KR20140011354A - Coating liquid for diffusing impurity - Google Patents
Coating liquid for diffusing impurity Download PDFInfo
- Publication number
- KR20140011354A KR20140011354A KR1020137025806A KR20137025806A KR20140011354A KR 20140011354 A KR20140011354 A KR 20140011354A KR 1020137025806 A KR1020137025806 A KR 1020137025806A KR 20137025806 A KR20137025806 A KR 20137025806A KR 20140011354 A KR20140011354 A KR 20140011354A
- Authority
- KR
- South Korea
- Prior art keywords
- coating liquid
- impurity
- group
- pva
- diffusion
- Prior art date
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- 238000000576 coating method Methods 0.000 title claims abstract description 103
- 239000011248 coating agent Substances 0.000 title claims abstract description 101
- 239000007788 liquid Substances 0.000 title claims abstract description 85
- 239000012535 impurity Substances 0.000 title claims abstract description 73
- 238000009792 diffusion process Methods 0.000 claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 42
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 42
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 32
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000007127 saponification reaction Methods 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000010419 fine particle Substances 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 229910052696 pnictogen Inorganic materials 0.000 claims description 9
- 229910052795 boron group element Inorganic materials 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 55
- 239000000758 substrate Substances 0.000 abstract description 35
- 238000007650 screen-printing Methods 0.000 abstract description 17
- 238000007639 printing Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- -1 phosphorus compound Chemical class 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 20
- 229910052698 phosphorus Inorganic materials 0.000 description 19
- 239000011574 phosphorus Substances 0.000 description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000013329 compounding Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000000180 1,2-diols Chemical group 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- MWWXARALRVYLAE-UHFFFAOYSA-N 2-acetyloxybut-3-enyl acetate Chemical compound CC(=O)OCC(C=C)OC(C)=O MWWXARALRVYLAE-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 235000010338 boric acid Nutrition 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000003254 anti-foaming effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
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- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- 239000004254 Ammonium phosphate Substances 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KIOOPXXIFXEVLQ-UHFFFAOYSA-N Cl[P]Cl Chemical class Cl[P]Cl KIOOPXXIFXEVLQ-UHFFFAOYSA-N 0.000 description 1
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- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
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- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
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- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/2225—Diffusion sources
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/228—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a liquid phase, e.g. alloy diffusion processes
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- Engineering & Computer Science (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)
- Paints Or Removers (AREA)
Abstract
폴리비닐 알코올계 수지(A), 불순물(B), 및 비점이 100℃ 이상의 다가 알코올(C)을 함유하고, 상기 다가 알코올(C)의 함유량이 도포액 중의 70중량% 이상의 불순물 확산용 도포액이다. 이 때문에, 스크린 인쇄에 매우 적합하고, 장시간의 연속 인쇄나 휴지 기간을 둔 인쇄가 가능하며, 피막 형성 후의 반도체 기판을 직립 상태로 소성하였다고 하도 저항값의 상하의 차이가 작은 반도체를 얻을 수 있다.A polyvinyl alcohol-based resin (A), an impurity (B), and a boiling point containing a polyhydric alcohol (C) having a temperature of 100 ° C. or more, wherein the content of the polyhydric alcohol (C) is 70 wt% or more in the coating liquid for impurity diffusion coating liquid to be. For this reason, a semiconductor which is very suitable for screen printing and capable of printing for a long period of continuous printing or a rest period can be obtained, and a semiconductor having a small difference in the upper and lower resistance values can be obtained when the semiconductor substrate after film formation is fired in an upright state.
Description
본 발명은 반도체 기판에 불순물 확산층을 형성할 때에, 기판상에 도포되는 불순물 확산용 도포액에 관한 것으로, 더욱 상세하게는 스크린 인쇄에 의한 도포에 매우 적합한 불순물 확산용 도포액에 관한 것이다.The present invention relates to an impurity diffusion coating liquid applied to a substrate when forming an impurity diffusion layer on a semiconductor substrate, and more particularly, to an impurity diffusion coating liquid that is very suitable for application by screen printing.
트랜지스터, 다이오드, 태양전지 등의 반도체소자에 이용되는 반도체의 제조법으로서 게르마늄, 실리콘 등의 반도체 기판상에 인이나 붕소 등의 불순물을 함유하는 액상 재료를 도포하여 피막을 형성한 후, 소성함으로써 기판 중에 불순물의 확산층을 형성하는 방법이 널리 이용되고 있다.As a method for manufacturing a semiconductor used in semiconductor devices such as transistors, diodes, and solar cells, a liquid material containing impurities such as phosphorus and boron is coated on a semiconductor substrate such as germanium and silicon to form a film, and then fired in the substrate. The method of forming the diffusion layer of impurities is widely used.
이와 같은 액상 재료를 기판상에 도포하는 방법으로서는 스핀 코트법이 널리 이용되고 있지만, 최근, 제조 비용 삭감을 위해서 기판의 대형화가 진행되고, 직경 4인치 이상이 되면, 이와 같은 스핀 코트법에서는 균일한 막 두께의 피막 형성이 곤란해진다. As a method of applying such a liquid material onto a substrate, the spin coating method is widely used. However, in recent years, in order to reduce manufacturing costs, the substrate is enlarged in size, and when the diameter is 4 inches or more, the spin coating method is uniform. Film formation of a film thickness becomes difficult.
따라서, 대형 웨이퍼에도 대응 가능한 도포법으로서 스크린 인쇄법이 검토되어, 이와 같은 인쇄법에 매우 적합한 불순물 함유 확산용 도포액이 제안되고 있다.Therefore, the screen printing method is examined as a coating method that can be applied to a large wafer, and an impurity-containing diffusion coating liquid which is very suitable for such a printing method has been proposed.
예를 들면, 스크린 인쇄에 의해서 반도체 기판상에 균일한 피막을 형성하는 것이 가능한 확산용 도포액으로서 불순물로서 인 화합물이나 붕소 화합물, 수용성 고분자, 물을 함유하고, 점도가 특정 범위인 확산용 도포액이 제안되고 있다.For example, a diffusion coating liquid capable of forming a uniform film on a semiconductor substrate by screen printing, which contains a phosphorus compound, a boron compound, a water-soluble polymer, and water as impurities, and has a viscosity in a specific range. Is being proposed.
(예를 들면, 특허 문헌 1, 2 참조.)(See, for example, Patent Documents 1 and 2.)
특허 문헌 1, 또는 2의 도포액을 스크린 인쇄하고, 소성하여 얻어진 반도체는, 불순물의 함유량이 많고, 피막의 균일성이 높기 때문에, 저항값의 격차가 작고, 매우 뛰어난 것이지만, 사용시의 환경에 따라서는 도포액 중의 물이 휘발, 증점하는 경우가 있었다.Although the semiconductor obtained by screen-printing and baking the coating liquid of patent document 1 or 2 has a lot of impurity content, and the uniformity of a film is high, the difference of resistance value is small and it is very outstanding, but according to the environment at the time of use The water in the coating liquid may volatilize and thicken.
따라서, 용제로서 물보다 휘발성이 낮은 고비등점의 유기용제를 이용하여 유기용제에 가용인 유기 인 화합물, 유기용제에 가용인 폴리초산비닐 등의 유기 바인더, 및 틱소트로피 (thixotrophy)제를 함유하는 확산용 도포액이 제안되고 있다.Therefore, using a high boiling point organic solvent having a lower volatility than water as a solvent, an organic phosphorus soluble in an organic solvent, an organic binder such as polyvinyl acetate soluble in an organic solvent, and a thixotrophy agent are included. A coating liquid for solvents has been proposed.
(예를 들면, 특허 문헌 3 참조.)(See, eg, Patent Document 3.)
표면에 불순물 확산용 도포액에 의한 피막이 형성된 반도체 기판은, 건조 후, 소성함으로써 기판 중에 불순물이 확산하여 확산층이 형성되지만, 통상, 이와 같은 소성은, 다수의 기판을 로 안에 직립시켜 나열한 상태로 실시된다.A semiconductor substrate having a film formed by a coating liquid for impurity diffusion on its surface is dried and then baked to cause impurities to diffuse in the substrate to form a diffusion layer. However, such firing is usually performed in a state in which many substrates are arranged upright in a furnace. do.
그러나 특허 문헌 3의 도포액으로 얻어진 피막은, 소성의 초기 단계에서 유동하여, 기판 하부로 이동하여서인지 상하에서 불순물 농도의 차이가 발생하고, 얻어진 반도체의 저항값에 상하의 차이가 생기는 경향이 있었다.However, the film obtained from the coating liquid of Patent Document 3 tended to flow in the initial stage of firing, move to the lower part of the substrate, and cause a difference in impurity concentrations up and down, and a difference in up and down occurs in the resistance value of the obtained semiconductor.
즉 본 발명은, 스크린 인쇄에 매우 적합한 도포액에 있어서, 피막 형성 후의 반도체 기판을 직립 상태로 소성한다고 하여도 저항값의 상하의 차이가 작은 반도체를 얻을 수 있는 불순물 확산용 도포액의 제공을 목적으로 하는 것이다.That is, the present invention is intended to provide a coating liquid for impurity diffusion in which a coating liquid which is very suitable for screen printing can obtain a semiconductor having a small difference in resistance value even if the semiconductor substrate after film formation is fired in an upright state. It is.
본 발명자는, 상기 사정을 감안하여 예의 연구한 결과, 폴리비닐알코올계 수지 (이하, PVA계 수지와 약기한다.) (A), 불순물(B), 및 비점이 100℃ 이상의 다가 알코올(C)을 함유하고, 상기 다가 알코올(C)의 함유량이 도포액 중의 70중량% 이상인 불순물 확산용 도포액에 의해서 본 발명의 과제가 해결되는 것을 발견하여 본 발명을 완성하였다.MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in view of the said situation, polyvinyl alcohol-type resin (it abbreviates as PVA-type resin hereafter.) (A), an impurity (B), and a polyhydric alcohol (C) with a boiling point of 100 degreeC or more. It was found that the problem of the present invention was solved by the impurity diffusion coating liquid containing a content of the polyhydric alcohol (C) of 70% by weight or more in the coating liquid, and completed the present invention.
즉 본 발명은, 불순물 확산용 도포액에서, 용제의 주성분으로서 비점 100℃ 이상의 다가 알코올을 이용하고, 다시 PVA계 수지를 함유시키는 것을 최대의 특징으로 하는 것이다.That is, the present invention is characterized in that the polyvalent alcohol having a boiling point of 100 ° C. or higher is used as the main component of the solvent in the impurity diffusion coating liquid, and the PVA-based resin is further contained.
또한, 불순물 확산용 도포액에 PVA계 수지를 이용하는 것은 특허 문헌 1, 2 등에 있어 공지이지만, 모두 물이 주용제인 도포액에 수용성 수지인 PVA계 수지를 이용한 것으로, 통상의 유기용제에는 불용이며, 용해했다고 해도 불안정하며, 환경 변화에 따라서는 석출할 가능성이 있는 PVA계 수지를 유기용제를 주체로 하는 도포액에 이용하는 것은, 통상 생각하기 어려운 것이다.The use of PVA-based resins in the coating solution for impurity diffusion is well known in Patent Literatures 1 and 2, but all of them use PVA-based resins, which are water-soluble resins, in coating liquids in which water is the main solvent. Even if it melt | dissolves, it is unstable, and it is difficult to think normally about using PVA system resin which has a possibility of precipitation according to an environmental change to the coating liquid which mainly uses an organic solvent.
본 발명의 불순물 확산용 도포액은 반도체 기판상에 스크린 인쇄하는 것에 의해서 균일한 피막을 얻을 수 있는 점, 점도 안정성이 뛰어나기 때문에, 장시간의 연속 인쇄나 휴지 기간을 둔 인쇄가 가능한 점, 피막 형성 후의 반도체 기판을 직립 상태로 소성하였다고 해도 불순물 농도의 상하차이, 즉 저항값의 상하 불균형이 작은 반도체를 얻을 수 있다는 점, 등의 이점을 갖는 것으로, 공업적으로 지극히 유용하다.The coating liquid for impurity diffusion of the present invention is capable of obtaining a uniform film by screen printing on a semiconductor substrate, and is excellent in viscosity stability, so that it is possible to print for a long period of continuous printing or a rest period, and to form a film. Even if the following semiconductor substrate is fired in an upright state, it is extremely useful industrially because it has advantages such as a semiconductor having a small up and down difference in impurity concentration, that is, a small up and down imbalance in resistance value.
이하에 기재하는 구성 요건의 설명은, 본 발명의 실시형태의 일예 (대표예)이며, 이러한 내용에 특정되는 것은 아니다.Description of the element | module described below is an example (representative example) of embodiment of this invention, and is not specific to this content.
이하, 본 발명에 대해 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 불순물 확산용 도포액은, PVA계 수지(A), 불순물(B), 및 비점이 100℃ 이상의 다가 알코올(C)을 함유하고, 도포액 중의 다가 알코올(C)의 함유량이 70중량% 이상의 것이다.The coating liquid for impurity diffusion of this invention contains PVA system resin (A), an impurity (B), and a polyhydric alcohol (C) with a boiling point of 100 degreeC or more, and content of the polyhydric alcohol (C) in a coating liquid is 70 weight Is more than%.
이하, 각 순서로 설명한다.Hereinafter, each order is demonstrated.
〔PVA계 수지(A)〕[PVA system resin (A)]
우선, 본 발명에서 이용되는 PVA계 수지(A)에 대해 설명한다.First, the PVA system resin (A) used by this invention is demonstrated.
PVA계 수지(A)는, 비닐에스테르계 단량체를 공중합하여 얻어진 폴리비닐에스테르계 수지를 비누화하여 얻어지는 것이며, 비누화도 상당한 비닐 알코올 구조 단위와 초산비닐 구조 단위로 구성된다.PVA-type resin (A) is obtained by saponifying the polyvinyl ester-type resin obtained by copolymerizing a vinyl ester-type monomer, and saponification is comprised from a considerable vinyl alcohol structural unit and a vinyl acetate structural unit.
상기 비닐에스테르계 모노머로서는, 포름산비닐, 초산비닐, 프로피온산비닐, 발레르산비닐, 부티르산비닐, 이소부티르산비닐, 피바린산비닐, 카프린산비닐, 라우린산비닐, 스테아린산비닐, 안식향산비닐, 바사틱크산비닐 등을 들 수 있지만, 경제적으로 초산비닐이 바람직하게 이용된다.Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, and basatic acid. Although vinyl etc. are mentioned, Vinyl acetate is used preferably economically.
본 발명에서 이용되는 PVA계 수지(A)의 평균 중합도 (JIS K 6726에 준거하여 측정)는, 통상, 100∼4000이며, 특히 200∼2000, 또한 300∼1500의 것이 바람직하게 이용된다.The average degree of polymerization (measured based on JIS K 6726) of the PVA-based resin (A) used in the present invention is usually 100 to 4000, particularly preferably 200 to 2000 and 300 to 1500.
이와 같은 평균 중합도가 너무 작으면 도포액이 저점도가 되어, 양호한 스크린 인쇄가 곤란해지거나 도막이 박막이 되어, 불순물의 공급량이 부족하는 경우가 있다. 반대로 너무 커도 스크린 인쇄에는 부적합하고, 인쇄 불량이 발생하기 쉬워지는 경향이 있다.When such average polymerization degree is too small, coating liquid may become low viscosity, favorable screen printing may become difficult, or a coating film may become a thin film and the supply amount of an impurity may be insufficient. On the contrary, even if it is too large, it is unsuitable for screen printing, and there exists a tendency for a bad printing to occur easily.
또, 본 발명에서 이용되는 PVA계 수지(A)로서는, 통상, 비누화도 (JIS K 6726에 준거하여 측정)가 50∼100몰%의 것을 이용하는 것이 가능하다.Moreover, as PVA-type resin (A) used by this invention, it is possible to use the thing of 50-100 mol% of saponification degree (measured based on JIS K 6726) normally.
그 중에서도, 본 발명의 도포액은, 그 용제의 주성분이, 비점이 100℃ 이상의 다가 알코올이기 때문에, 도포액의 균일성의 관점에서, 이와 같은 용제로의 용해성이 뛰어난 것이 바람직하고, 이와 같은 PVA계 수지(A)로서는, 비누화도가 낮은 것이나, 다가 알코올과의 친화성이 뛰어난 변성 PVA를 이용하는 것이 바람직하다.Especially, since the main component of this solvent is a polyhydric alcohol whose boiling point is 100 degreeC or more, it is preferable that the coating liquid of this invention is excellent in the solubility to such a solvent from the viewpoint of the uniformity of a coating liquid, and such a PVA system As resin (A), it is preferable to use modified PVA which is low in saponification degree and excellent in affinity with polyhydric alcohol.
예를 들면, 본 발명의 PVA계 수지(A)로서 미변성의 PVA를 이용하는 경우에는, 비누화도가 50∼90 몰%의 것이 바람직하고, 또한 60∼85 몰%, 특히 70∼80 몰%의 것이 바람직하다.For example, when unmodified PVA is used as the PVA-based resin (A) of the present invention, the saponification degree is preferably 50 to 90 mol%, more preferably 60 to 85 mol%, particularly 70 to 80 mol%. It is preferable.
미변성 PVA의 경우, 그 비누화도가 너무 높으면 다가 알코올을 주체로 하는 용제에의 용해성이 저하되어 함유량을 줄이지 않을 수 없는 경우가 있다. 또, 비누화도가 너무 낮으면 도포액에 의해서 도포 피막이 형성된 반도체 기판을 직립시켜 소성하였을 경우, 얻어진 반도체의 저항값이 기판의 상하에서 차이가 생기는 경우가 있다.In the case of unmodified PVA, when the saponification degree is too high, the solubility to the solvent mainly containing polyhydric alcohol falls, and content may be forced to be reduced. When the degree of saponification is too low, when the semiconductor substrate on which the coating film is formed is erected with a coating liquid and fired, there may be a difference in the resistance value of the obtained semiconductor between the upper and lower sides of the substrate.
또, 변성 PVA계 수지로서는, 폴리비닐 에스테르계 수지의 제조시에 각종 단량체를 공중합시키고, 이를 비누화해 얻어지는 것이나, 미변성 PVA에 후변성에 의해서 각종 관능기를 도입한 것을 이용할 수 있다.Moreover, as modified PVA system resin, what is obtained by copolymerizing various monomers at the time of manufacture of polyvinyl ester resin, saponifying this, and what introduce | transduced various functional groups by postmodification to unmodified PVA can be used.
비닐 에스테르계 모노머와의 공중합에 이용되는 단량체로서는, 에틸렌이나 프로필렌, 이소부틸렌,α-옥텐,α-도데센,α-옥타데센 등의 올레핀류, 3-부텐-1-올, 4-펜텐-1-올, 5-헥센-1-올, 3,4-디히드록시-1-부텐 등의 히드록시기 함유α-올레핀류 및 그 아실 화합물 등의 유도체, 아크릴산, 메타크릴산, 크로톤산, 말레인산, 무수말레인산, 이타콘산 등의 불포화 산류, 그 염, 모노에스테르, 또는 디알킬에스테르, 아크릴로니트릴, 메타아크릴로니트릴 등의 니트릴류, 디아세톤아크릴아미드, 아크릴아미드, 메타크릴아미드 등의 아미드류, 에틸렌술폰산, 아릴술폰산, 메타아릴술폰산 등의 올레핀 설폰산류 또는 그 염, 알킬비닐 에테르류, 디메틸아릴 비닐케톤, N-비닐피롤리돈, 염화 비닐, 비닐에틸렌카보네이트, 2,2-디알킬-4-비닐-1,3-디옥소런, 글리세린모노아릴에테르, 3,4-디아세톡시-1-부텐, 등의 비닐 화합물, 초산이소프로페닐, 1-메톡시비닐아세테이트 등의 치환 초산비닐류, 염화비닐리덴, 1,4-디아세톡시-2-부텐, 비닐렌카보네이트, 등을 들 수 있다.As a monomer used for copolymerization with a vinyl ester monomer, olefins, such as ethylene, propylene, isobutylene, (alpha)-octene, (alpha)-dodecene, (alpha)-octadecene, 3-butene-1-ol, and 4-pentene Hydroxy group-containing α-olefins such as -1-ol, 5-hexene-1-ol, 3,4-dihydroxy-1-butene and derivatives such as acyl compounds, acrylic acid, methacrylic acid, crotonic acid, maleic acid Unsaturated acids such as maleic anhydride and itaconic acid, salts thereof, monoesters, or nitriles such as dialkyl esters, acrylonitrile and methacrylonitrile, amides such as diacetone acrylamide, acrylamide and methacrylamide Olefin sulfonic acids or salts thereof, such as ethylene sulfonic acid, aryl sulfonic acid, and metaaryl sulfonic acid, alkyl vinyl ethers, dimethyl aryl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2-dialkyl- 4-vinyl-1,3-dioxolon, glycerin monoaryl Vinyl compounds such as le, 3,4-diacetoxy-1-butene, substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinylacetate, vinylidene chloride, 1,4-diacetoxy-2- Butene, vinylene carbonate, and the like.
또, 후반응에 의해서 관능기가 도입된 PVA계 수지로서는, 디케톤과의 반응에 의한 아세트아세틸기를 갖는 것, 에틸렌옥시드와의 반응에 의한 폴리알킬렌옥시드기를 갖는 것, 에폭시화합물 등과의 반응에 의한 히드록시알킬기를 갖는 것, 또는 각종 관능기를 갖는 알데히드 화합물을 PVA와 반응시켜 얻어지는 것 등을 들 수 있다.Moreover, as PVA system resin in which a functional group was introduce | transduced by post-reaction, what has an acetacetyl group by reaction with a diketone, what has a polyalkylene oxide group by reaction with ethylene oxide, reaction with an epoxy compound, etc. The thing which has the hydroxyalkyl group by this, or what is obtained by making the aldehyde compound which has various functional groups react with PVA, etc. are mentioned.
이와 같은 변성 PVA계 수지 중의 변성 종, 즉 공중합 체내의 각종 단량체에 유래하는 구성 단위, 또는 후반응에 의해서 도입된 관능기의 함유량은, 변성종에 의해서 특성이 크게 다르기 때문에, 일률적으로는 말할 수 없지만, 통상, 1∼20 몰%이며, 특히 2∼10 몰%의 범위가 바람직하게 이용된다.The content of the modified species in such modified PVA-based resins, ie, the structural units derived from various monomers in the copolymer, or the functional groups introduced by the post-reaction, varies greatly depending on the modified species. Usually, it is 1-20 mol%, Especially the range of 2-10 mol% is used preferably.
이러한 각종 변성 PVA계 수지 중에서도, 본 발명에서는, 하기 화학식 1로 표시되는 측쇄에 1,2-디올 구조를 갖는 구조 단위를 갖는 PVA계 수지가 바람직하게 이용된다.Among these various modified PVA resins, in the present invention, PVA resins having a structural unit having a 1,2-diol structure in the side chain represented by the following general formula (1) are preferably used.
또한, 화학식 1에 있어서의 R1, R2, 및 R3는 각각 독립하여 수소 원자 또는 유기기를 나타내고, X는 단결합 또는 결합쇄를 나타내며, R4, R5, 및 R6는 각각 독립하여 수소 원자 또는 유기기를 나타내는 것이다.In addition, R 1 , R 2 , and R 3 in Formula 1 each independently represent a hydrogen atom or an organic group, X represents a single bond or a chain, and R 4 , R 5 , and R 6 each independently It represents a hydrogen atom or an organic group.
그 중에서도, 화학식 1로 표시되는 1,2-디올 구조 단위 중의 R1∼R3, 및 R4∼R6가 모두 수소 원자이며, X가 단결합인, 하기 화학식 2로 표현되는 구조 단위를 갖는 PVA계 수지가 가장 바람직하다.Especially, R <1> -R <3> and R <4> -R <6> in a 1, 2- diol structural unit represented by General formula (1) are a hydrogen atom, and X has a structural unit represented by following General formula (2) which is a single bond. PVA resin is the most preferable.
또한, 이와 같은 화학식 1로 표시되는 구조 단위 중의 R1∼R3, 및 R4∼R6는, 수지 특성을 큰 폭으로 해치지 않는 정도의 양이면 유기기라도 좋고, 그 유기기로서는, 예를 들면 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, tert-부틸기 등의 탄소수 1∼4의 알킬기를 들 수 있고, 이와 같은 유기기는, 필요에 따라서, 할로겐기, 수산기, 에스테르기, 카르본산기, 술폰산기 등의 관능기가 있어도 된다.In addition, as long as R <1> -R <3> and R <4> -R <6> in the structural unit represented by such general formula (1) are the quantity which does not harm a resin characteristic largely, you may be an organic group, As the organic group, For example, a C1-C4 alkyl group, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- butyl group, is mentioned, Such an organic group is halogen as needed. There may be functional groups such as a group, a hydroxyl group, an ester group, a carboxylic acid group and a sulfonic acid group.
또, 화학식 1로 표시되는 1, 2-디올 구조 단위 중의 X는 열안정성의 점이나 고온하나 산성 조건하에서의 안정성의 점에서 단결합인 것이 가장 바람직하지만, 본 발명의 효과를 저해하지 않는 범위라면 결합쇄라도 좋고, 이와 같은 결합쇄로서는, 알킬렌, 알케닐렌, 알키닐렌, 페닐렌, 나프틸렌 등의 탄화수소 (이들 탄화수소는 불소, 염소, 브롬 등의 할로겐 등으로 치환되어 있어도 좋다) 외, -O-, -(CH2O)m-, -(OCH2)m-, -(CH2O)mCH2-, -CO-, -COCO-, -CO(CH2)mCO-, -CO(C6H4)CO-, -S-, -CS-, -SO-, -SO2-, -NR-, -CONR-, -NRCO-, -CSNR-, -NRCS-, -NRNR-, -HPO4-, -Si(OR)2-, -OSi(OR)2-, -OSi(OR)2O-, -Ti(OR)2-, -OTi(OR)2-, -OTi(OR)2O-, -Al(OR)-, -OAl(OR)-, -OAl(OR)O-, 등 (R은 각각 독립하여 임의의 치환기이며, 수소 원자, 알킬기가 바람직하고, 또 m은 1∼5의 정수)을 들 수 있다. 그 중에서도 제조시 또는 사용시의 안정성의 점에서 탄소수 6 이하의 알킬렌기, 특히 메틸렌기, 또는 -CH2OCH2-가 바람직하다.In addition, X in the 1, 2-diol structural unit represented by the general formula (1) is most preferably a single bond in terms of thermal stability or stability under high temperature and acidic conditions, but bonds as long as it does not impair the effects of the present invention. Chains may be used. Examples of such a bonding chain include hydrocarbons such as alkylene, alkenylene, alkynylene, phenylene, and naphthylene (these hydrocarbons may be substituted with halogen such as fluorine, chlorine, bromine, etc.); -,-(CH 2 O) m -,-(OCH 2 ) m -,-(CH 2 O) m CH 2- , -CO-, -COCO-, -CO (CH 2 ) m CO-, -CO (C 6 H 4 ) CO-, -S-, -CS-, -SO-, -SO 2- , -NR-, -CONR-, -NRCO-, -CSNR-, -NRCS-, -NRNR-, -HPO 4- , -Si (OR) 2- , -OSi (OR) 2- , -OSi (OR) 2 O-, -Ti (OR) 2- , -OTi (OR) 2- , -OTi (OR ) 2 O-, -Al (OR)-, -OAl (OR)-, -OAl (OR) O-, etc. (R is each independently an arbitrary substituent, a hydrogen atom, an alkyl group is preferable, and m is Integers of 1 to 5). Among them, the number of carbon atoms of 6 or lower alkylene group, particularly methylene group, or -CH 2 OCH 2 in terms of stability during manufacture or in use - is preferred.
이와 같은 PVA계 수지의 제조법으로서는, 특별히 한정되지 않지만, (i) 비닐 에스테르계 모노머와 하기 화학식 3으로 표시되는 화합물과의 공중합체를 비누화하는 방법이나, (ii) 비닐 에스테르계 모노머와 하기 화학식 4로 표시되는 화합물과의 공중합체를 비누화 및 탈탄산하는 방법이나, (iii) 비닐 에스테르계 모노머와 하기 화학식 5로 표시되는 화합물과의 공중합체를 비누화 및 탈케탈화하는 방법이 바람직하게 이용된다.Although it does not specifically limit as such a manufacturing method of PVA-type resin, (i) The method of saponifying the copolymer of a vinyl ester monomer and the compound represented by following formula (3), (ii) A vinyl ester monomer and a formula (4) The method of saponifying and decarboxylation of the copolymer with the compound represented by the following, and (iii) The method of saponifying and deketalizing the copolymer of a vinyl ester monomer and the compound represented by following formula (5) is used preferably.
상기 화학식 3, 4, 5 중의 R1, R2, R3, X, R4, R5, R6은, 모두 화학식 1의 경우와 같다. 또, R7 및 R8는 각각 독립하여 수소 원자 또는 R9-CO- (식 중, R9는 알킬기이다)이다. R10 및 R11은 각각 독립하여 수소 원자 또는 알킬기이다.R 1 , R 2 , R 3 , X, R 4 , R 5 , and R 6 in Formulas 3, 4, and 5 are the same as in the case of Formula 1. R 7 and R 8 are each independently a hydrogen atom or R 9 -CO- (wherein R 9 is an alkyl group). R 10 and R 11 are each independently a hydrogen atom or an alkyl group.
(i), (ii), 및 (iii) 방법에서는, 예를 들면, 일본 특허공개공보 제2006-95825호에 설명되고 있는 방법을 이용할 수 있다. 그 중에서도, 공중합 반응성 및 공업적인 취급성이 뛰어난다는 점에서, (i) 방법에서, 화학식 3으로 표시되는 화합물로서 3,4-디아실록시-1-부텐을 이용하는 것이 바람직하고, 특히 3,4-디아세톡시-1-부텐이 바람직하게 이용된다.In the methods (i), (ii) and (iii), for example, the method described in Japanese Patent Laid-Open No. 2006-95825 can be used. Especially, since it is excellent in copolymerization reactivity and industrial handleability, in the method (i), it is preferable to use 3, 4- diacyloxy-1-butene as a compound represented by General formula (3), and especially 3,4 -Diacetoxy-1-butene is preferably used.
본 발명에서, 이와 같은 화학식 1로 표시되는 구조 단위를 갖는 PVA계 수지를 이용하는 경우, 비누화도가 50∼100 몰%의 것을 이용하는 것이 가능하고, 또한 60∼90 몰%, 특히 70∼80 몰%의 것이 바람직하게 이용된다. 이것은, 측쇄의 1, 2-디올 구조에 의해서, 미변성 PVA보다 비누화도가 높아도, 다가 알코올로의 용해성이 향상한 것에 따른 것이다.In the present invention, when using a PVA-based resin having such a structural unit represented by the formula (1), it is possible to use a 50 to 100 mol% saponification degree, and also 60 to 90 mol%, in particular 70 to 80 mol% Is preferably used. This is because the solubility to polyhydric alcohol improved even if the degree of saponification was higher than unmodified PVA by the 1, 2-diol structure of side chain.
또, 이와 같은 PVA계 수지에 포함되는 1,2-디올 구조 단위의 함유량은, 통상, 1∼30 몰%이며, 또한, 3∼20 몰%, 특히 5∼10 몰%의 것이 바람직하게 이용된다. 이와 같은 함유량이 너무 낮으면, 고비누화도의 것의 경우, 다가 알코올에의 용해성이 불충분하게 되는 경우가 있고, 반대로 너무 높으면, 건조성이 저하되어 생산성이 저하하는 경향이 있다.Moreover, content of the 1, 2- diol structural unit contained in such PVA system resin is 1-30 mol% normally, Furthermore, 3-20 mol%, Especially 5-10 mol% are used preferably. . When such content is too low, in the case of a high saponification degree, the solubility to polyhydric alcohol may become inadequate, On the contrary, when it is too high, there exists a tendency for dryness to fall and productivity to fall.
또한, PVA계 수지(A) 중의 1,2-디올 구조 단위의 함유율은, PVA계 수지를 완전하게 비누화한 것의 1H-NMR 스펙트럼 (용매：DMSO-d6, 내부 표준：테트라메틸실란)으로부터 구할 수 있고, 구체적으로는 1,2-디올 단위 중의 수산기프로톤, 메틴프로톤, 및 메틸렌프로톤, 주쇄의 메틸렌프로톤, 주쇄에 연결하는 수산기의 프로톤 등에 유래하는 피크 면적으로 산출하면 좋다.In addition, the content rate of the 1, 2-diol structural unit in PVA system resin (A) is calculated | required from the 1 H-NMR spectrum (solvent: DMSO-d6, internal standard: tetramethylsilane) of what completely saponified PVA system resin. Specifically, the peak area derived from the hydroxyl group protons, methine protons and methylene protons in the 1,2-diol unit, the methylene protons in the main chain, the protons of the hydroxyl group connected to the main chain, and the like may be calculated.
또, 본 발명에서 이용되는 PVA계 수지(A)는, 1종류나 2종류 이상의 혼합물이라도 좋고, 이 경우는, 상술의 미변성 PVA 끼리, 미변성 PVA와 화학식 1로 표시되는 구조 단위를 갖는 PVA계 수지, 비누화도, 중합도, 변성도 등이 다른 화학식 1로 표시되는 구조 단위를 갖는 PVA계 수지끼리, 미변성 PVA, 또는 화학식 1로 표시되는 PVA계 수지와 다른 변성 PVA계 수지 등의 조합을 이용할 수 있다.Moreover, the PVA system resin (A) used by this invention may be one type, or 2 or more types of mixtures, In this case, PVA which has unmodified PVA mentioned above, unmodified PVA, and the structural unit represented by General formula (1). PVA-based resins having structural units represented by the general formula (1) having different resins, degree of saponification, degree of polymerization, degree of modification, etc., unmodified PVA, or combinations of PVA-based resins represented by the general formula (1) with other modified PVA-based resins It is available.
본 발명의 불순물 확산용 도포액 중의 PVA계 수지(A)의 함유량은, 통상 1∼40중량%이며, 특히 3∼30중량%, 특히 5∼25중량%의 범위가 바람직하게 이용된다. 이와 같은 PVA계 수지(A)의 함유량이 너무 작으면, 도포액의 점도가 낮아지고, 도막이 안정되어 형성되기 어려워지는 경향이 있어, 반대로, 너무 많으면, 도포액의 점도가 높아지기 때문에, 도포 작업성이 저하하거나 스크린 인쇄에 있어서의 스크린 메쉬의 로딩이 일어나기 쉬워지는 경향이 있다.Content of PVA system resin (A) in the impurity diffusion coating liquid of this invention is 1-40 weight% normally, Especially 3-30 weight%, Especially the range of 5-25 weight% is used preferably. When the content of such PVA-based resin (A) is too small, the viscosity of the coating liquid is lowered, and the coating film is stable and tends to be difficult to be formed. On the contrary, when the content is too large, the viscosity of the coating liquid becomes high. There exists a tendency for this fall or the loading of the screen mesh in screen printing to become easy to occur.
〔불순물(B)〕[Impurity (B)]
이어서, 본 발명에서 이용되는 불순물(B)에 대해 설명한다. Next, the impurity (B) used by this invention is demonstrated.
이와 같은 불순물(B)로서는, 예를 들면, 13족 원소 화합물이나 15족 원소 화합물이 이용된다. 또, 이들 화합물은, 단독으로 이용해도 좋고, 병용해도 좋다.As such an impurity (B), a group 13 element compound and a group 15 element compound are used, for example. Moreover, these compounds may be used independently and may be used together.
상기 15족 원소 화합물은, 일반적으로 N형 반도체의 제조에서, 불순물로서 이용되는 것이며, 인 화합물이나 안티몬 화합물을 들 수 있지만, 그 중에서도 인 화합물이 바람직하게 이용된다.The Group 15 element compound is generally used as an impurity in the manufacture of an N-type semiconductor, and phosphorus compounds and antimony compounds are mentioned, and among them, phosphorus compounds are preferably used.
이와 같은 인 화합물로서는, 일반적으로 N형 반도체의 제조에서 불순물로서 이용되는 것이면 사용 가능하고, 구체적으로는, 인산, 5산화2인 등의 인산류； 인산 멜라민, 인산 암모늄 등의 인산염류； 염화인, 옥시 염화인 등의 염화물； 인산 에스테르류 등을 들 수 있다.As such a phosphorus compound, it can be used if it is generally used as an impurity in manufacture of an N-type semiconductor, Specifically, phosphoric acid, such as phosphoric acid and diphosphoric pentaoxide; Phosphate, such as melamine phosphate and ammonium phosphate; Phosphorus chloride Chlorides such as phosphorus and oxychloride; and phosphoric acid esters.
그 중에서도, 용제의 주성분으로서 이용되는 비점 100℃ 이상의 다가 알코올에의 용해성이 뛰어나기 때문에 인산이나 5산화2인, 인산 에스테르류를 들 수 있고, 특히 인산 에스테르류가 바람직하게 이용된다.Especially, since it is excellent in the solubility to the polyhydric alcohol of boiling point 100 degreeC or more used as a main component of a solvent, phosphoric acid and pentoxide phosphate which are pentoxide are mentioned, Especially phosphoric acid ester is used preferably.
본 발명에서 이용되는 인산 에스테르류는 인산이 갖는 3개의 수소의 전부, 또는 일부가 유기기로 치환된 것으로, 공지의 각종 화합물을 이용하는 것이 가능하지만, 그 중에서도 하기 화학식 6로 표시되는 엑시드포스폭시(메타)아크릴레이트류가 오토 도프의 억제의 점에서 바람직하게 이용된다.Phosphoric acid esters used in the present invention are those in which all or part of three hydrogens of phosphoric acid are substituted with an organic group, and various known compounds can be used. ) Acrylates are used preferably from the point of suppression of auto dope.
상기 화학식 6 중의 R12는 수소 또는 메틸기이며, R13는 수소, 메틸기, 또는 -CH2Cl기이며, R14는 수소, 탄소수 1∼10의 알킬기, 페닐기, 또는 -NH3C2H4OH기이며, n는 1∼10의 정의 정수이며, m, l는 1 또는 2이며, m＋l=3이다.R 12 in Formula 6 is hydrogen or a methyl group, R 13 is hydrogen, a methyl group, or a —CH 2 Cl group, R 14 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or —NH 3 C 2 H 4 OH N is a positive integer of 1-10, m and l are 1 or 2, and m + l = 3.
이와 같은 화학식 6으로 표시되는 엑시드포스폭시(메타)아크릴레이트류의 시판품으로서는, 유니케미칼사 제조의 호스마시리즈, 니혼카가쿠사 제조의 가야마-시리즈, 교오에이샤유시사 제조의 라이트 에스테르 시리즈, 다이하치카가쿠사 제조의 MR시리즈, AR시리즈, PS시리즈, 신나카무라카가쿠사 제조의 NK에스테르 시리즈, 등을 들 수 있다.As a commercial item of the acid phosphoxy (meth) acrylate represented by such a formula (6), the Hosuma series by the Unichemical company, the Kayama series by the Nippon Chemical Co., Ltd., the light ester series by the Kyowa Corporation company, MR series, AR series, PS series, the Shin-Nakamura Kagaku company NK ester series, etc. made by Daihachi Chemical Co., Ltd. are mentioned.
그 구체적인 예로서는 R12가 메틸기, R13이 수소, R14가 수소, n이 1, m이 1, l이 2인 화합물 (예를 들면, 유니케미칼사 제 「호스마 M」)이나, R12가 메틸기, R13이 수소, R14가 -NH3C2H4OH, n이 1, m이 1, l이 2인 화합물 (예를 들면, 유니케미칼사제조 「호스마 MH」), R12가 메틸기, R13이 수소, R14가 수소, n이 4∼5, m이 1, l이 2인 화합물 (예를 들면, 유니케미칼사 제조 「호스마 PE」등을 들 수 있다.Specific examples thereof include a compound in which R 12 is a methyl group, R 13 is hydrogen, R 14 is hydrogen, n is 1, m is 1 and 1 is 2 (for example, "Hosema M" manufactured by Unichemical), or R 12 Is a methyl group, R 13 is hydrogen, R 14 is -NH 3 C 2 H 4 OH, n is 1, m is 1, 1 is a compound (e.g., "Hosema MH" manufactured by Unichemical), R A compound in which a divalent methyl group, R 13 is hydrogen, R 14 is hydrogen, n is 4 to 5, m is 1, and 1 is 2 (for example, "Hosema PE" manufactured by Unichemical).
그 중에서도, 본 발명에서 이용되는 PVA계 수지와의 친화성의 관점에서, 화학식 6에서, R12가 메틸기인 엑시드포스폭시메타크릴레이트류, R13이 수소이며 n이 5 이하, 특히 1인 것, R14가 수소인 것, 및 m이 1, l이 2인 것이 바람직하게 이용된다.Among these, from the affinity consideration of securing of the PVA-based resin used in the present invention, in formula 6, R 12 is a methyl group Exceed force epoxy methacrylates, R 13 is hydrogen and that when n is 5 or less, in particular 1, It is preferably used that R 14 is hydrogen and m is 1 and 1 is 2.
본 발명의 불순물 확산용 도포액 중의 15족 원소 화합물의 함유량은, 통상 0.1∼30중량%이며, 특히 0.1∼10중량%, 특히 0.1∼5중량%의 범위가 바람직하게 이용된다.The content of the Group 15 element compound in the coating solution for impurity diffusion of the present invention is usually 0.1 to 30% by weight, particularly preferably 0.1 to 10% by weight, particularly 0.1 to 5% by weight.
또, 15족 원소 화합물의 PVA계 수지(A) 100 중량부에 대한 함유량은, 통상 1∼300 중량부이며, 특히 2∼200 중량부, 특히 3∼50 중량부의 범위가 이용된다. Moreover, content with respect to 100 weight part of PVA-type resin (A) of a group 15 element compound is 1-300 weight part normally, Especially 2-200 weight part, especially the range of 3-50 weight part is used.
이와 같은 15족 원소 화합물의 함유량이 작으면 확산층안의 15족 원소 (인 등)의 함유량이 작아져서 충분한 저항값을 얻을 수 없는 경우가 있다. 또, 15족 원소 화합물의 함유량이 너무 많으면, PVA계 수지(A)의 용해성이 불충분해지는 경우가 있다.When content of such a group 15 element compound is small, content of group 15 elements (phosphorus etc.) in a diffusion layer may become small, and sufficient resistance value may not be obtained. Moreover, when there is too much content of a group 15 element compound, the solubility of PVA system resin (A) may become inadequate.
또한, 이와 같은 15족 원소 화합물은, 단일 화합물이라도 좋고, 2종 이상의 것을 조합하여 이용해도 된다.In addition, such a group 15 element compound may be a single compound, and may be used in combination of 2 or more type.
또, 상기 13족 원소 화합물은, 일반적으로 P형 반도체의 제조에서, 불순물로서 이용되는 것이며, 붕소 화합물이나 알루미늄 화합물을 들 수 있지만, 그 중에서도 붕소 화합물이 바람직하게 이용된다.Moreover, the said Group 13 element compound is generally used as an impurity in manufacture of a P-type semiconductor, A boron compound and an aluminum compound are mentioned, Especially, a boron compound is used preferably.
이와 같은 붕소 화합물의 구체적인 예로서는, 붕산, 삼산화2붕소 등의 붕산류； 붕산 암모늄 등의 붕산염류； 3불화 붕소, 3염화 붕소, 3브롬화 붕소, 3옥화 붕소 등의 할로겐 화물； 붕산트리메틸, 붕산트리에틸, 붕산트리이소프로필 등의 붕산 에스테르류； 질화 붕소 등을 들 수 있다.Specific examples of such a boron compound include boric acids such as boric acid and diboron trioxide; borates such as ammonium borate; halides such as boron trifluoride, boron trichloride, boron tribromide, and boron trifluoride; trimethyl borate, and boric tri Boric acid esters such as ethyl and triisopropyl borate; boron nitride and the like.
그 중에서도, 취급의 용이성 때문에, 붕산이나, 붕산염류, 붕산 에스테르류, 질화 붕소가 바람직하게 이용된다.Among them, boric acid, borates, boric acid esters, and boron nitride are preferably used for ease of handling.
본 발명에서 이용되는 붕산 에스테르류란, 붕산이 갖는 3개의 수소의 전부, 또는 일부가 유기기로 치환된 것으로, 공지의 각종 화합물을 이용하는 것이 가능하지만, 그 중에서도 붕산트리메틸, 붕산트리에틸이 불순물 확산성의 점에서 바람직하게 이용된다.The boric acid esters used in the present invention are those in which all or part of three hydrogens of boric acid are substituted with an organic group, and various known compounds can be used. Among them, trimethyl borate and triethyl borate are impurity diffusive. It is preferably used at the point.
본 발명의 불순물 확산용 도포액 중의 13족 원소 화합물의 함유량은, 통상 0.1∼30중량%이며, 특히 0.1∼10중량%, 특히 0.1∼5중량%의 범위가 바람직하게 이용된다.The content of the Group 13 element compound in the coating solution for impurity diffusion of the present invention is usually 0.1 to 30% by weight, in particular 0.1 to 10% by weight, particularly preferably in the range of 0.1 to 5% by weight.
또, 13족 원소 화합물의 PVA계 수지(A) 100 중량부에 대한 함유량은, 통상 1∼300 중량부이며, 특히 3∼200 중량부, 특히 5∼50 중량부의 범위가 이용된다.Moreover, content with respect to 100 weight part of PVA-type resin (A) of a group 13 element compound is 1-300 weight part normally, Especially 3-200 weight part, especially the range of 5-50 weight part is used.
이와 같은 13족 원소 화합물의 함유량이 작으면 확산층안의 13족 원소 (붕소 등)의 함유량이 작아져, 충분한 저항값을 얻을 수 없는 경우가 있다.When content of such a group 13 element compound is small, content of group 13 element (boron etc.) in a diffusion layer may become small, and sufficient resistance value may not be obtained.
또, 13족 원소 화합물의 함유량이 너무 많으면, PVA계 수지(A)의 용해성이 불충분해지는 경우가 있다.Moreover, when there is too much content of a group 13 element compound, the solubility of PVA system resin (A) may become inadequate.
〔다가 알코올(C)〕[Polyhydric alcohol (C)]
본 발명의 불순물 확산용 도포액은, 그 용제의 주성분으로서 비점이 100℃ 이상인 다가 알코올(C)을 이용하는 것을 특징으로 하는 것이다.The coating liquid for impurity diffusion of this invention uses the polyhydric alcohol (C) whose boiling point is 100 degreeC or more as a main component of the solvent.
이와 같은 다가 알코올류(C)를 주성분으로서 이용하는 것에 의해서, 도포액이 뛰어난 점도 안정성을 얻을 수 있다.By using such polyhydric alcohols (C) as a main component, the viscosity stability excellent in a coating liquid can be obtained.
이와 같은 다가 알코올(C)은, 비점이 100℃ 이상의 것이지만, 또한 150∼400℃, 특히 175∼300℃의 것이 바람직하게 이용된다.Although such a polyhydric alcohol (C) is a thing with a boiling point of 100 degreeC or more, Furthermore, the thing of 150-400 degreeC, especially 175-300 degreeC is used preferably.
또, 이와 같은 다가 알코올로서는, 지방족 알코올, 방향족 알코올의 모두 사용할 수 있지만, PVA계 수지(A)의 용해성의 점에서 지방족 알코올이 바람직하다.Moreover, as such a polyhydric alcohol, both an aliphatic alcohol and an aromatic alcohol can be used, but an aliphatic alcohol is preferable at the point of the solubility of PVA-type resin (A).
이와 같은 다가 알코올(C)로서는, 구체적으로는, 에틸렌글리콜 (197℃), 디에틸렌글리콜 (244℃), 트리에틸렌글리콜 (287℃), 테트라에틸렌글리콜 (314℃), 프로필렌글리콜 (188℃) 등의 2가 알코올류；글리세린(290℃), 트리메티롤프로판(292℃), 솔비톨(296℃), 만니톨(290∼295℃), 펜타에리쓰리톨(276℃), 폴리글리세린 등의 3가 이상의 다가 알코올류, 등을 들 수 있다. 또한, ( ) 안의 값은 비점이다.As such polyhydric alcohol (C), specifically, ethylene glycol (197 degreeC), diethylene glycol (244 degreeC), triethylene glycol (287 degreeC), tetraethylene glycol (314 degreeC), propylene glycol (188 degreeC) Dihydric alcohols such as glycerin (290 ° C), trimetholpropane (292 ° C), sorbitol (296 ° C), mannitol (290-295 ° C), pentaerythritol (276 ° C), and polyglycerol Or more polyhydric alcohols, and the like. Also, the value in () is a boiling point.
이들은 단독으로 이용하는 것도 가능하지만, 점도의 조정, PVA계 수지나 인 화합물의 용해성, 각종 첨가물의 용해성이나 분산성, 기재로의 습윤성 등을 조제하기 위해서, 2종 이상의 것을 병용하여 이용하는 것이 바람직한 실시형태이다. 그 중에서도, 에틸렌글리콜과 글리세린의 조합이 바람직하게 이용되며 이때의 에틸렌글리콜과 글리세린의 배합 비율은 원하는 특성에 따라서 다르지만, 통상, 에틸렌글리콜/글리세린의 값이 20/80∼100/0이며, 또한 30/70∼90/10, 특히 50/50∼80/20의 범위로부터 선택된다.Although these can also be used independently, it is preferable to use together 2 or more types, in order to adjust viscosity, the solubility of PVA-type resin and a phosphorus compound, the solubility and dispersibility of various additives, wettability to a base material, etc. to be. Among them, a combination of ethylene glycol and glycerin is preferably used, and the mixing ratio of ethylene glycol and glycerin at this time varies depending on the desired characteristics, but usually, the value of ethylene glycol / glycerine is 20/80 to 100/0, and 30 / 70 to 90/10, especially 50/50 to 80/20.
또, 다가 알코올 이외의 용제를 병용하는 것도 가능하고, 이와 같은 용제로서는, 물, 이소부틸산-3-히드록시-2,2,4-트리메틸펜틸에스테르 (TPM)나, 메탄올, 에탄올, 이소프로판올 등의 저급 알코올계 용제, 메틸카르비톨, 에틸카르비톨, 부틸 카르비톨 등의 카르비톨계 용제, 에틸셀로솔브, 이소아밀셀로솔브, 헥실셀로솔브 등의 셀로솔브계 용제, 그 외 지방족 탄화수소계 용제, 고급 지방산계 용제, 방향족 탄화수소계 용제 등을 들 수 있다. Moreover, it is also possible to use together solvents other than polyhydric alcohol, As such a solvent, water, isobutyl-acid 3-hydroxy-2,2,4-trimethyl pentyl ester (TPM), methanol, ethanol, isopropanol, etc. Lower alcohol solvents, carbitol solvents such as methyl carbitol, ethyl carbitol, butyl carbitol, cellosolve solvents such as ethyl cellosolve, isoamyl cellosolve, hexyl cellosolve, and other aliphatic hydrocarbons Solvents, higher fatty acid solvents, aromatic hydrocarbon solvents, and the like.
이와 같은 다가 알코올 이외의 용제의 배합량은, 통상, 용제의 전량에 대해서 20중량% 이하이며, 특히 10중량% 이하이다.The compounding quantity of solvents other than such polyhydric alcohol is 20 weight% or less with respect to whole quantity of a solvent normally, especially 10 weight% or less.
본 발명의 불순물 확산용 도포액에 있어서의 다가 알코올(C)의 함유량은, 70 중량% 이상이며, 또한 70∼90 중량%, 특히 75∼90중량%의 범위가 바람직하게 이용된다. 이와 같은 다가 알코올(C)의 함유량이 너무 적으면 도포액의 점도가 너무 높아져서, 도포 작업성이 저하하거나 스크린 인쇄에 있어서의 스크린 메쉬의 로딩이 일어나기 쉬워지는 경향이 있다. 반대로 너무 많으면 도포액의 점도가 너무 낮아져서 도막이 안정되어 형성되기 어려워지거나 건조하게 장시간을 필요로 하는 경향이 있고, 또한, 확산층안의 불순물의 함유량이 너무 적게 되는 경우가 있다.Content of the polyhydric alcohol (C) in the impurity diffusion coating liquid of this invention is 70 weight% or more, and 70-90 weight%, especially the range of 75-90 weight% is used preferably. When there is too little content of such polyhydric alcohol (C), the viscosity of a coating liquid will become high too much, and it exists in the tendency for application | coating workability to fall or loading of the screen mesh in screen printing easily occurs. On the contrary, when too much, the viscosity of a coating liquid will become low too much, it may become difficult to form a stable coating film, or it may require a long time to dry, and also the content of the impurity in a diffusion layer may become too small.
〔계면활성제(D)〕[Surfactant (D)]
본 발명의 불순물 확산용 도포액에는, 반도체 표면으로의 습윤성을 향상시켜, 도포액의 발포를 억제하고, 기포에 기인하는 인쇄 불량의 방지 등을 목적으로 하여 계면활성제(D)를 배합하는 것이 바람직하다. 본 발명의 도포액에 이용되는 계면활성제로서는, 공지의 비이온계 계면활성제, 양이온계 계면활성제, 음이온계 계면활성제를 들 수 있고 모두 사용할 수 있지만, 반도체로의 금속 성분 등의 반입이 적기 때문에 비이온계 계면활성제가 바람직하다.It is preferable to mix | blend surfactant (D) with the impurity diffusion coating liquid of this invention for the purpose of improving the wettability to the semiconductor surface, suppressing foaming of a coating liquid, and preventing printing defects resulting from a bubble. Do. As surfactant used for the coating liquid of this invention, a well-known nonionic surfactant, a cationic surfactant, and an anionic surfactant can be mentioned and all can be used, but since there are few imports of a metal component etc. to a semiconductor, Ionic surfactants are preferred.
이와 같은 비이온계 계면활성제로서는, 공지의 것을 사용하는 것이 가능하고, 구체적으로는 에틸렌옥시드-프로필렌옥시드의 블록 공중합체, 아세틸렌 글리콜 유도체 등의 탄화수소계 계면활성제나, 실리콘계 계면활성제, 불소계 계면활성제나 유기 변성 폴리실록산과 특수 폴리머의 혼합물 등을 들 수 있다.As such a nonionic surfactant, a well-known thing can be used, Specifically, hydrocarbon type surfactant, such as a block copolymer of ethylene oxide propylene oxide, an acetylene glycol derivative, a silicone type surfactant, and a fluorine type interface The mixture of an activator, organic modified polysiloxane, and a special polymer, etc. are mentioned.
그 중에서도, 본 발명의 도포액에 대해 발포의 억제, 및 소포성이 뛰어난 점에서, 탄화수소계 계면활성제, 특히 아세틸렌 글리콜 유도체가 바람직하게 이용된다.Among these, hydrocarbon-based surfactants, in particular, acetylene glycol derivatives, are preferably used in view of suppressing foaming and antifoaming properties of the coating liquid of the present invention.
이와 같은 아세틸렌 글리콜 유도체로서는, 하기 화학식 7로 표시되는 것이 바람직하게 이용된다.As such an acetylene glycol derivative, what is represented by following formula (7) is used preferably.
상기 화학식 7 중의 R15, R18은 각각 독립하여 탄소수 1∼20의 알킬기를 나타내고, 특히 탄소수 1∼5의 것이 바람직하고, 특히 탄소수 3∼5의 것이 바람직하게 이용된다. 또, R16 , R17은 각각 독립하여 탄소수 1∼3의 알킬기를 나타내며, 특히 메틸기가 바람직하게 이용된다. 또한, R15와 R18, 및 R16와 R17은 각각 동일하거나 다른 것이라도 좋지만, 각각 동일 구조의 것이 바람직하게 이용된다.R <15> , R <18> in the said Formula (7) represents a C1-C20 alkyl group each independently, Especially a C1-C5 thing is preferable, Especially a C3-C5 thing is used preferably. In addition, R 16 and R 17 each independently represent an alkyl group having 1 to 3 carbon atoms, and in particular, a methyl group is preferably used. In addition, although R <15> and R <18> and R <16> and R <17> may respectively be same or different, the thing of the same structure is used preferably, respectively.
또, s, t는 각각 0∼30의 정수이며, 또한 s＋t가 1∼10, 특히 1∼5, 특히 1∼3인 것이 바람직하게 이용된다.S and t are each an integer of 0 to 30, and s + t is preferably 1 to 10, particularly 1 to 5, and particularly preferably 1 to 3, respectively.
이와 같은 아세틸렌 글리콜 유도체로서는, 구체적으로, 2,5,8,11-테트라메틸-6-도데신-5,8-디올의 에틸렌옥시드 부가물, 5,8-디메틸-6-도데신-5,8-디올의 에틸렌옥시드 부가물, 2,4,7,9-테트라메틸-5-데신-4,7 디올의 에틸렌옥시드 부가물, 4,7-디메틸-5-데신-4,7-디올의 에틸렌옥시드 부가물, 2,3,6,7-테트라메틸-4-옥틴-3,6-디올의 에틸렌옥시드 부가물, 3,6-디메틸-4-옥틴-3,6-디올의 에틸렌옥시드 부가물, 2,5-디메틸-3-헥신-2,5-디올의 에틸렌옥시드 부가물 등을 들 수 있다.Specific examples of such acetylene glycol derivatives include ethylene oxide adducts of 2,5,8,11-tetramethyl-6-dodecine-5,8-diol, and 5,8-dimethyl-6-dodecine-5. Ethylene oxide adducts of 8-diol, 2,4,7,9-tetramethyl-5-decine-4,7 ethylene oxide adducts of diol, 4,7-dimethyl-5-decine-4,7 Ethylene oxide adducts of diols, ethylene oxide adducts of 2,3,6,7-tetramethyl-4-octin-3,6-diol, 3,6-dimethyl-4-octin-3,6- Ethylene oxide adducts of diols, ethylene oxide adducts of 2,5-dimethyl-3-hexine-2,5-diol, and the like.
이들 중에서도, 2,4,7,9-테트라메틸-5-데신-4,7-디올의 에틸렌옥시드 부가물이며, 에틸렌옥시드의 부가량 (m＋n)이 1∼2인 것이 바람직하게 이용된다.Among these, an ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decine-4,7-diol, and an addition amount (m + n) of ethylene oxide of 1 to 2 is preferably used. .
이와 같은 아세틸렌 글리콜 유도체인 계면활성제의 시판품으로서는, 닛신카가쿠고교사 제조 서피놀시리즈 등을 들 수 있다.As a commercial item of the surfactant which is such an acetylene glycol derivative, Nisshin Kagaku Kogyo Sufinol series etc. are mentioned.
본 발명의 불순물 확산용 도포액에 배합되는 계면활성제(D)의 배합량은, 통상, 도포액 중 0.1∼10 중량%이며, 특히 0.3∼8 중량%, 특히 0.5∼5 중량%의 범위가 바람직하게 이용된다. 이와 같은 계면활성제(D)의 배합량이 너무 적으면, 억포·소포효과가 불충분한 경우가 있고, 반대로 너무 많으면 액으로부터 분리하여 균일 용액을 얻을 수 없게 되는 경우가 있다.The compounding quantity of surfactant (D) mix | blended with the impurity diffusion coating liquid of this invention is 0.1-10 weight% normally in a coating liquid, Especially 0.3-8 weight%, Especially the range of 0.5-5 weight% is preferable. Is used. If the amount of such surfactant (D) is too small, the suppression and antifoaming effect may be insufficient. On the contrary, if the amount of the surfactant (D) is too large, the homogeneous solution may not be obtained by separating from the liquid.
〔무기 미립자(E)〕[Inorganic fine particles (E)]
본 발명의 불순물 확산용 도포액에는, 스크린 인쇄 특성을 개선하는 목적으로, 각종의 무기 미립자(E)를 배합하는 것이 가능하다.Various inorganic fine particles (E) can be mix | blended with the impurity diffusion coating liquid of this invention in order to improve screen printing characteristics.
이와 같은 무기 미립자(E)로서는, 콜로이달 실리카, 비정질 실리카, 흄드 살리카 (fumed silica) 등의 실리카류가 매우 적합하고, 그 중에서도 콜로이달 실리카가 바람직하게 이용된다.As such inorganic fine particles (E), silica, such as colloidal silica, amorphous silica, and fumed silica, is very suitable. Among them, colloidal silica is preferably used.
이와 같은 무기 미립자(E)의 배합량은, 통상, 도포액 중 0.5∼20 중량%이며, 특히 1∼10 중량%의 범위가 바람직하게 이용된다.The compounding quantity of such inorganic microparticles | fine-particles (E) is 0.5-20 weight% normally in a coating liquid, Especially the range of 1-10 weight% is used preferably.
〔불순물 확산용 도포액〕[Coating Liquid for Impurity Diffusion]
본 발명의 불순물 확산용 도포액은, 상술의 PVA계 수지(A), 불순물(B), 및 비점이 100℃ 이상의 다가 알코올(C)을 함유하고, 상기 다가 알코올(C)의 함유량이 도포액중의 70중량%인 것이며, 필요에 따라서, 또한 계면활성제(D), 및 무기 미립자(E), 및 그 외의 첨가제를 함유하는 것이다.The coating liquid for impurity diffusion of this invention contains the above-mentioned PVA-type resin (A), an impurity (B), and the boiling point 100 degreeC or more polyhydric alcohol (C), and content of the said polyhydric alcohol (C) is a coating liquid It is 70 weight% in the inside, and also contains surfactant (D), an inorganic fine particle (E), and other additives as needed.
이와 같은 불순물 확산용 도포액의 20℃에 있어서의 점도는 통상 300∼100, 000mPa·s이며, 특히 500∼10,000mPa·s, 특히 700∼6,000mPa·s의 범위가 바람직하게 이용된다. 또한, 이와 같은 점도는 B형 점토계를 이용한 측정한 것이다.The viscosity at 20 degrees C of such an impurity diffusion coating liquid is 300-10000 mPa * s normally, Especially 500-10,000 mPa * s, Especially 700-6,000 mPa * s range is used preferably. In addition, such a viscosity is measured using the B-type clay meter.
이와 같은 도포액의 농도, 및 점도가 너무 작으면 도막이 안정되어 형성되기 어려워지거나 확산층안의 불순물의 함유량이 불충분하게 되는 경우가 있고, 반대로 농도, 및 점도가 너무 크면, 도포 작업성이 저하하거나 스크린 인쇄에 있어서의 스크린 메쉬의 로딩이 일어나기 쉬워지는 경향이 있다.If the coating liquid concentration and viscosity are too small, the coating film may become stable and difficult to be formed, or the content of impurities in the diffusion layer may be insufficient. Conversely, if the concentration and viscosity are too large, the coating workability may be reduced or screen printing may be performed. There is a tendency for loading of the screen mesh in the device to occur easily.
본 발명의 불순물 확산용 도포액의 조제법은 특히 한정되지 않지만, 예를 들면, 상술의 PVA계 수지(A)와 불순물(B)을 순서대로, 또는 동시에 다가 알코올(C)에 용해하는 방법, PVA계 수지(A), 및 불순물(B)의 다가 알코올(C) 용액을 따로따로 조제하고, 이들을 혼합하는 방법 등을 들 수 있고, 이와 같은 용해, 조제 시에는, 가열, 교반하면서 실시하는 것이 바람직하다.Although the preparation method of the impurity-diffusion coating liquid of this invention is not specifically limited, For example, the method of melt | dissolving the above-mentioned PVA system resin (A) and an impurity (B) in order or simultaneously in polyhydric alcohol (C), PVA And a method of separately preparing a polyhydric alcohol (C) solution of a system resin (A) and an impurity (B), and mixing them. Examples of such dissolution and preparation are preferably performed while heating and stirring. Do.
또, 계면활성제(D), 무기 미립자(E), 그 외의 첨가제에 대해서는, 상기 도포액의 조제 후에 배합, 또는 상기 조제의 과정에서 배합의 어느 방법도 채용할 수 있다.Moreover, about surfactant (D), an inorganic fine particle (E), and another additive, any method of compounding can be employ | adopted after preparation of the said coating liquid or in the process of the said preparation.
이렇게 하여 얻어진 본 발명의 불순물 확산용 도포액은 보존 안정성이 뛰어나므로, 대량으로 조제하여 보관하거나 작게 나누어 이동하거나 할 수 있고, 또, 도중까지 사용하여 나머지를 보존하는 것도 가능하다.Since the coating liquid for impurity diffusion of this invention obtained in this way is excellent in storage stability, it can be prepared and stored in large quantities, it can carry out by dividing small, and it can also use it to the middle, and can preserve | rest the remainder.
〔반도체〕〔semiconductor〕
이어서, 본 발명의 불순물 확산용 도포액을 이용하여 얻어진 반도체에 대해 설명한다. Next, the semiconductor obtained using the coating liquid for impurity diffusion of this invention is demonstrated.
이와 같은 반도체는, 실리콘이나 게르마늄 등의 반도체 기판상에 본 발명의 불순물 확산용 도포액을 도포하여, 건조, 소성, 확산의 각 공정을 거쳐, 반도체 기판 중에 불순물의 확산층을 형성하는 것으로 제조된다.Such a semiconductor is produced by applying the impurity diffusion coating liquid of the present invention onto a semiconductor substrate such as silicon, germanium, or the like, and forming a diffusion layer of impurities in the semiconductor substrate through respective steps of drying, firing, and diffusion.
반도체 기판상에 불순물 확산용 도포액을 도포하는 방법으로서는, 공지의 방법을 이용하는 것이 가능하고, 구체적으로는, 스크린 인쇄법, 그라비아 인쇄법, 철판 인쇄법 (letterpress printing), 평판 인쇄법, 스핀 코터법, 콤마 코터법, 다이 헤드 코터법, 다이립 코터법, 등을 들 수 있다.As a method for applying the impurity diffusion coating liquid onto a semiconductor substrate, a known method can be used, and specifically, a screen printing method, a gravure printing method, a letterpress printing method, a flat plate printing method, a spin coater A method, a comma coater method, a die head coater method, a die lip coater method, etc. are mentioned.
그 중에서도, 본 발명의 도포액은 스크린 인쇄법으로 이용하는 것으로 최대의 효과를 얻을 수 있어 4인치 이상의 대형 웨이퍼에서도 균일한 도포막을 얻을 수 있다. 반도체 기판상으로의 도포액의 도포량은, 기판의 종류나 반도체의 용도, 도포액중의 불순물 화합물의 함유량과 원하는 불순물 함유량에 따라서 다르지만, 통상, 1∼100g/㎡이며, 특히 1∼50g/㎡의 범위에서 실시된다.Especially, the coating liquid of this invention can obtain a maximum effect by using by the screen printing method, and can obtain a uniform coating film even in a large wafer of 4 inches or more. The coating amount of the coating liquid onto the semiconductor substrate varies depending on the type of substrate, the use of the semiconductor, the content of the impurity compound in the coating liquid, and the desired impurity content, but is usually 1 to 100 g / m 2, particularly 1 to 50 g / m 2. Is carried out in the range of.
계속되는 건조 공정에서 도포막으로부터 물 등의 휘발 성분이 제거되며, 그 조건으로서는, 적절히 설정하면 좋지만, 통상, 20∼300℃, 특히 100∼200℃에서의 온도 조건하, 1∼60분, 특히 5∼30분의 건조 시간이 이용된다. 건조 방법에 대해서도 특별히 한정되지 않고, 열풍 건조, 적외선 가열 건조, 진공 건조, 등의 공지의 방법을 이용할 수 있다.In the subsequent drying process, volatile components such as water are removed from the coating film, and the conditions may be appropriately set, but usually 1 to 60 minutes, especially 5 to 20 ° C under temperature conditions at 100 to 200 ° C. A drying time of ˜30 minutes is used. It does not specifically limit also about a drying method, Well-known methods, such as hot air drying, infrared heat drying, vacuum drying, can be used.
또한, 필요에 따라서 도포 공정과 건조 공정을 연속하여 실시하는 것도 가능하다.Moreover, it is also possible to perform a coating process and a drying process continuously as needed.
계속되는 소성공정 (탈지 공정)에서는, 전기로 등을 이용하여 도포막 중의 유기 성분의 대부분이 제거된다. 이와 같은 공정의 조건은, 도포액의 조성이나 도포막의 두께에 의해서 적절히 조절할 필요가 있지만, 통상, 300∼1000℃, 특히 400∼800℃의 온도 조건, 1∼120분, 특히 5∼60분의 시간으로 실시된다.In the subsequent firing step (degreasing step), most of the organic components in the coating film are removed using an electric furnace or the like. Although the conditions of such a process need to be adjusted suitably according to the composition of a coating liquid and the thickness of a coating film, it is usually 300-1000 degreeC, especially 400-800 degreeC temperature conditions, 1-120 minutes, especially 5-60 minutes Is carried out in time.
또한, 확산 공정으로 반도체 기판 중에 불순물이 확산되어 확산층이 형성되지만, 소성 공정과 동일하게 전기로 등을 이용하여 800∼1400℃의 온도 조건하, 한 장 또는 복수 장을 맞춘 상태로 실시된다.In addition, although the impurity diffuses in a semiconductor substrate by a diffusion process and a diffusion layer is formed, it implements in the state which matched one or several sheets under the temperature conditions of 800-1400 degreeC using the electric furnace etc. similarly to a baking process.
또한, 소성 공정과 확산 공정을 한 공정으로 실시한다, 또는, 소성 공정에서 확산이 진행하여, 원하는 저항값을 얻을 수 있는 경우, 확산 공정을 생략하는 것도 가능하다.In addition, when a baking process and a diffusion process are performed in one process, or a diffusion progresses in a baking process and a desired resistance value can be obtained, it is also possible to omit a diffusion process.
이와 같은 반도체의 표면 저항은, 불순물의 함유량이나 확산 온도, 확산 시간 등에 의해서 제어할 수 있어 통상, 0.03∼10000Ω／□의 범위에서, 목적으로 하는 용도에 적절한 표면 저항의 것을 얻는 것이 가능하다.The surface resistance of such a semiconductor can be controlled by content of an impurity, a diffusion temperature, a diffusion time, etc., and it is possible to obtain the thing of the surface resistance suitable for the target use normally in the range of 0.03-10000 ohms / square.
(실시예)(Example)
이하, 본 발명을 실시예를 들어 설명하지만, 본 발명은 그 요지를 넘지 않는 이상 실시예의 기재로 한정되는 것은 아니다.Hereinafter, although an Example is given and demonstrated this invention, this invention is not limited to description of an Example, unless the summary is exceeded.
또한, 실시예 중, 「부」, 「%」는, 특별한 언급이 없는 한 중량 기준을 의미한다.In addition, in an Example, "part" and "%" mean a basis of weight unless there is particular notice.
제조예 1Production Example 1
〔PVA계 수지(A1)의 제조〕[Manufacture of PVA system resin (A1)]
환류 냉각기, 적하 깔때기, 교반기를 구비한 반응 용기에, 초산비닐 1500부, 메탄올 648부, 아조비스이소부티로니트릴을 0.33 몰% (첨가된 초산비닐 기준으로) 투입하여, 교반하면서 질소 기류하에서 온도를 상승시켜, 60℃에서 중합을 개시하였다. 초산비닐의 중합율이 90%가 된 시점에서, m-디니트로벤젠을 첨가하여 중합을 종료하고, 계속하여, 메탄올 증기를 취입하는 방법에 의해 미반응의 초산비닐 모노머를 계외로 제거하여 공중합체의 메탄올 용액으로 하였다.Into a reaction vessel equipped with a reflux condenser, a dropping funnel, and a stirrer, 1500 parts of vinyl acetate, 648 parts of methanol, and 0.33 mol% (based on the added vinyl acetate) were added thereto, followed by stirring under a nitrogen stream. Was raised to initiate polymerization at 60 ° C. When the polymerization rate of vinyl acetate reached 90%, m-dinitrobenzene was added to terminate the polymerization, and then unreacted vinyl acetate monomer was removed out of the system by blowing methanol vapor. It was set as the methanol solution of.
이어서, 상기 메탄올 용액을 다시 메탄올로 희석하고, 농도 30%로 조정하고 니더에 넣어, 용액 온도를 35℃에 유지하면서, 수산화나트륨의 2% 메탄올 용액을 공중합체내의 초산비닐 구조 단위의 1몰에 대해서 Na량으로서 3.4밀리몰이 되는 비율로 더하여 비누화를 실시하였다. 비누화가 진행함과 동시에 비누화물이 석출하여 입자 형태가 된 시점에서 여과 구별하여, 메탄올로 잘 세정하고 열풍 건조기 중에서 건조하여 목적으로 하는 PVA계 수지(A1)를 제작하였다.The methanol solution was then diluted again with methanol, adjusted to a concentration of 30% and placed in a kneader, while maintaining the solution temperature at 35 ° C. while adding a 2% methanol solution of sodium hydroxide to 1 mole of the vinyl acetate structural unit in the copolymer. Saponification was performed in addition to the ratio of 3.4 mmol as the Na content. As the saponification proceeded and the saponified precipitates and became a particle form, the filtration was separated, washed well with methanol, dried in a hot air dryer, and the target PVA-based resin (A1) was produced.
얻어진 PVA계 수지(A1)의 비누화도는, 잔존 초산비닐의 가수분해에 필요로 하는 알칼리 소비량에서 분석한바, 78.0 몰%이었다. 또, 평균 중합도는, JIS K 6726에 준하여 분석을 한바 1400이었다. (표 1)The saponification degree of the obtained PVA system resin (A1) was 78.0 mol% when it analyzed with the alkali consumption amount required for hydrolysis of residual vinyl acetate. In addition, the average degree of polymerization was 1400 when analyzed according to JIS K 6726. (Table 1)
제조예 2Production Example 2
〔PVA계 수지(A2)의 제조〕[Manufacture of PVA system resin (A2)]
환류 냉각기, 적하 깔때기, 교반기를 구비한 반응 용기에, 초산비닐 1000부, 메탄올 700부, 3,4-디아세톡시-1-부텐 88부를 넣고, 아조비스이소부티로니트릴을 1.5몰% (첨가된 초산비닐 기준으로) 투입하여, 교반하면서 질소 기류하에서 온도를 상승시켜 (약 60℃), 중합을 개시하였다. 중합 개시와 동시에 HANNA법에 의해, 3,4-디아세톡시-1-부텐 31부와 메탄올 122.3부의 혼합액을 적하하고, 도중, 2시간째와 4시간째의 시점에서 아조비스이소부티로니트릴을 각각 0.5몰% (첨가된 초산비닐 기준으로) 추가하였다. 중합 개시부터 9시간째의, 초산비닐의 중합율이 93.9%가 된 시점에서, m-디니트로벤젠을 첨가하여 중합을 종료하고, 계속하여 메탄올 증기를 취입하는 방법에 의해 미반응의 초산비닐 모노머를 계외로 제거하고 공중합체의 메탄올 용액으로 하였다.Into a reaction vessel equipped with a reflux condenser, a dropping funnel and a stirrer, 1000 parts of vinyl acetate, 700 parts of methanol, and 88 parts of 3,4-diacetoxy-1-butene were added, and 1.5 mol% of azobisisobutyronitrile was added. On the basis of the prepared vinyl acetate), and the temperature was raised (about 60 ° C) under a nitrogen stream while stirring to initiate polymerization. Simultaneously with the start of polymerization, a mixture of 31 parts of 3,4-diacetoxy-1-butene and 122.3 parts of methanol was added dropwise by the HANNA method, and azobisisobutyronitrile was added at the time points of 2 hours and 4 hours. 0.5 mole% each (based on the added vinyl acetate) was added. When the polymerization rate of vinyl acetate reached 93.9% from the start of the polymerization, the polymerization was terminated by adding m-dinitrobenzene to terminate the polymerization, and then unreacted vinyl acetate monomer by blowing the methanol vapor. Was removed out of the system to obtain a methanol solution of the copolymer.
이어서, 상기 메탄올 용액을 다시 메탄올로 희석하고, 농도 30%로 조정하고 니더에 넣고, 용액 온도를 35℃로 유지하면서, 수산화나트륨의 2% 메탄올 용액을 공중합체내의 초산비닐 구조 단위 및 3,4-디아세톡시-부텐 구조 단위의 합계량 1 몰에 대해서 Na량으로서 3.4밀리몰이 되는 비율로 더하여 비누화를 실시하였다. 비누화가 진행함과 동시에 비누화물이 석출하여, 입자 형태가 된 시점에서 여과 구별하여 메탄올로 잘 세정하고 열풍 건조기 중에서 건조하여 목적으로 하는 PVA계 수지(A2)를 제작하였다.The methanol solution was then diluted again with methanol, adjusted to a concentration of 30% and placed in a kneader, while maintaining the solution temperature at 35 ° C, a 2% methanol solution of sodium hydroxide was added to the vinyl acetate structural unit and 3,4 in the copolymer. Saponification was carried out by adding at a ratio of 3.4 mmol by the amount of Na to 1 mol of the total amount of the diacetoxy-butene structural unit. As the saponification proceeded, the saponified precipitates, and when the particles were in the form of particles, they were separated by filtration, washed well with methanol, and dried in a hot air dryer to prepare a target PVA resin (A2).
얻어진 PVA계 수지(A2)의 비누화도는, 잔존 초산비닐 및 3,4-디아세톡시-1-부텐의 가수분해에 필요로 하는 알칼리 소비량에서 분석한바 79.7몰%이었다. 또, 평균 중합도는, JIS K 6726에 준하여 분석을 실시한바 450이었다. 또, 화학식 1에 나타내는 1,2-디올 구조 단위의 함유량은, 1H-NMR (300 MHz 프로톤 NMR, d6-DMSO 용액, 내부 표준 물질；테트라메틸실란, 50℃)에서 측정한 적분값으로 산출한바, 6몰%이었다. (표 1) The saponification degree of the obtained PVA system resin (A2) was 79.7 mol% when it analyzed with the alkali consumption required for the hydrolysis of residual vinyl acetate and 3, 4- diacetoxy 1-butene. In addition, the average degree of polymerization was 450 as a result of analyzing in accordance with JIS K 6726. In addition, content of the 1 , 2- diol structural unit shown in General formula (1) is computed by the integral value measured by 1H-NMR (300 MHz proton NMR, d6-DMSO solution, internal standard substance; tetramethylsilane, 50 degreeC). It was 6 mol%. (Table 1)
실시예 1Example 1
＜인 확산용 도포액의 제작＞<Production of coating liquid for phosphorus diffusion>
에틸렌글리콜 (C) 85부에, 비누화도 78.0 몰%, 평균 중합도 1400인 미변성 PVA계 수지(A1) 10부를 더하여 가열교반 하면서 용해하였다. 또한, 불순물(B)로서 5산화2인(B2) 3부를 배합하여, 계면활성제(D)로서 화학식76에서, R15, R18이 2-메틸 프로필기, R16 , R17이 메틸기, s＋t≒1.3인 2,4,7,9-테트라메틸-5-데신-4,7-디올의 에틸렌옥시드 부가물 (닛신카가쿠고교사 제조「서피놀 420」)(D1) 2부를 배합하고, 인 확산용 도포액을 제작하였다.10 parts of unmodified PVA-based resins (A1) having a saponification degree of 78.0 mol% and an average degree of polymerization of 1400 were added to 85 parts of ethylene glycol (C) and dissolved while heating and stirring. In addition, the pentoxide 2 (B2) 3 combined unit as an impurity (B), in the formula 76 as a surfactant (D), R 15, R 18 is 2-methylpropyl group, R 16, R 17 is a methyl group, s + t 2 parts of ethylene oxide adducts ("Synol 420" manufactured by Nisshin Kagaku Kogyo Co., Ltd.) (D1) of 2,4,7,9-tetramethyl-5-decine-4,7-diol which is X1.3, The coating liquid for phosphorus diffusion was produced.
＜반도체 기판으로의 도포, 인쇄성 평가＞<Coating to Semiconductor Substrate, Printability Evaluation>
상기 제작의 인 확산용 도포액을 이용해 P형 반도체 기판 (다결정 실리콘, 156mm각, 200㎛ 두께)에, 하기 인쇄 조건에서 스크린 인쇄를 하고 스크렙퍼로 도포액을 공급한 상태로 일정시간 (30, 60분) 방치한 후, 재차 인쇄를 실시하였다.Using the phosphorus diffusion coating liquid prepared as described above, screen printing was performed on the P-type semiconductor substrate (polycrystalline silicon, 156 mm square, 200 μm thick) under the following printing conditions, and the coating liquid was supplied to the scraper for a predetermined time (30, 60 minutes), and it printed again.
얻어진 인쇄면 상태를 육안으로 관찰하여 하기 평가 조건에서 인쇄성을 평가하였다. 결과를 표 3에 나타내었다.The obtained printing surface state was visually observed and the printability was evaluated on the following evaluation conditions. The results are shown in Table 3.
(인쇄 조건) 인쇄기：뉴롱그세이미츠고교사 제조 「LS-34 GX」(Printing condition) Printing machine: New Longige Seizit Kogyo Co., Ltd. "LS-34GX"
스퀴지：뉴롱그세이미츠고교사 제조 NM스퀴지 (경도：60) Squeegee: New Longige Seizit Kogyo Co., Ltd. NM squeegee (hardness: 60)
스퀴지각：80도 Squeegee angle: 80 degrees
스크렙퍼：뉴롱그세이미츠고교사 제조 NM스퀴지 (경도：60) Scraper: Nlong squeegee made by Neulongs Seimitsu Kogyo Co., Ltd. (hardness: 60)
스크렙퍼각：86도 Scraper angle: 86 degrees
인쇄압：0.2MPa Print pressure: 0.2MPa
스크린판： 도쿄 프로세스 서비스사 제조Screen version: Tokyo Process Service Co., Ltd.
판 사이즈： 450mm각 Plate size ： 450mm each
메쉬종：V330 Mesh type: V330
유제종：TN-1 Oil species: TN-1
유제 두께：10㎛ Emulsion thickness ： 10㎛
패턴：L/S=80∼220㎛, 20㎛마다/L×3 30mm 각의 베타 패턴이 2개소Pattern: L / S = 80 to 220 µm, each of 20 µm, two beta patterns of / L × 3 30mm
인쇄 환경： 23℃, 60%RH Printing environment: 23 degrees Celsius, 60% RH
(평가 조건)(Evaluation condition)
○：전 패턴이 인쇄되고 있었다.(Circle): All patterns were printed.
△：인쇄된 전 패턴의 일부에 긁힘이 인정되었다.(Triangle | delta): Scratches were fixed at the part of the whole pattern printed.
×：패턴에 일부, 분명한 흠이 인정되었다.X: The part and clear flaw were recognized by the pattern.
＜반도체의 제작, 표면 저항 측정＞<Semiconductor Fabrication, Surface Resistance Measurement>
상기 제작된 인 확산용 도포액을 이용하여 상기와 같은 인쇄 조건에서, 150mm 각의 베타 패턴으로 스크린 인쇄된 반도체 기판을, 열풍 순환 건조기 중 150℃에서 2분간 건조하였다. 그 후, 온도： 850℃, 가스종： 질소＋산소(4%), 가스 유량：50L/분의 튜브로에 반도체 기판을 직립한 상태로 투입하여, 15분간 홀드 후, 꺼내, 46% 불화수소 수용액 중에서 요동시키면서 세정하였다. 이와 같이 하여, 반도체 기판 중에 인의 확산층을 갖는 반도체를 얻었다. 얻어진 반도체의 확산층의 상 부(소성시와 같이 반도체를 직립 상태로 했을 때의, 확산층 위로부터 30mm의 부분), 및 하부 (소성시와 같이 반도체를 직립 상태로 했을 때의, 확산층 아래로부터 30mm의 부분)의 표면 저항값을, 저항 측정기 (미츠비시아나리테크사 제조 「로레스타」, PSP 프로브 사용)를 이용하여 측정하였다. 결과를 표 3에 나타내었다.Under the above printing conditions, the semiconductor substrate screen-printed with a beta pattern of 150 mm was dried at 150 ° C. in a hot air circulation dryer for 2 minutes using the produced phosphorus diffusion coating liquid. Thereafter, the temperature was 850 占 폚, the gas species was nitrogen + oxygen (4%), and the gas flow rate was introduced into the tube furnace of 50 L / min in an upright state, held for 15 minutes, and then taken out. The solution was washed while shaking in an aqueous solution. In this way, a semiconductor having a diffusion layer of phosphorus in the semiconductor substrate was obtained. The upper portion of the obtained diffusion layer of the semiconductor (30 mm from the top of the diffusion layer when the semiconductor is upright as in firing), and the lower portion (30 mm from the bottom of the diffusion layer when the semiconductor is upright as in the firing The surface resistance value of the part was measured using the resistance measuring instrument ("Lolesta" by Mitsubishi Naaritech Co., Ltd., using a PSP probe). The results are shown in Table 3.
실시예 2Example 2
실시예 1에서, 불순물(B)로서 인산 에스테르 (화학식 6에서 R12가 메틸기, R13이 수소, R14가 수소, n이 1, m이 1, l이 2인 엑시드포스폭시메타아크릴레이트(유니케미칼사 제조 「호스마 M」))(B1) 7부를 이용하여 다가 알코올(C)로서 에틸렌글리콜과 글리세린의 혼합물을 사용하고, 계면활성제(D)로서 아미노알콕시실란을 주성분으로 하는 화합물 (토오레·다우코닝사 제조 「SH-21」)(D2)를 이용하여 각 성분의 배합량을 표 2에 나타내는 대로 하였다. 그 이외는 실시예 1과 같이 하여 인 확산용 도포액을 제작하여 동일하게 평가하였다. 평가 결과를 표 3에 나타낸다.In Example 1, as an impurity (B), a phosphate ester (Ex phosphoxymethacrylate having R 12 is a methyl group, R 13 is hydrogen, R 14 is hydrogen, n is 1, m is 1, 1 is 2, Using a mixture of ethylene glycol and glycerin as polyhydric alcohol (C), using 7 parts of `` Hosema M '')) (B1) manufactured by Unichemical Co., Ltd. Using Ore Dow Corning Corporation "SH-21") (D2), the compounding quantity of each component was as showing in Table 2. Other than that was carried out similarly to Example 1, the coating liquid for phosphorus diffusion was produced, and it evaluated similarly. The evaluation results are shown in Table 3.
실시예 3Example 3
실시예 1에서, 다가 알코올(C)로서 에틸렌글리콜과 글리세린의 혼합물을 사용하여, 다시 무기 미립자(E)로서 물 80wt%에 20wt%의 콜로이달 실리카가 분산되고 있는 콜로이달 실리카 용액 (후지미코포레이션사 제조 「PLANERLITE 4101」) 10부를 배합하고, 각 성분의 배합량을 표 2에 나타내는 대로 하였다. 그 이외는 실시예 1과 동일하게 하여 인 확산용 도포액을 제작하고, 동일하게 평가하였다. 평가 결과를 표 3에 나타낸다.In Example 1, using a mixture of ethylene glycol and glycerin as the polyhydric alcohol (C), colloidal silica solution in which 20 wt% of colloidal silica is dispersed in 80 wt% of water as inorganic fine particles (E) (Fujimi Corporation) 10 parts of manufacture "PLANERLITE 4101" were mix | blended, and the compounding quantity of each component was as showing in Table 2. Other than that was carried out similarly to Example 1, the coating liquid for phosphorus diffusion was produced, and it evaluated similarly. The evaluation results are shown in Table 3.
실시예 4Example 4
실시예 2에서, PVA계 수지(A)로서 제조예 2에서 얻어진 PVA계 수지(A2)를 이용해 다가 알코올(C)로서 에틸렌글리콜과 글리세린의 혼합물을 사용하여, 계면활성제(D)를 배합하지 않고, 각 성분의 배합량을 표 2에 나타내는 대로로 하였다. 그 이외는 실시예 1과 같게 하여 인 확산용 도포액을 제작하여 동일하게 평가하였다. 평가 결과를 표 3에 나타낸다.In Example 2, a mixture of ethylene glycol and glycerin was used as the polyhydric alcohol (C) using the PVA resin (A2) obtained in Production Example 2 as the PVA-based resin (A), without blending the surfactant (D). And the compounding quantity of each component as it is shown in Table 2. Other than that was carried out similarly to Example 1, the coating liquid for phosphorus diffusion was produced, and it evaluated similarly. The evaluation results are shown in Table 3.
실시예 5Example 5
실시예 4에서, 계면활성제(D)로서 유기 변성 폴리실록산과 특수 폴리머의 혼합물을 함유하는 수계 에멀젼 (쿄에이샤카가쿠사 제조 「아쿠아 렌 SB-630」(D3)을 이용하여 각 성분의 배합량을 표 2에 나타내는 대로 하였다. 그 이외는 실시예 4와 동일하게 하여 인 확산용 도포액을 제작하고 동일하게 평가하였다. 평가 결과를 표 3에 나타낸다.In Example 4, the compounding quantity of each component is shown using the aqueous emulsion (Aqualen SB-630 by Kyoeisha Chemical Co., Ltd. (D3) which contains the mixture of organic modified polysiloxane and a special polymer as surfactant (D). The coating liquid for phosphorus diffusion was produced and evaluated similarly in the same manner as in Example 4. The evaluation result is shown in Table 3.
실시예 6Example 6
실시예 1에서 불순물(B)로서 붕산(B3) 2부를 이용하여 에틸렌글리콜 (C1)을 86부로 하였다. 그 이외는 실시예 1과 동일하게 하여 불순물 확산용 도포액을 제작하였다. 얻어진 도포액을 이용해 반도체 기판으로서 N형 반도체 기판을 이용한 것 이외는 실시예 1과 동일하게 반도체 기판에 스크린 인쇄를 하여 인쇄성 평가를 하였다. 또, 상기 도포액을 이용하여 이하의 기준에 따라 반도체의 제작, 표면 저항 측정을 하였다. 결과를 표 3에 나타낸다.In Example 1, ethylene glycol (C1) was 86 parts using 2 parts of boric acid (B3) as the impurity (B). A coating liquid for impurity diffusion was produced in the same manner as in Example 1 except for the above. Except having used the N type semiconductor substrate as a semiconductor substrate using the obtained coating liquid, it carried out the screen printing to the semiconductor substrate similarly to Example 1, and evaluated printability. Moreover, using the said coating liquid, the semiconductor was produced and surface resistance measurement was performed according to the following criteria. The results are shown in Table 3.
＜반도체의 제작, 표면 저항 측정＞<Semiconductor Fabrication, Surface Resistance Measurement>
얻어진 불순물 확산용 도포액을 이용하여 상기와 같은 인쇄 조건에서, 150mm 각의 베타패턴으로 스크린 인쇄된 반도체 기판을, 열풍 순환 건조기 중 150℃에서 2분간 건조하였다. 그 후, 온도：950℃, 가스종：질소, 가스 유량：50L/분의 튜브로에 반도체 기판을 직립한 상태로 투입하여, 15분간 홀드 후, 질소를 멈추고 산소를 동류량으로 15분 흘렸다. 이어서, 기판을 꺼내, 46% 불화수소 수용액 중에서 요동시키면서 세정하고, 반도체 기판 중에 붕소의 확산층을 갖는 반도체를 얻어, 그 확산층의 상부 및 하부의 표면 저항값을, 실시예 1과 동일하게 측정하였다. 결과를 표 3에 나타낸다.Using the obtained impurity diffusion coating liquid, the semiconductor substrate screen-printed by the 150 mm square beta pattern was dried for 2 minutes at 150 degreeC in a hot air circulation dryer under the above printing conditions. Thereafter, the semiconductor substrate was placed in an upright state in a tube furnace having a temperature of 950 ° C., a gas species of nitrogen, and a gas flow rate of 50 L / min. After holding for 15 minutes, nitrogen was stopped and oxygen was flowed for 15 minutes at the same flow rate. Subsequently, the substrate was taken out and washed while shaking in a 46% hydrogen fluoride aqueous solution to obtain a semiconductor having a boron diffusion layer in the semiconductor substrate, and the surface resistance values of the upper and lower portions of the diffusion layer were measured in the same manner as in Example 1. The results are shown in Table 3.
실시예 7Example 7
실시예 2에서 불순물(B)로서 붕산트리에틸(B4) 7부를 이용한 것 이외는 실시예 2와 동일하게 하여 불순물 확산용 도포액을 제작하고, 실시예 6과 동일하게 하여 평가하였다. 평가 결과를 표 3에 나타낸다.Except for using 7 parts of triethyl borate (B4) as an impurity (B) in Example 2, the coating liquid for impurity diffusion was produced like Example 2, and it evaluated similarly to Example 6. The evaluation results are shown in Table 3.
비교예 1Comparative Example 1
실시예 1에서 용제로서 에틸렌글리콜과 함께 물을 이용하여 각 성분의 배합량을 표 2에 나타내는 대로 한 것 이외는 실시예 1과 동일하게 하여 인 확산용 도포액을 제작하여 동일하게 평가하였다. 평가 결과를 표 3에 나타낸다.Except having made the compounding quantity of each component as shown in Table 2 using water with ethylene glycol as a solvent in Example 1, the coating liquid for phosphorus diffusion was produced and evaluated similarly to Example 1. The evaluation results are shown in Table 3.
비교예 2Comparative Example 2
실시예 1에서 PVA계 수지(A)를 대신하여 평균 중합도 450의 폴리초산비닐을 이용하여 불순물(B)로서 인산 에스테르(B1)를 이용하여 용제로서 이소부틸산-3-히드록시-2,2,4-트리메틸펜틸에스테르 (TPM)를 이용하여 계면활성제(D)를 배합하지 않고, 무기 미립자(E)로서 콜로이달 실리카 (후지미코포레이션사 제조 「PLANERLITE 4101」)를 배합하여 각 성분의 배합량을 표 2에 나타내는 대로 하였다. 그 이외는 실시예 1과 동일하게 하여 인 확산용 도포액을 제작하고 동일하게 평가하였다. 평가 결과를 표 3에 나타낸다.In Example 1 isobutyl acid-3-hydroxy-2,2 as a solvent using phosphate ester (B1) as an impurity (B) using polyvinyl acetate having an average degree of polymerization of 450 in place of PVA-based resin (A) The compound amount of each component is mix | blended by mixing colloidal silica ("PLANERLITE 4101" by Fujimi Corporation) as inorganic fine particles (E), without mix | blending surfactant (D) using 4, 4- trimethyl pentyl ester (TPM). It was as shown in 2. Other than that was carried out similarly to Example 1, the coating liquid for phosphorus diffusion was produced, and it evaluated similarly. The evaluation results are shown in Table 3.
본 발명의 인 확산용 도포액은 스크린 인쇄에서, 일정시간 방치한 다음에도 뛰어난 인쇄성을 얻을 수 있었다. 또, 본 발명의 도포액으로부터 얻어진 반도체는, 상하의 표면 저항값의 차이가 작은 것이었다. Phosphorus diffusion coating liquid of the present invention was screen printed, and excellent printability was obtained even after being left for a certain time. Moreover, the semiconductor obtained from the coating liquid of this invention had a small difference of the upper and lower surface resistance values.
한편, 물을 주체로 하는 용제를 이용한 비교예 1의 도포액은, 30분 방치한 후의 인쇄성이 뒤떨어지는 것이며, 바인더로서 폴리초산비닐을 이용한 비교예 2의 도포액은 얻어진 반도체의 상하의 표면 저항값의 차이가 큰 것이었다.On the other hand, the coating liquid of the comparative example 1 using the solvent which mainly uses water is inferior to the printability after leaving for 30 minutes, and the coating liquid of the comparative example 2 using polyvinyl acetate as a binder has the upper and lower surface resistance of the obtained semiconductor. The difference in value was large.
또한, 상기 실시예에서는, 본 발명에 있어서의 구체적인 형태에 대해 나타냈지만, 상기 실시예는 단순한 예시에 지나지 않고, 한정적으로 해석되는 것은 아니다. 당업자에게 분명한 여러 가지 변형은, 본 발명의 범위 내인 것으로 포함될 수 있다.While the present invention has been shown and described with reference to specific embodiments thereof, it is to be understood that these embodiments are merely illustrative and not restrictive. Various modifications apparent to those skilled in the art can be included within the scope of the present invention.
(산업상의 이용 가능성)(Industrial availability)
본 발명의 불순물 확산용 도포액은, 장시간의 연속 인쇄나 휴지 기간을 둔 인쇄가 가능하고, 피막 형성 후의 반도체 기판을 직립 상태로 소성하였다고 하여도 저항값의 상하 불균형이 작은 반도체를 얻을 수 있기 때문에 공업적으로 지극히 유용하다.Since the impurity diffusion coating liquid of the present invention can be printed for a long period of continuous printing or with a rest period, even if the semiconductor substrate after film formation is fired in an upright state, a semiconductor having a small up and down imbalance in resistance value can be obtained. Extremely useful industrially.
Claims (6)
폴리비닐 알코올계 수지(A)는, 비누화도가 50∼90 몰%의 폴리비닐 알코올계 수지(A)인 것을 특징으로 하는 불순물 확산용 도포액.The method according to claim 1,
The polyvinyl alcohol-based resin (A) is a polyvinyl alcohol-based resin (A) having a saponification degree of 50 to 90 mol%, wherein the coating liquid for impurity diffusion.
폴리비닐 알코올계 수지(A)는, 하기 화학식 1로 표시되는 구조 단위를 5∼10 몰% 함유하는 폴리비닐 알코올계 수지인 것을 특징으로 하는 불순물 확산용 도포액.
[화학식 1]
[식 중, R1, R2 및 R3는 각각 독립적으로 수소 원자 또는 유기기를 나타내며, X는 단결합 또는 결합쇄를 나타내고, R4, R5 및 R6은 각각 독립하여 수소 원자 또는 유기기를 나타낸다.]The method according to claim 1 or 2,
Polyvinyl alcohol-type resin (A) is polyvinyl alcohol-type resin containing 5-10 mol% of structural units represented by following formula (1), The impurity diffusion coating liquid characterized by the above-mentioned.
[Chemical Formula 1]
[Wherein, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an organic group, X represents a single bond or a bond chain, and R 4 , R 5 and R 6 each independently represent a hydrogen atom or an organic group; Is displayed.]
불순물(B)은 13족 원소 화합물 및 15족 원소 화합물의 적어도 하나인 것을 특징으로 하는 불순물 확산용 도포액.4. The method according to any one of claims 1 to 3,
The impurity (B) is an impurity diffusion coating liquid, characterized in that at least one of a Group 13 element compound and a Group 15 element compound.
계면활성제(D)를 함유하는 것을 특징으로 하는 불순물 확산용 도포액.5. The method according to any one of claims 1 to 4,
It contains surfactant (D), The coating liquid for impurity diffusion characterized by the above-mentioned.
무기 미립자(E)를 함유하는 것을 특징으로 하는 불순물 확산용 도포액.6. The method according to any one of claims 1 to 5,
An inorganic fine particle (E) is contained, The impurity diffusion coating liquid characterized by the above-mentioned.
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| JP3522940B2 (en) * | 1995-12-26 | 2004-04-26 | 東京応化工業株式会社 | Boron diffusion coating solution |
| JP3916941B2 (en) * | 2000-12-15 | 2007-05-23 | 日本合成化学工業株式会社 | New vinyl alcohol resin and its use |
| JP4541328B2 (en) * | 2005-07-22 | 2010-09-08 | 日本合成化学工業株式会社 | Phosphorus diffusion coating solution |
| JP4541243B2 (en) * | 2005-07-22 | 2010-09-08 | 日本合成化学工業株式会社 | Boron diffusion coating solution |
| JP4589907B2 (en) * | 2006-10-16 | 2010-12-01 | 株式会社島田電機製作所 | Braille plate and braille light emitting display device |
| US8314175B2 (en) * | 2007-03-22 | 2012-11-20 | The Nippon Synthetic Chemical | Aqueous composition for recording medium, and ink-jet recording medium using the same |
| KR100959136B1 (en) * | 2008-07-16 | 2010-05-25 | 한국전자통신연구원 | Direct memory access controller and data transmitting method of direct memory access channel |
| JP5470779B2 (en) * | 2008-09-03 | 2014-04-16 | 富士通株式会社 | Method for manufacturing integrated circuit device |
| JP2010161317A (en) * | 2009-01-09 | 2010-07-22 | Tokyo Ohka Kogyo Co Ltd | Diffusing agent composition, method for forming impurity diffusion layer, and solar cell |
| KR20130141547A (en) * | 2010-11-29 | 2013-12-26 | 닛폰고세이가가쿠고교 가부시키가이샤 | Coating liquid for impurity diffusion |
-
2012
- 2012-05-18 CN CN2012800170092A patent/CN103460346A/en active Pending
- 2012-05-18 JP JP2012114383A patent/JP2013008953A/en active Pending
- 2012-05-18 WO PCT/JP2012/062745 patent/WO2012161107A1/en active Application Filing
- 2012-05-18 KR KR1020137025806A patent/KR20140011354A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CN103460346A (en) | 2013-12-18 |
| WO2012161107A1 (en) | 2012-11-29 |
| JP2013008953A (en) | 2013-01-10 |
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