CN113024700A - 硅片硼扩散用可喷涂硼源及其应用 - Google Patents
硅片硼扩散用可喷涂硼源及其应用 Download PDFInfo
- Publication number
- CN113024700A CN113024700A CN202110251406.7A CN202110251406A CN113024700A CN 113024700 A CN113024700 A CN 113024700A CN 202110251406 A CN202110251406 A CN 202110251406A CN 113024700 A CN113024700 A CN 113024700A
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- Prior art keywords
- boron
- silicon wafer
- diffusion
- boron source
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 145
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 126
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 55
- 239000010703 silicon Substances 0.000 title claims abstract description 55
- 238000009792 diffusion process Methods 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- -1 boron modified acrylate Chemical class 0.000 claims abstract description 32
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000005507 spraying Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000007641 inkjet printing Methods 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 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 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- KUGSJJNCCNSRMM-UHFFFAOYSA-N ethoxyboronic acid Chemical compound CCOB(O)O KUGSJJNCCNSRMM-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- UYVXZUTYZGILQG-UHFFFAOYSA-N methoxyboronic acid Chemical compound COB(O)O UYVXZUTYZGILQG-UHFFFAOYSA-N 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- JMVWCCOXRGFPJZ-UHFFFAOYSA-N propoxyboronic acid Chemical compound CCCOB(O)O JMVWCCOXRGFPJZ-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 claims 15
- 229920000178 Acrylic resin Polymers 0.000 abstract description 5
- 239000004925 Acrylic resin Substances 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 150000003384 small molecules Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- RCZNLTJRUAXFOQ-UHFFFAOYSA-N 2-prop-2-enoyloxyethoxyboronic acid Chemical compound OB(O)OCCOC(=O)C=C RCZNLTJRUAXFOQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F130/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了提供一种硅片硼扩散用可喷涂硼源,该硼源为硼改性丙烯酸酯类聚合物,其合成方法为:以(取代)硼酸和(α‑取代)丙烯酸羟烷基酯为原料,在阻聚剂和带水剂存在下进行酯化反应得到含硼的(α‑取代)丙烯酸酯单体,再对此单体进行自由基聚合得到含硼的丙烯酸树脂。本发明还提供该硼源的应用。本发明硼源可溶于乙醇或乙醇与水的混合液,从而形成适于喷涂和喷墨打印的硼源溶液,且可提高硼源喷涂的均匀性。
Description
技术领域
本发明涉及硼源,具体涉及一种硅片硼扩散用可喷涂硼源及其应用。
背景技术
最近几年,将液体硼源作为扩散源的硼扩散工艺得到发展迅速,其通过旋涂、喷涂或者丝网印刷技术在硅片表面沉积一层液体硼源,然后再进行扩散。旋涂硼源扩散的方阻均匀性比较好,但该工艺不适合大批量连续化作业,生产效率低。此外旋涂工艺会出现硼源溢流到硅片背面的现象,由于硅片中心与边缘的等效掺杂源浓度有所差异,限制了旋涂均匀性的进一步提高,同时也增加了后道工艺的难度。
相比较而言,喷涂工艺可以连续化作业,进一步与链式扩散设备结合,可实现高产量、高自动化的工业化生产。中国专利CN106449383A公开了一种硼扩散技术,采用硼源溶液喷涂或喷墨打印在硅片表面,再高温扩散形成PN结,但该技术所用液体硼源其实是一种悬浊液分散体系,采用的是含硼氧化物粉体或硼氮化合物粉体作为硼源。这类悬浊液体系存在诸多弊端:首先,悬浊液体系本身是不稳定的,悬浮粉体受胶体力、无规热运动力以及粘性力的共同作用,在喷涂过程中,气流急速推动悬浊液分散体系,形成气、液、固三相混合体,会导致悬浮粉体颗粒在高速流动过程中聚集;同时,从喷头喷出的混合体系的固液比例也会随着体系分散的不均匀而使涂敷到硅片表面的含硼粉体颗粒分布不均匀。其次,当悬浊液喷涂于硅表面时,溶液不再均匀,溶液在硅片表面的表面张力是急剧不均衡的,因为溶剂多的部位的表面张力与仅仅有粉体处的表面张力完全不同;而且无机粉体也会在气流作用下,沿着硅片表面翻滚,呈放射状的运动轨迹,使得喷涂均匀性更难以控制。
若采用含硼有机小分子分散体系作为硼源,由于低分子量和分子结构的原因,含硼有机小分子受到喷口速度变化影响的敏感性高;而且,小分子结构在硅片表面的空间位阻性能低,会受到液流轨迹影响,同样不利于最后沉积到硅片表面的含硼小分子的分布均匀性。而具有一定分子量的含硼聚合物能够有效解决这些矛盾,但通常的含硼聚合物都不好溶解,或者必须溶于少数极性较强溶剂,如二甲基甲酰胺、四氢呋喃等,而这些都是有毒溶剂,不适于产线喷涂操作。
发明内容
本发明的目的在于提供一种硅片硼扩散用可喷涂硼源及其应用,该硼源可溶于乙醇或乙醇与水的混合液,从而形成适于喷涂和喷墨打印的硼源溶液,且可提高硼源喷涂的均匀性。
为实现上述目的,本发明提供一种硅片硼扩散用可喷涂硼源,该硼源为硼改性丙烯酸酯类聚合物,该硼改性丙烯酸酯类聚合物具有如式(I)的通式:
其中,n为1~100000;m为1~3;R独立选自氢原子、烷基或芳基;R′、R″各自独立的选自氢原子、烷基、芳基、羟基或烷氧基。
本发明还提供一种硅片硼扩散用可喷涂硼源溶液,该硼源溶液含有溶剂以及上述的硼源,硼源与溶剂的质量比为0.5~50:100;所述溶剂为乙醇或乙醇与水的混合液;所述混合液中乙醇的质量百分含量不低于0.5%。
本发明还提供一种硅片的硼扩散方法,将上述的硼源溶液喷涂或喷墨打印在硅片表面,通过高温处理后扩散形成PN结。
本发明的优点和有益效果在于:提供一种硅片硼扩散用可喷涂硼源及其应用,该硼源可溶于乙醇或乙醇与水的混合液,从而形成适于喷涂和喷墨打印的硼源溶液,且可提高硼源喷涂的均匀性。
1)如背景技术中所述:悬浊液体系本身是不稳定的,悬浮粉体受胶体力、无规热运动力以及粘性力的共同作用,在喷涂过程中,气流急速推动悬浊液分散体系,形成气、液、固三相混合体,会导致悬浮粉体颗粒在高速流动过程中聚集;从喷头喷出的混合体系的固液比例也会随着体系分散的不均匀而使涂敷到硅片表面的含硼粉体颗粒分布不均匀;若采用含硼有机小分子分散体系作为硼源,由于低分子量和分子结构的原因,含硼有机小分子受到喷口速度变化影响的敏感性高;小分子结构在硅片表面的空间位阻性能低,会受到液流轨迹影响,同样不利于最后沉积到硅片表面的含硼小分子的分布均匀性。
为改善和解决上述问题,本发明采用硼改性丙烯酸酯类聚合物作为硼源,由于该聚合物含有较多支链,聚合物分子链之间的作用力会加强,导致它在流动以及喷涂过程中受到气流的影响会减小很多,所以从喷口而出的溶液中溶质与溶剂的比例更加均一。
2)又如背景技术中所述:当悬浊液喷涂与硅表面时,溶液不再均匀,溶液在硅片表面的表面张力是急剧不均衡的,因为溶剂多的部位的表面张力与仅仅有粉体处的表面张力完全不同;无机粉体也会在气流作用下,沿着硅片表面翻滚,呈放射状的运动轨迹,使得喷涂均匀性更难以控制。
为改善和解决上述问题,本发明采用硼改性丙烯酸酯类聚合物作为硼源,因为硼聚合物溶液不再含有上述这些粉体,它所配制成的也不是悬浊液;当含有硼聚合物的溶液从喷口出来后在硅片表面铺展时,硼聚合物分子是有个逐步接触硅片表面的过程,同时由于其分子的空间位阻效应,聚合物分子一旦与硅片表面接触后,无法在硅片表面翻滚;这些作用使得硼源喷涂均匀性得到改善。
3)本发明采用硼改性丙烯酸酯类聚合物作为硼源,硼聚合物均匀附着于硅片表面后,在扩散炉内随着温度升高以及氧气的通入,硼聚合物会脱去碳、氢,转变为氧化硼,通过与硅反应,硼被掺入硅。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
本发明提供一种硅片硼扩散用可喷涂硼源,该硼源为硼改性丙烯酸酯类聚合物,该硼改性丙烯酸酯类聚合物具有如式(I)的通式:
其中,n为1~100000;m为1~3;R独立选自氢原子、烷基或芳基;R′、R″各自独立的选自氢原子、烷基、芳基、羟基或烷氧基。
作为优选方案之一,所述硼改性丙烯酸酯类聚合物具有如式(II)的通式:
其中,n1为1~100000;m为1~3;R独立选自氢原子、烷基或芳基。
作为优选方案之二,所述硼改性丙烯酸酯类聚合物具有如式(III)的通式:
其中,n1、n2各自独立的为1~100000;m为1~3;R独立选自氢原子、烷基或芳基;R′独立选自氢原子或丙烯酸酯结构单元。
作为优选方案之三,所述硼改性丙烯酸酯类聚合物具有如式(IV)的通式:
其中,n1、n2、n3各自独立的为1~100000;m为1~3;R独立选自氢原子、烷基或芳基。
作为优选方案之四,所述硼改性丙烯酸酯类聚合物具有如式(V)的通式:
其中,n1为1~100000;m为1~3;R独立选自氢原子、烷基或芳基;R′独立选自氢原子、烷基或芳基。
作为优选方案之五,所述硼改性丙烯酸酯类聚合物具有如式(VI)的通式:
其中,n1、n3各自独立的为1~100000;m为1~3;R独立选自氢原子、烷基或芳基;R′独立选自氢原子、烷基或芳基。
作为优选方案之六,所述硼改性丙烯酸酯类聚合物具有如式(VII)的通式:
其中,n1为1~100000;m为1~3;R独立选自氢原子、烷基或芳基;R′、R″各自独立的选自氢原子、烷基或芳基。
本发明还提供一种硅片硼扩散用可喷涂硼源溶液,该硼源溶液含有溶剂以及上述的硼源,硼源与溶剂的质量比为0.5~50:100;所述溶剂为乙醇或乙醇与水的混合液;所述混合液中乙醇的质量百分含量不低于0.5%。
本发明还提供一种硅片的硼扩散方法,将上述的硼源溶液喷涂或喷墨打印在硅片表面,通过高温处理后扩散形成PN结。
更具体的,上述硅片的硼扩散方法,其具体步骤包括:
1)制备含硼的(α-取代)丙烯酸酯单体:以(取代)硼酸和(α-取代)丙烯酸羟烷基酯为原料,在阻聚剂和带水剂存在下进行酯化反应,然后蒸馏除去溶剂得到含硼的(α-取代)丙烯酸酯单体;
所述(取代)硼酸选自硼酸、甲基硼酸、乙基硼酸、丙基硼酸、苯硼酸、芳基硼酸、2-羟基-1,3,2-苯并二氧硼烷中的一种;
所述(α-取代)丙烯酸羟烷基酯选自丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯中的一种;
所述阻聚剂选自对叔丁基邻苯二酚、2,6-二叔丁基对甲基苯酚、对羟基苯甲醚、对苯二酚、四氯苯醌、1,4-萘醌、吩噻嗪中的一种;
所述带水剂选自环己烷、四氯化碳、苯、甲苯中的一种;
制备含硼的(α-取代)丙烯酸酯单体的反应条件为:回流溶剂带水6~120小时,(取代)硼酸、(α-取代)丙烯酸羟烷基酯、阻聚剂的摩尔比为1:1~100:0.00001~0.1;
2)制备硼改性丙烯酸酯类聚合物:以步骤1)制得的含硼的(α-取代)丙烯酸酯单体为原料,在引发剂和第一溶剂中以自由基聚合的方式得到硼改性丙烯酸酯类聚合物;该硼改性丙烯酸酯类聚合物可溶于甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇或叔丁醇中;
所述引发剂选自异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化苯甲酰、过氧化苯甲酸叔丁酯、过硫酸钾、过硫酸钠、过硫酸铵、偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯中的一种或多种(引发剂优选偶氮二异丁腈);
所述第一溶剂选自水、甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、叔丁醇、乙醚、甲基叔丁基醚、乙二醇单甲醚、乙二醇二甲醚、乙二醇单乙醚、乙二醇二乙醚、二氧六环、四氢呋喃、丙酮、甲基异丁基酮、乙酸乙酯、乙酸丁酯、二氯甲烷、氯仿、四氯化碳、乙腈、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、苯、甲苯、二甲苯、氯苯中的一种;
制备硼改性丙烯酸酯类聚合物的反应条件为:于30~150℃反应1~72小时;
3)制备硼源溶液:以步骤2)制得的硼改性丙烯酸酯类聚合物为硼源,将硼源溶解于第二溶剂中,制得硼源溶液;
所述硼源与第二溶剂的质量比为0.5~50:100;第二溶剂为乙醇或乙醇与水的混合液;混合液中乙醇的质量百分含量不低于0.5%;
4)在硅片表面喷涂或喷墨打印硼源溶液;
5)高温扩散:扩散温度为800~1000℃,扩散时间为5~180min。
本发明的具体实施例如下:
1)将78.084g甲基丙烯酸羟乙酯(0.6mol)、37.08g硼酸(0.6mol)、0.12g对苯二酚(0.001mol)分别加入带有干燥三口烧瓶中,然后加入150mL甲苯;三口烧瓶上接分水器,分水器上接球形冷凝管,三口烧瓶其他口接温度计和玻璃塞;打开搅拌和循环水,升温至回流,将分水器中收集到的水放出来称重,回流72小时后生成的水接近理论值时,停止反应;将反应体系中的甲苯蒸掉后得到含硼的甲基丙烯酸酯单体,包括以下三种结构(单丙烯酰氧乙基硼酸酯、二丙烯酰氧乙基硼酸酯、三丙烯酰氧乙基硼酸酯):
单体为粘稠液体,产率97%。
2)将20g上述得到的含硼的甲基丙烯酸酯单体、0.4g偶氮二异丁腈溶解于21g乙酸乙酯中,然后将此溶液于室温下滴加到预先已加热至80℃的盛有9g乙酸乙酯的三口烧瓶中;保持反应体系温度为80℃,2小时滴加完毕,再80℃保温2小时后停止反应;将反应体系中的溶剂蒸掉后得到含硼丙烯酸树脂白色固体,产率98%,包括以下三种结构:
(包含于式II中,n1为1~100000)
(包含于式III中,n1、n2各自独立的为1~100000)
(包含于式IV中,n1、n2、n3各自独立的为1~100000)
3)将上述得到的含硼丙烯酸树脂溶解在乙醇中,得到含硼丙烯酸树脂质量分数为1%的溶液,将此溶液作为喷涂的硼源。
4)在硅片表面喷涂或喷墨打印硼源溶液。
5)将喷涂硼源的硅片放入炉管内扩散,扩散温度为980℃,扩散时间为80min。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (13)
8.硅片硼扩散用可喷涂硼源溶液,其特征在于,该硼源溶液含有溶剂以及权利要求1至7中任一项所述的硼源,硼源与溶剂的质量比为0.5~50:100;所述溶剂为乙醇或乙醇与水的混合液;所述混合液中乙醇的质量百分含量不低于0.5%。
9.硅片的硼扩散方法,其特征在于,将权利要求8所述的硼源溶液喷涂或喷墨打印在硅片表面,通过高温处理后扩散形成PN结。
10.根据权利要求9所述的硅片的硼扩散方法,其特征在于,其具体步骤包括:
1)制备含硼的(α-取代)丙烯酸酯单体:以(取代)硼酸和(α-取代)丙烯酸羟烷基酯为原料,在阻聚剂和带水剂存在下进行酯化反应,然后蒸馏除去溶剂得到含硼的(α-取代)丙烯酸酯单体;
所述(取代)硼酸选自硼酸、甲基硼酸、乙基硼酸、丙基硼酸、苯硼酸、芳基硼酸、2-羟基-1,3,2-苯并二氧硼烷中的一种;
所述(α-取代)丙烯酸羟烷基酯选自丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯中的一种;
所述阻聚剂选自对叔丁基邻苯二酚、2,6-二叔丁基对甲基苯酚、对羟基苯甲醚、对苯二酚、四氯苯醌、1,4-萘醌、吩噻嗪中的一种;
所述带水剂选自环己烷、四氯化碳、苯、甲苯中的一种;
2)制备硼改性丙烯酸酯类聚合物:以步骤1)制得的含硼的(α-取代)丙烯酸酯单体为原料,在引发剂和第一溶剂中以自由基聚合的方式得到硼改性丙烯酸酯类聚合物;
所述引发剂选自异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化苯甲酰、过氧化苯甲酸叔丁酯、过硫酸钾、过硫酸钠、过硫酸铵、偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯中的一种或多种;
所述第一溶剂选自水、甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、叔丁醇、乙醚、甲基叔丁基醚、乙二醇单甲醚、乙二醇二甲醚、乙二醇单乙醚、乙二醇二乙醚、二氧六环、四氢呋喃、丙酮、甲基异丁基酮、乙酸乙酯、乙酸丁酯、二氯甲烷、氯仿、四氯化碳、乙腈、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、苯、甲苯、二甲苯、氯苯中的一种;
3)制备硼源溶液:以步骤2)制得的硼改性丙烯酸酯类聚合物为硼源,将硼源溶解于第二溶剂中,制得硼源溶液;
所述硼源与第二溶剂的质量比为0.5~50:100;第二溶剂为乙醇或乙醇与水的混合液;混合液中乙醇的质量百分含量不低于0.5%;
4)在硅片表面喷涂或喷墨打印硼源溶液;
5)高温扩散:扩散温度为800~1000℃,扩散时间为5~180min。
11.根据权利要求10所述的硅片的硼扩散方法,其特征在于,步骤1)制备含硼的(α-取代)丙烯酸酯单体的反应条件为:回流溶剂带水6~120小时,(取代)硼酸、(α-取代)丙烯酸羟烷基酯、阻聚剂的摩尔比为1:1~100:0.00001~0.1。
12.根据权利要求10所述的硅片的硼扩散方法,其特征在于,步骤2)制备硼改性丙烯酸酯类聚合物的反应条件为:于30~150℃反应1~72小时。
13.根据权利要求10所述的硅片的硼扩散方法,其特征在于,所述硼改性丙烯酸酯类聚合物可溶于甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇或叔丁醇中。
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