle diameter occupies about 10% of the field of view. 100 particles are randomly selected from the observed particle images that are overlapped and the outer shape cannot be confirmed, and parallel two lines selected so as to have the maximum distance among the two parallel lines circumscribing each etching component image. Measure the distance between straight lines. An average value is obtained for these 100 values and is defined as the number average particle diameter. When 100 particles cannot be selected from one field of view, measurement is performed from a plurality of fields.
また、分散後の成分（Ａ）及び（Ｃ）の粒径（分散粒径）はスクリーン印刷精度の点から１００μｍが好ましく、粘度特性の点から０．０１μｍ以上であることが好ましい。
尚、分散粒径はレーザー散乱法粒度分布測定装置を用い体積平均粒径として求められる。具体的には，ユニバーサルリキッドモジュールを装着したレーザー散乱法粒度分布測定装置（例えば、ＬＳ１３ ３２０，ベックマンコールタ製）を用い、光源の安定のため本体電源を入れて３０分間放置した後、リキッドモジュールにペースト組成物で用いている溶媒のみを測定プログラムからＲｉｎｓｅコマンドにより導入し、測定プログラムからＤｅ−ｂｕｂｂｌｅ，Ｍｅａｓｕｒｅ Ｏｆｆｓｅｔ，Ａｌｉｇｎ，Ｍｅａｓｕｒｅ Ｂａｃｋｇｒｏｕｎｄを行う。続いて、測定プログラムのＭｅａｓｕｒｅ Ｌｏａｄｉｎｇを用い、ペースト組成物をリキッドモジュールに測定プログラムがサンプル量ＬｏｗからＯＫになるまで添加する。その後、測定プログラムからＭｅａｓｕｒｅを行い、粒度分布を取得する。レーザー散乱法粒度分布測定装置の設定として、Ｐｕｍｐ Ｓｐｅｅｄ：７０％、Ｉｎｃｌｕｄｅ ＰＩＤＳ ｄａｔａ： ＯＮ、Ｒｕｎ Ｌｅｎｇｔｈ： ９０ ｓｅｃｏｎｄｓを用いる。分散媒及び分散質の屈折率には、エッチング成分及び溶媒の屈折率をそれぞれ用いる。Further, the particle diameter (dispersed particle diameter) of the components (A) and (C) after dispersion is preferably 100 μm from the viewpoint of screen printing accuracy, and preferably 0.01 μm or more from the viewpoint of viscosity characteristics.
The dispersed particle diameter is obtained as a volume average particle diameter using a laser scattering particle size distribution analyzer. Specifically, using a laser scattering particle size distribution measuring apparatus (for example, LS13 320, manufactured by Beckman Coulter) equipped with a universal liquid module, the liquid module is left for 30 minutes after the main unit is turned on to stabilize the light source. Only the solvent used in the paste composition is introduced from the measurement program by the Rinse command, and De-bubble, Measurement Offset, Align, and Measurement Background are performed from the measurement program. Subsequently, using the measurement program Measurement Loading, the paste composition is added to the liquid module until the measurement program reaches the OK from the sample amount Low. Thereafter, Measurement is performed from the measurement program to obtain a particle size distribution. As settings of the laser scattering method particle size distribution measuring apparatus, Pump Speed: 70%, Include PIDS data: ON, and Run Length: 90 seconds are used. As the refractive index of the dispersion medium and the dispersoid, the refractive indexes of the etching component and the solvent are used, respectively.
本発明のエッチング組成物は、上述した成分（Ａ）及び（Ｂ）、並びに、必要に応じて配合される成分（Ｃ）及び（Ｄ）、その他、上記添加剤等を混合することにより製造できる。
尚、本発明の組成物は、上記成分（Ａ）及び（Ｂ）と、任意に上述した成分（Ｃ）、（Ｄ）及び添加剤の少なくとも１つから実質的になっていてもよく、また、これらの成分のみからなっていてもよい。「実質的になる」とは、上記組成物が、主に上記成分（Ａ）及び（Ｂ）と、任意に上述した成分（Ｃ）、（Ｄ）、及び添加剤の少なくとも１つからからなること、例えば、これら成分が原料全体に対し、９０質量％以上、９５質量％以上、又は９８質量％以上であることを意味する。The etching composition of the present invention can be produced by mixing the components (A) and (B) described above, the components (C) and (D) blended as necessary, and other additives as described above. .
The composition of the present invention may consist essentially of the above components (A) and (B) and optionally at least one of the above components (C), (D) and additives, , Or may be composed only of these components. “Substantially” means that the composition mainly comprises the components (A) and (B) and optionally at least one of the components (C), (D), and additives described above. For example, it means that these components are 90% by mass or more, 95% by mass or more, or 98% by mass or more with respect to the whole raw material.
組成物の均一性を向上させるために、プロペラ撹拌、超音波分散装置（例、日本精機製作所製、超音波ホモジナイザー）、自転公転ミキサー（例、シンキー製、泡取り錬太郎）、高速乳化・分散機（例、プライミクス社製ＴＫホモミクサーシリーズ）、らいかい機、３本ロールミル、ビーズミル、サンドミル、ポットミル等の分散機を使用して混合させることが好ましい。尚、分散はこれら装置を単独で、又は組合せて実施することができる。
分散後、組成物中に気泡が発生した場合は、減圧下への放置、減圧下での撹拌脱泡等により組成物中の気泡を除去することができる。In order to improve the uniformity of the composition, propeller agitation, ultrasonic dispersing device (eg, Nippon Seiki Seisakusho, ultrasonic homogenizer), revolving mixer (eg, Shinky, Foaming Rentaro), high-speed emulsification / dispersion It is preferable to mix using a disperser such as a machine (eg, TK homomixer series manufactured by PRIMIX Co., Ltd.), a rake machine, a three-roll mill, a bead mill, a sand mill, or a pot mill. In addition, dispersion | distribution can implement these apparatuses individually or in combination.
If air bubbles are generated in the composition after dispersion, the air bubbles in the composition can be removed by standing under reduced pressure, stirring and degassing under reduced pressure, or the like.
本発明のエッチング組成物は、無機薄膜、例えば、ケイ素化合物膜、又はシリコン（ケイ素）膜のエッチングに好適に使用できる。ケイ素化合物としては、窒化ケイ素、酸化ケイ素、ホウ化ケイ素、ガラス（クオーツ、窓ガラス、ホウケイ酸ガラス、無アルカリガラス）を例示できる。使用目的よっては不純物を含んでもよく、酸化されていてもよい。また、結晶、非晶の状態は問わず、表面の形状も問わない。 The etching composition of the present invention can be suitably used for etching an inorganic thin film such as a silicon compound film or a silicon (silicon) film. Examples of the silicon compound include silicon nitride, silicon oxide, silicon boride, and glass (quartz, window glass, borosilicate glass, and alkali-free glass). Depending on the purpose of use, it may contain impurities or may be oxidized. Moreover, the shape of the surface is not ask | required regardless of a crystal | crystallization and an amorphous state.
本発明のエッチング組成物は、特に、窒化ケイ素（ＳｉＮ）膜を選択的にエッチングすることができる。例えば、本発明のエッチング組成物のＳｉＮ膜のエッチング速度は、酸化ケイ素膜のエッチング速度よりも格段に速い。ＳｉＮ膜は、ＣＭＯＳ等の半導体素子の層間絶縁膜、パッシベーション膜等や、太陽電池等の反射防止膜等として使用されている。ＳｉＮ膜は化学蒸着法（ＣＶＤ）等、公知の方法で形成される。尚、「ＳｉＮ」は化学量論比（Ｓｉ：Ｎ）が１：１であることを意味するものではない。 In particular, the etching composition of the present invention can selectively etch a silicon nitride (SiN) film. For example, the etching rate of the SiN film of the etching composition of the present invention is much faster than the etching rate of the silicon oxide film. The SiN film is used as an interlayer insulating film of a semiconductor element such as a CMOS, a passivation film, an antireflection film of a solar cell, or the like. The SiN film is formed by a known method such as chemical vapor deposition (CVD). “SiN” does not mean that the stoichiometric ratio (Si: N) is 1: 1.
本発明の無機薄膜の除去方法は、上述した本発明のエッチング組成物を使用して、無機薄膜を除去する工程を有する。例えば、本発明の組成物を、印刷法により無機薄膜上に塗布する工程（印刷工程）と、加熱により無機薄膜を除去する工程（エッチング工程）と、を有する方法が挙げられる。 The method for removing an inorganic thin film of the present invention includes a step of removing the inorganic thin film using the above-described etching composition of the present invention. For example, the method which has the process (printing process) of apply | coating the composition of this invention on an inorganic thin film with a printing method, and the process (etching process) of removing an inorganic thin film by heating is mentioned.
印刷方法としては、例えば、有版印刷として、スクリーン印刷、フレキソ印刷、マイクロコンタクトプリント等、無版印刷として、インクジェット印刷、スリット印刷、ディスペンサ印刷等が適用できる。
なかでも、非接触でパターニング可能な印刷方法が、印刷圧力の印加による基板の損傷を回避できるため好ましい。As the printing method, for example, plate printing, screen printing, flexographic printing, microcontact printing, etc., and plateless printing, inkjet printing, slit printing, dispenser printing, etc. can be applied.
In particular, a printing method capable of patterning without contact is preferable because damage to the substrate due to application of a printing pressure can be avoided.
エッチング組成物の粘度は、印刷方法や印刷装置に依存することから、特に限定されず、各々の印刷法に適するように調製することができる。
例えば、スクリーン印刷では２５℃における粘度が、１００ｍＰａ・ｓ以上であることが好ましく、特に、１Ｐａ・ｓ以上であることが好ましい。
インクジェット印刷では、３〜２０ｍＰａ・ｓが一般的に好ましい範囲である。Since the viscosity of the etching composition depends on the printing method and the printing apparatus, it is not particularly limited and can be prepared so as to be suitable for each printing method.
For example, in screen printing, the viscosity at 25 ° C. is preferably 100 mPa · s or more, and particularly preferably 1 Pa · s or more.
In inkjet printing, 3 to 20 mPa · s is generally a preferred range.
印刷工程では、上述した公知の印刷法により、ペースト組成物をケイ素化合物上の所望のパターンを形成する。パターンの下部に位置するケイ素化合物が最終的に除去（エッチング）される。
印刷後、必要であれば加熱や減圧により、ペースト組成物の溶媒を揮発、除去する。溶媒の除去は、エッチング工程における加熱と兼ねてもよいが、それぞれの温度条件が異なる場合もあるため、適宜選択する。In the printing step, the paste composition is formed into a desired pattern on the silicon compound by the known printing method described above. The silicon compound located at the bottom of the pattern is finally removed (etched).
After printing, if necessary, the solvent of the paste composition is volatilized and removed by heating or reduced pressure. The removal of the solvent may be combined with the heating in the etching step, but is appropriately selected because each temperature condition may be different.
エッチング工程では、通常１００〜２５０℃、より好ましくは１００〜２２０℃、特に好ましくは１２０〜１８０℃で、通常１〜６０分間加熱することが好ましい。２５０℃を超えると、例えば、太陽電池の場合、ｎ＋層等の内にドープされているドーパントが拡散し、Ｐ型／Ｎ型界面に相互拡散層が生じ、太陽電池の特性が低下する場合がある。 In an etching process, it is preferable that it is normally 100-250 degreeC, More preferably, it is 100-220 degreeC, Most preferably, it is 120-180 degreeC, and it is preferable to heat for 1 to 60 minutes normally. When the temperature exceeds 250 ° C., for example, in the case of a solar cell, the dopant doped in the n + layer or the like diffuses, and an interdiffusion layer is formed at the P-type / N-type interface, which may deteriorate the characteristics of the solar cell. is there.
エッチング工程後、残留物がある場合は、残留物を取り除くための洗浄工程を設ける。
洗浄工程としては、純水を用いた超音波洗浄、ブラシ洗浄、スプレー洗浄、流水洗浄等が挙げられる。If there is a residue after the etching process, a cleaning process is provided to remove the residue.
Examples of the cleaning step include ultrasonic cleaning using pure water, brush cleaning, spray cleaning, running water cleaning, and the like.
基板上に形成された無機薄膜を、本発明の方法でパターン状にエッチングすることにより、本発明の基板が得られる。無機薄膜を形成した基板としては、Ｓｉを主成分とする場合、ガラス（クオーツ、窓ガラス、ホウケイ酸ガラス、無アルカリガラス）、シリコンウェハ等を例示できる。また、樹脂基板でもよい。
本発明の基板は、各種半導体装置や太陽電池セルの中間加工品となる。例えば、太陽電池セルの場合、受光面及び／又は裏面上に本発明のエッチング組成物を任意のパターンに印刷し、そのパターン状にＳｉＮ等の無機薄膜を除去し、金属ペースト等使用して給電配線（電極）を形成することにより太陽電池セルが作製できる。尚、露出したシリコン表面にリン等のドーパントをドーピングしてｎ＋部を形成してもよい。The substrate of the present invention is obtained by etching the inorganic thin film formed on the substrate into a pattern by the method of the present invention. Examples of the substrate on which the inorganic thin film is formed include glass (quartz, window glass, borosilicate glass, non-alkali glass), silicon wafer, and the like when Si is the main component. A resin substrate may also be used.
The substrate of the present invention is an intermediate processed product for various semiconductor devices and solar cells. For example, in the case of a solar cell, the etching composition of the present invention is printed in an arbitrary pattern on the light receiving surface and / or the back surface, an inorganic thin film such as SiN is removed in the pattern, and power is supplied using a metal paste or the like. A solar battery cell can be manufactured by forming wiring (electrode). The n + portion may be formed by doping an exposed silicon surface with a dopant such as phosphorus.
実施例Ａ１
（１）組成物（エッチングペースト）の調製
ヘキサフルオロリン酸ナトリウム（和光純薬工業株式会社製）１．５４ｇ、三フッ化ホウ素モノエチルアミン錯体（和光純薬工業株式会社製）０．３９ｇ、長粒状の酸化アルミニウムナノ粒子（昭和電工株式会社製）３．２ｇ、κ−カラジーナン（和光純薬工業株式会社製）０．３９ｇ、純水２．２４ｇ、ポリエチレングリコール（和光純薬工業株式会社製）２．２４ｇをメノウ乳鉢で混ぜ合わせて，超音波ホモジナイザ（株式会社日本精機製作所製）にて分散させた後エッチングペーストを得た。Example A1
(1) Preparation of composition (etching paste) 1.54 g of sodium hexafluorophosphate (Wako Pure Chemical Industries, Ltd.), boron trifluoride monoethylamine complex (Wako Pure Chemical Industries, Ltd.) 0.39 g, long Granular aluminum oxide nanoparticles (Showa Denko Co., Ltd.) 3.2 g, κ-carrageenan (Wako Pure Chemical Industries, Ltd.) 0.39 g, pure water 2.24 g, polyethylene glycol (Wako Pure Chemical Industries, Ltd.) 2.24 g was mixed in an agate mortar and dispersed with an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain an etching paste.
（２）エッチングペーストの印刷及びＳｉＮ膜のエッチング
鏡面上にＰＥ−ＣＶＤ（プラズマＣＶＤ）によりＳｉＯ２膜を１５０ｎｍ、及び、ＳｉＮ膜を９０ｎｍ積層したＰ型シリコンウェハ（１〜５０Ω）（水戸精工株式会社）をＳｉＮ付きシリコン基板として用いた。
エッチングペーストをスクリーン印刷により、幅が７５μｍ、１００μｍ、及び１５０μｍである直線を印刷した。
印刷したＳｉＮ膜付きシリコン基板を、１７０℃に加熱したホットプレート上で５分加熱処理した後、放冷し、超純水中で超音波洗浄した。
エッチング処理後のＳｉＮ付きシリコン基板では、印刷部の下部のＳｉＮ膜が除去されていた。
印刷部の線幅とエッチング部の線幅の実測値を表１に示す。また、図１に線幅１００μｍでエッチングペーストを印刷したＳｉＮ付きシリコン基板のエッチング後の写真を示す。(2) 150 nm of SiO 2 film by PE-CVD on the etching mirror surface of the print and the SiN film of the etching paste (plasma CVD), and, P-type silicon wafer an SiN film was 90nm laminated (1～50Omu) (Mito Seiko stock Company) was used as a silicon substrate with SiN.
A straight line having a width of 75 μm, 100 μm, and 150 μm was printed by screen printing of the etching paste.
The printed silicon substrate with the SiN film was heat-treated on a hot plate heated to 170 ° C. for 5 minutes, then allowed to cool and ultrasonically cleaned in ultrapure water.
In the SiN-attached silicon substrate after the etching process, the SiN film at the lower part of the printing part has been removed.
Table 1 shows the measured values of the line width of the printed part and the line width of the etched part. Moreover, the photograph after the etching of the silicon substrate with SiN which printed the etching paste with the line | wire width of 100 micrometers in FIG. 1 is shown.
比較例Ａ１
三フッ化ホウ素モノエチルアミン錯体１．９３ｇ、長粒状の酸化アルミニウムナノ粒子３．２ｇ、κ−カラジーナン０．３９ｇ、純水２．２４ｇ、ポリエチレングリコール２．２４ｇをメノウ乳鉢で混ぜ合わせて、エッチングペーストを得た。
実施例Ａ１と同様に窒化ケイ素膜付きシリコン基板上にスクリーン印刷を行い、１７０℃で５分加熱し、超音波洗浄を行った。
その結果、印刷部下部のＳｉＮ膜はエッチングされなかった。Comparative Example A1
Etching paste by mixing 1.93 g of boron trifluoride monoethylamine complex, 3.2 g of long granular aluminum oxide nanoparticles, 0.39 g of κ-carrageenan, 2.24 g of pure water and 2.24 g of polyethylene glycol in an agate mortar. Got.
Screen printing was performed on a silicon substrate with a silicon nitride film in the same manner as in Example A1, and heating was performed at 170 ° C. for 5 minutes to perform ultrasonic cleaning.
As a result, the SiN film under the printing part was not etched.
実施例Ｂ１
（１）エッチング組成物（エッチングペースト）の調製
ヘキサフルオロリン酸アンモニウム（和光純薬工業株式会社製）１．５０ｇ及び三フッ化ホウ素モノエチルアミン錯体０．３８ｇに、純水１．４５ｇ、ポリエチレングリコール２．９０ｇを加え、５０℃程度に加熱し固体を溶解させた。これにカルボキシメチルセルロースアンモニウム（和光純薬工業株式会社製）０．６３ｇを加え、撹拌し溶液を得た。１００ｍｌのポリ容器に長粒状の酸化銅粒子（自社合成：粒子径２００ｎｍ、アスペクト比３）３．１３ｇ秤量し、先に調製した溶液を加え、水浴で冷却しながら超音波ホモジナイザを用い、出力６００Ｗ/振動数１９．５ｋＨｚ/振幅数２６．５μｍで、途中スパチュラを用いて撹拌しながら合計３分間(１分×３回)分散処理しエッチングペーストを得た。Example B1
(1) Preparation of etching composition (etching paste) 1.50 g of ammonium hexafluorophosphate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.38 g of boron trifluoride monoethylamine complex, 1.45 g of pure water, polyethylene glycol 2.90 g was added and heated to about 50 ° C. to dissolve the solid. To this, 0.63 g of carboxymethyl cellulose ammonium (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain a solution. Weigh out 3.13 g of long-grained copper oxide particles (in-house synthesis: particle size 200 nm, aspect ratio 3) in a 100 ml plastic container, add the solution prepared above, and use an ultrasonic homogenizer while cooling in a water bath, output 600 W / A vibration frequency of 19.5 kHz / amplitude number of 26.5 μm, and a dispersion treatment was performed for a total of 3 minutes (1 minute × 3 times) while stirring with a spatula on the way to obtain an etching paste.
（２）エッチングペーストの印刷及びＳｉＮ膜のエッチング
鏡面上にＰＥ−ＣＶＤにより酸化ケイ素（ＳｉＯ２）膜を１５０ｎｍ、及び、ＳｉＮ膜を９０ｎｍ積層したＰ型シリコンウェハ（１〜５０Ω）をＳｉＮ付きシリコン基板として用いた。
エッチングペーストを用いて、スクリーン印刷により、幅が７５μｍ、１００μｍ、及び１５０μｍである直線を印刷した。
印刷したＳｉＮ膜付きシリコン基板を、１６０℃に加熱したホットプレート上で５分加熱処理した後、放冷し、超純水中で超音波洗浄した。
エッチング処理後のＳｉＮ付きシリコン基板では、印刷部の下部のＳｉＮ膜が除去されていた。
印刷部の線幅とエッチング部の線幅の実測値を表２に示す。また、図２に線幅１００μｍでエッチングペーストを印刷したＳｉＮ付きシリコン基板のエッチング後の写真を示す。(2) Etching paste printing and SiN film etching A P-type silicon wafer (1-50Ω) in which a silicon oxide (SiO 2 ) film of 150 nm and a SiN film of 90 nm are laminated on a mirror surface by PE-CVD is applied to silicon with SiN. Used as a substrate.
Using the etching paste, straight lines having widths of 75 μm, 100 μm, and 150 μm were printed by screen printing.
The printed silicon substrate with the SiN film was heat-treated on a hot plate heated to 160 ° C. for 5 minutes, then allowed to cool and ultrasonically cleaned in ultrapure water.
In the SiN-attached silicon substrate after the etching process, the SiN film at the lower part of the printing part has been removed.
Table 2 shows measured values of the line width of the printed portion and the line width of the etched portion. Moreover, the photograph after the etching of the silicon substrate with SiN which printed the etching paste with the line | wire width of 100 micrometers in FIG. 2 is shown.
実施例Ｂ２
ヘキサフルオロリン酸アンモニウム２．０ｇ、三フッ化ホウ素モノエチルアミン錯体０．５０ｇ、長粒状のアルミナ粒子（昭和電工株式会社製：粒子径５００ｎｍ、アスペクト比２）３．２ｇ、カルボキシメチルセルロースアンモニウム０．４０ｇ、純水１．３ｇ、ポリエチレングリコール２．６０ｇをメノウ乳鉢で混ぜ合わせて、超音波ホモジナイザにて分散させて、エッチングペーストを得た。
実施例Ｂ１と同様に窒化ケイ素膜付きシリコン基板上にスクリーン印刷を行い、１６０℃で５分加熱し、超音波洗浄を行った。
印刷部の線幅とエッチング部の線幅の実測値を表３に示す。また、図３に線幅１００μｍでエッチングペーストを印刷したＳｉＮ付きシリコン基板のエッチング後の写真を示す。Example B2
2.0 g of ammonium hexafluorophosphate, 0.50 g of boron trifluoride monoethylamine complex, 3.2 g of long granular alumina particles (manufactured by Showa Denko KK: particle diameter 500 nm, aspect ratio 2), 0.40 g of carboxymethyl cellulose ammonium Then, 1.3 g of pure water and 2.60 g of polyethylene glycol were mixed in an agate mortar and dispersed with an ultrasonic homogenizer to obtain an etching paste.
Screen printing was performed on a silicon substrate with a silicon nitride film in the same manner as in Example B1, and heating was performed at 160 ° C. for 5 minutes to perform ultrasonic cleaning.
Table 3 shows actually measured values of the line width of the printed portion and the line width of the etched portion. FIG. 3 shows a photograph after etching of the SiN-attached silicon substrate on which an etching paste is printed with a line width of 100 μm.
比較例Ｂ１
比較例Ａ１と同様にして、エッチングペーストを得た。
実施例Ｂ１と同様に窒化ケイ素膜付きシリコン基板上にスクリーン印刷を行い、１６０℃で５分加熱し、超音波洗浄を行った。
その結果、印刷部下部のＳｉＮ膜はエッチングされなかった。Comparative Example B1
An etching paste was obtained in the same manner as in Comparative Example A1.
Screen printing was performed on a silicon substrate with a silicon nitride film in the same manner as in Example B1, and heating was performed at 160 ° C. for 5 minutes to perform ultrasonic cleaning.
As a result, the SiN film under the printing part was not etched.
実施例Ａ１及び比較例Ａ１の結果から、また、実施例Ｂ１、Ｂ２及び比較例Ｂ１の結果から、本発明の組成物は比較的低い温度で、簡便に無機薄膜をエッチングすることができることがわかる。 From the results of Example A1 and Comparative Example A1, and from the results of Examples B1, B2 and Comparative Example B1, it can be seen that the composition of the present invention can easily etch an inorganic thin film at a relatively low temperature. .
本発明のエッチング組成物は、無機薄膜、特にケイ素化合物膜の除去に好適である。
本発明のケイ素化合物を除去する方法は、各種半導体素子や太陽電池の製造工程に使用できる。The etching composition of the present invention is suitable for removing inorganic thin films, particularly silicon compound films.
The method for removing a silicon compound of the present invention can be used in the production process of various semiconductor elements and solar cells.
上記に本発明の実施形態及び／又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び／又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.
Claims (13)
ホウ素及び該ホウ素と結合したハロゲンとを構造中に含むルイス酸、前記ルイス酸の塩、並びに前記ルイス酸を発生する化合物から選択される少なくとも１つのホウ素化合物と、
溶媒と、
を含有し、
前記フッ素原子とリン原子が単結合で結合した構造を有する陰イオンと、陽イオンからなる塩の含有率が、全体に対して、５〜９０質量％であり、ＳｉＮ膜エッチング用であるエッチング組成物。 An anion having a structure in which a fluorine atom and a phosphorus atom are bonded by a single bond, and a salt composed of a cation,
At least one boron compound selected from a Lewis acid containing boron and a halogen bonded to the boron in the structure, a salt of the Lewis acid, and a compound that generates the Lewis acid;
A solvent,
Containing
And an anion which the fluorine atom and a phosphorus atom has a structure bonded by a single bond, the content of the salt comprising cations, for the entire, Ri 5 to 90% by mass, Ru der for SiN film etching Etching composition.
ホウ素及び該ホウ素と結合したハロゲンとを構造中に含むルイス酸、前記ルイス酸の塩、並びに前記ルイス酸を発生する化合物から選択される少なくとも１つのホウ素化合物と、
溶媒と、
を含有するエッチング組成物。
［ＮＲ４］＋・［ＰＸ６］− （１）
（式中、Ｒは水素原子であり、Ｘはそれぞれ独立にＦ、Ｃｌ、Ｂｒ又はＩであり、Ｘの少なくとも１つはＦである。） A compound represented by the following general formula (1), which is a salt of an ammonium ion and a phosphate ion;
At least one boron compound selected from a Lewis acid containing boron and a halogen bonded to the boron in the structure, a salt of the Lewis acid, and a compound that generates the Lewis acid;
A solvent,
An etching composition containing
[NR 4 ] + · [PX 6 ] − (1)
(Wherein R is a hydrogen atom, X is independently F, Cl, Br or I, and at least one of X is F.)
前記塗布後に加熱することにより、ＳｉＮ膜を除去する工程と、を有する、請求項１０に記載のＳｉＮ膜の除去方法。 Applying the composition according to claim 1 onto a SiN film by a printing method;
The method of removing the SiN film according to claim 10, further comprising: removing the SiN film by heating after the application.
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| JP2013116099 | 2013-05-31 | ||
| JP2013116098 | 2013-05-31 | ||
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| JP2013116098 | 2013-05-31 | ||
| PCT/JP2014/002702 WO2014192266A1 (en) | 2013-05-31 | 2014-05-22 | Etching composition |
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| GB2276349A (en) * | 1993-03-25 | 1994-09-28 | Ciba Geigy Ag | Printing of porous substrates. |
| GB2373367A (en) * | 2000-12-12 | 2002-09-18 | Univ Montfort | Formation and processing of porous semiconductors using etching solution of oxidant and fluorine-containing Lewis acid |
| DE10150040A1 (en) | 2001-10-10 | 2003-04-17 | Merck Patent Gmbh | Etching passivating and antireflection layers made from silicon nitride on solar cells comprises applying a phosphoric acid and/or etching medium containing a salt of phosphoric acid the surface regions to be etched |
| JP2005162786A (en) * | 2003-11-28 | 2005-06-23 | Mitsubishi Gas Chem Co Inc | Cleaning liquid composition |
| JP4225548B2 (en) * | 2004-01-06 | 2009-02-18 | 三菱瓦斯化学株式会社 | Etching solution composition and etching method |
| DE102005007743A1 (en) | 2005-01-11 | 2006-07-20 | Merck Patent Gmbh | Printable medium for the etching of silicon dioxide and silicon nitride layers |
| US9058975B2 (en) * | 2006-06-09 | 2015-06-16 | Lam Research Corporation | Cleaning solution formulations for substrates |
| CN101639769B (en) * | 2008-07-30 | 2013-03-06 | 国际商业机器公司 | Method and device for splitting and sequencing dataset in multiprocessor system |
| WO2010022849A2 (en) * | 2008-09-01 | 2010-03-04 | Merck Patent Gmbh | Edge deletion of thin-layer solar modules by etching |
| WO2010139390A1 (en) * | 2009-06-04 | 2010-12-09 | Merck Patent Gmbh | Two component etching |
| EP2499277B1 (en) * | 2009-11-09 | 2017-09-27 | Carnegie Mellon University | Metal ink compositions, conductive patterns, methods, and devices |
| JP2013533631A (en) * | 2010-07-16 | 2013-08-22 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Aqueous cleaning agent to remove residues after etching |
| JP2012033561A (en) * | 2010-07-28 | 2012-02-16 | Sanyo Chem Ind Ltd | Etchant for silicon nitride |
| JP2012099550A (en) * | 2010-10-29 | 2012-05-24 | Sanyo Chem Ind Ltd | Etchant for silicon nitride |
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