TWI580065B - Diffusion method of impurity diffusion component and manufacturing method of solar cell - Google Patents
Diffusion method of impurity diffusion component and manufacturing method of solar cell Download PDFInfo
- Publication number
- TWI580065B TWI580065B TW102125552A TW102125552A TWI580065B TW I580065 B TWI580065 B TW I580065B TW 102125552 A TW102125552 A TW 102125552A TW 102125552 A TW102125552 A TW 102125552A TW I580065 B TWI580065 B TW I580065B
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- Taiwan
- Prior art keywords
- type
- diffusing agent
- impurity diffusion
- diffusing
- impurity
- Prior art date
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- 238000009792 diffusion process Methods 0.000 title claims description 184
- 239000012535 impurity Substances 0.000 title claims description 131
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 203
- 239000000758 substrate Substances 0.000 claims description 83
- 239000004065 semiconductor Substances 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 46
- 238000010304 firing Methods 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 30
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 24
- 229910052796 boron Inorganic materials 0.000 claims description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 description 63
- -1 boronic acid ester Chemical class 0.000 description 33
- 125000000217 alkyl group Chemical group 0.000 description 23
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- 229920005862 polyol Polymers 0.000 description 18
- 150000003077 polyols Chemical class 0.000 description 17
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 16
- 239000003960 organic solvent Substances 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 13
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- 125000001424 substituent group Chemical group 0.000 description 7
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- GCGOSWDCNJRBCH-UHFFFAOYSA-N 2,2-diethoxyundecane Chemical compound CCCCCCCCCC(C)(OCC)OCC GCGOSWDCNJRBCH-UHFFFAOYSA-N 0.000 description 2
- YNICHAOCDICNOT-UHFFFAOYSA-N 2,2-dimethoxyundecane Chemical compound CCCCCCCCCC(C)(OC)OC YNICHAOCDICNOT-UHFFFAOYSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- 150000001639 boron compounds Chemical class 0.000 description 2
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- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
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- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 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
- 239000000594 mannitol Substances 0.000 description 1
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- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- FFWSICBKRCICMR-UHFFFAOYSA-N methyl isopentyl ketone Natural products CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- KDQYHGMMZKMQAA-UHFFFAOYSA-N trihexyl borate Chemical compound CCCCCCOB(OCCCCCC)OCCCCCC KDQYHGMMZKMQAA-UHFFFAOYSA-N 0.000 description 1
- DTBRTYHFHGNZFX-UHFFFAOYSA-N trioctyl borate Chemical compound CCCCCCCCOB(OCCCCCCCC)OCCCCCCCC DTBRTYHFHGNZFX-UHFFFAOYSA-N 0.000 description 1
- JLPJTCGUKOBWRJ-UHFFFAOYSA-N tripentyl borate Chemical compound CCCCCOB(OCCCCC)OCCCCC JLPJTCGUKOBWRJ-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- 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
-
- 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
- H01L21/225—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 solid phase, e.g. a doped oxide layer
- H01L21/2251—Diffusion into or out of group IV semiconductors
- H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
- H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table characterised by the doping material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
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- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Sustainable Development (AREA)
- Photovoltaic Devices (AREA)
Description
本發明係關於雜質擴散成分之擴散方法、及太陽能電池之製造方法。
近年來半導體製造相關區域,亦即太陽能電池製造區域中以改善製造產能為目的將包含硼之P型的雜質擴散成分與包含磷之N型的雜質擴散成分同時地使其擴散於半導體基板,尋求將P型之雜質擴散層與N型之雜質擴散層選擇性地形成於半導體基板之技術。以往具有P型及N型之雜質擴散層之半導體基板的製造方法使用作為雜質擴散成分的三氯氧磷(POCl3)或三溴化硼(BBr3),使其分別地氣體擴散形成雜質擴散層。此般之氣體擴散無法使硼與磷選擇性地且同時地擴散於半導體基板。
相對於此例如專利文獻1揭示P型摻雜劑源之塗佈液與N型摻雜劑源之塗佈液藉由噴墨印刷或網板印刷等於基板上選擇性地進行印刷形成各導電型之擴散劑圖型,從各擴散劑圖型擴散雜質擴散成分選擇性地形成各導
電型之雜質擴散層之技術。
[專利文獻1]日本特開2012-114452號公報
本發明者們經過重複精心研究關於不同導電型之雜質擴散成分選擇性地同時擴散之結果,於上述以往的方法認知到以下的課題。亦即,在半導體基板上形成P型及N型之擴散劑圖型之後加熱各擴散劑圖型進行同時擴散雜質擴散成分時雜質擴散成分從擴散劑圖型往外部飛散,此雜質擴散成分擴散於不預期的基板部位擴散,亦即引起到處外擴散的情形。此外擴散因不同導電型的雜質擴散成分在基板上選擇性地且同時擴散時之精度降低所導致。
本發明為本發明者們基於該認知所完成之發明,此目的為相對於基板提供較高的精度、不同導電型之雜質擴散成分選擇性地且同時地使其擴散之技術。
為解決上述課題,本發明之某態樣為雜質擴散成分的擴散方法。此雜質擴散成分的擴散方法,其特徵為包含在半導體基板之表面上形成含第1導電型之雜質擴散成分之第1擴散劑層之形成步驟、燒成前述第1擴散劑層之步驟、在去除前述第1擴散劑層所形成區域之前述半
導體基板之表面上形成包含第2導電型之雜質擴散成分之第2擴散劑層之步驟及以較燒成溫度更高之溫度加熱前述半導體基板,在前述半導體基板使第1導電型之雜質擴散成分及第2導電型之雜質擴散成分擴散之步驟。
本發明之其他的態樣為太陽能電池之製造方法。此太陽能電池之製造方法係包含使用上述態樣之雜質擴散成分的擴散方法,在半導體基板使第1導電型之雜質擴散成分及第2導電型之雜質擴散成分擴散,在前述半導體基板之表面形成第1導電型之第1雜質擴散層及第2導電型之第2雜質擴散層之步驟與在前述半導體基板之前述表面上設置第1電極及第2電極,電連接該第1電極與前述第1雜質擴散層,電連接該第2電極與前述第2雜質擴散層之步驟。
1‧‧‧半導體基板
1a‧‧‧刻紋部
2‧‧‧P型擴散劑層
3‧‧‧N型擴散劑層
4‧‧‧P型雜質擴散層
5‧‧‧N型雜質擴散層
6‧‧‧鈍化層
6a‧‧‧接觸孔
7‧‧‧抗反射膜
8、9‧‧‧電極
10‧‧‧太陽能電池
100‧‧‧晶圓
102a、102b‧‧‧P型擴散劑圖型
103a、103b‧‧‧N型擴散劑圖型
104b、104c、104d‧‧‧雜質擴散層
104a‧‧‧雜質擴散層
200‧‧‧加熱爐
201‧‧‧基部
202‧‧‧外筒
202a、b‧‧‧開口
203‧‧‧爐室
204‧‧‧載置台
206‧‧‧支持構件
208‧‧‧氣體供應管路
210‧‧‧氣體排出管路
212‧‧‧加熱器
[圖1]圖1(A)~圖1(C)為關於實施型態之雜質擴散成分的擴散方法及太陽能電池之製造方法的步驟圖。
[圖2]圖2(A)~圖2(D)為關於實施型態之雜質擴散成分的擴散方法及太陽能電池之製造方法的步驟圖。
[圖3]圖3(A)示意為在晶圓上形成之P型擴散劑圖型及N型擴散劑圖型的平面圖。圖3(B)示意為去除P型擴散劑圖型及N型擴散劑圖型之狀態的晶圓。
本發明將以相關文獻予以陳述於適宜之實施例。此為例示本發明但並沒有限縮本發明之範圍。
以下參照本發明適宜之實施的型態的圖示來進行說明。各圖示所示之同一個或相同之構成要素、構件、處理給予相同之符號並省略已重複之說明。又,實施之形態為不限定本發明之例示者,實施之形態所陳述之所有的特徵或是組合並不一定為本發明之本質。
參照圖1(A)~圖1(C)、及圖2(A)~圖2(D)說明關於實施形態之雜質擴散成分的擴散方法與太陽能電池之製造方法。圖1(A)~圖1(C)、及圖2(A)~圖2(D)為關於實施形態之雜質擴散成分的擴散方法及太陽能電池之製造方法的步驟圖。
P型擴散劑組成物係含有P型(第1導電型)之雜質擴散成分(A1)之硼酸酯與多元醇(B)與烷氧矽烷化合物(C)。又,P型擴散劑組成物作為任意成分包含有機溶劑(D)。以下詳細說明P型擴散劑組成物之各個成分。
硼酸酯為III族(13族)元素之化合物,含有係P型的雜質擴散成分之硼。硼酸酯可於N型之半導體基板內形
成P型之雜質擴散層(雜質擴散區域),可於P型之半導體基板內形成P+型(高濃度P型)之雜質擴散層。P型擴散劑組成物之硼酸酯的含量對應於半導體基板所形成之雜質擴散層的層厚等來適宜地調整者。例如硼酸酯相對於P型擴散劑組成物之全質量以包含0.1質量%以上者為佳,以包含1.0質量%以上者更佳。又,硼酸酯相對於P型擴散劑組成物之全質量以包含50質量%以下者為佳。又,硼酸酯中之硼原子相對於P型擴散劑組成物之全質量以包含0.01~10質量%之範圍為佳,以0.1~3質量%之範圍更佳。
本實施之形態之硼酸酯係具有下述一般式(1)所示之構造。
B(OR1)3 (1)[一般式(1)中R1分別獨立為碳原子數1~10之烷基、或碳原子數6~10之芳基。3個R1可為相同或不同]。
R1為烷基時,以碳原子數1~4之直鏈狀或支鏈狀之烷基更佳。芳基例如為苯基、萘基等。尚且,烷基及芳基亦可具有取代基。
作為硼酸酯之具體例,例如可列舉硼酸三甲酯、硼酸三乙酯、硼酸三丙酯、硼酸三丁酯、硼酸三戊酯、硼酸三己酯、硼酸三辛酯、硼酸三苯等。該等之硼酸酯之中從較容易發揮抑制凝集.析出之效果的觀點而言,以硼酸三甲酯、硼酸三乙酯為佳。該等之硼酸酯可單獨使
用亦可組合2種類以上者。
多元醇(B)表示為下述一般式(2)。
作為多元醇(B)之具體例,可列舉乙二醇、丙二醇、1,3-丁二醇、三羥甲丙烷、3-甲基戊烷-1,3,5-三醇、甘露醇等。該等之多元醇可單獨使用亦可組合2種類以上。
P型之雜質擴散成分以硼酸酯的型態同時包含於P型擴散劑組成物,特定構造之多元醇(B)包含於P型擴散劑組成物,在P型擴散劑組成物中多元醇(B)與硼酸酯有效率地形成錯合物藉由此抑制硼酸酯之水解抑制硼化合物之凝集及析出。又,因為可抑制硼化合物之凝集
及析出硼從塗佈於半導體基板等之P型擴散劑組成物的塗膜往外部飛散,附著在相鄰之基板或擴散劑組成物之未塗佈區域可抑制擴散之外擴散的發生。
P型擴散劑組成物中之硼酸酯及多元醇(B)的包含比為硼酸酯之含量為多元醇(B)之含量的5倍莫耳以下為佳,以2倍莫耳以下者較佳。又,從硼酸酯可有效地形成錯合物的觀點而言多元醇(B)之含量較硼酸酯之含量更多,亦即,硼酸酯之含量以未滿多元醇(B)之含量的1倍莫耳較佳。
烷氧矽烷化合物(C)係包含下述一般式(3)所示之水解烷氧矽烷所得之反應生成物(C1)。
R6 nSi(OR7)4-n (3)[一般式(3)中,R6為氫原子或有機基;R7為有機基;n為0、1、或是2之整數;R6為複數時複數之R6可為相同或不同,(OR7)為複數時,複數之(OR7)可為相同或不同]。
作為R6及R7之有機基,例如可列舉烷基、芳基、烯丙基、環氧丙基等。該等之中以烷基及芳基為佳。R6之有機基,例如以碳原子數1~20之直鏈狀或支鏈狀之烷基更佳,從反應性的觀點而言,以碳原子數1~4之直鏈狀或支鏈狀之烷基更佳。以R6中至少一個為烷基或芳基者為佳。芳基例如以碳原子數6~20者為佳,例如可列
舉苯基、萘基等。R7之有機基,例如以碳原子數1~5之直鏈狀或支鏈狀之烷基更佳,從反應性的觀點而言,以碳原子數1~3之烷基更佳。芳基例如以碳原子數6~20者為佳,例如可列舉苯基、萘基等。
上述一般式(3)中n為0時之烷氧矽烷(i),例如下述一般式(4)所示。
Si(OR21)a(OR22)b(OR23)c(OR24)d (4)[一般式(4)中,R21、R22、R23及R24分別獨立表示為與上述R7相同的有機基;a、b、c及d為0≦a≦4、0≦b≦4、0≦c≦4、0≦d≦4且滿足a+b+c+d=4的條件之整數]。
作為烷氧矽烷(i)之具體例,例如可列舉四烷氧矽烷、四乙氧矽烷、四丙氧矽烷、四丁氧矽烷、四戊氧基矽烷、四苯基氧基矽烷、三甲氧基單乙氧基矽烷、二甲氧基二乙氧基矽烷、三乙氧基單甲氧基矽烷、三甲氧基單丙氧基矽烷、單甲氧基三丁氧基矽烷、單甲氧基三戊基氧基矽烷、單甲氧基三苯基氧基矽烷、二甲氧基二丙氧基矽烷、三丙氧基單甲氧基矽烷、三甲氧基單丁氧基矽烷、二甲氧基二丁氧基矽烷、三乙氧基單丙氧基矽烷、二乙氧基二丙氧基矽烷、三丁氧基單丙氧基矽烷、二甲氧基單乙氧基單丁氧基矽烷、二乙氧基單甲氧基單丁氧基矽烷、二乙氧基單丙氧基單丁氧基矽烷、二丙氧基單甲氧基單乙氧基矽烷、二丙氧基單甲氧基單丁氧基矽烷、二丙氧基單乙
氧基單丁氧基矽烷、二丁氧基單甲氧基單乙氧基矽烷、二丁氧基單乙氧基單丙氧基矽烷、單甲氧基單乙氧基單丙氧基單丁氧基矽烷等之四烷氧矽烷,其中從反應性的觀點而言,以四烷氧矽烷、四乙氧矽烷為佳。
上述一般式(3)中,n為1時之烷氧矽烷(ii),例如下述一般式(5)所示。
R31Si(OR32)e(OR33)f(OR34)g (5)[一般式(5)中,R31表示與上述R6相同之氫原子或有機基;R32、R33及R34分別獨立地表示與上述R7相同之有機基;e、f及g為0≦e≦3、0≦f≦3、0≦g≦3且滿足e+f+g=3之條件的整數]。
作為烷氧矽烷(ii)之具體例,例如可列舉甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三丙氧基矽烷、甲基三丁氧基矽烷、甲基三戊基氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙基三丙氧基矽烷、乙基三丁氧基矽烷、乙基三戊基氧基矽烷、乙基三苯基氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、丙基三丁氧基矽烷、丙基三戊基氧基矽烷、丙基三苯基氧基矽烷、丁基三甲氧基矽烷、丁基三乙氧基矽烷、丁基三丙氧基矽烷、丁基三丁氧基矽烷、丁基三戊基氧基矽烷、丁基三苯基氧基矽烷、甲基單甲氧基二乙氧基矽烷、乙基單甲氧基二乙氧基矽烷、丙基單甲氧基二乙氧基矽烷、丁基單甲氧基二乙氧基矽烷、甲基單甲氧基二丙氧基矽烷、甲基單甲
氧基二戊基氧基矽烷、甲基單甲氧基二苯基氧基矽烷、乙基單甲氧基二丙氧基矽烷、乙基單甲氧基二戊基氧基矽烷、乙基單甲氧基二苯基氧基矽烷、丙基單甲氧基二丙氧基矽烷、丙基單甲氧基二戊基氧基矽烷、丙基單甲氧基二苯基氧基矽烷、丁基單甲氧基二丙氧基矽烷、丁基單甲氧基二戊基氧基矽烷、丁基單甲氧基二苯基氧基矽烷、甲基甲氧基乙氧基丙氧基矽烷、丙基甲氧基乙氧基丙氧基矽烷、丁基甲氧基乙氧基丙氧基矽烷、甲基單甲氧基單乙氧基單丁氧基矽烷、乙基單甲氧基單乙氧基單丁氧基矽烷、丙基單甲氧基單乙氧基單丁氧基矽烷、丁基單甲氧基單乙氧基單丁氧基矽烷等,其中從反應性的觀點而言甲基三烷氧矽烷,特別是甲基三甲氧基矽烷、甲基三乙氧基矽烷為佳。尚且,上述具體例中關於碳原子數3以上之烷基或烷氧基可為直鏈狀亦可為支鏈狀。對於丁基(或丁氧基),較佳為n-丁基(n-丁氧基)。對於以下之具體例也為相同之情形。
上述一般式(3)中,n為2時之烷氧矽烷(iii),例如下述一般式(6)所示。
R41R42Si(OR43)h(OR44)i (6)[一般式(6)中,R41及R42表示與上述R6相同之氫原子或有機基;R43及R44分別獨立地表示與上述R7相同之有機基;h及i為0≦h≦2、0≦i≦2且滿足h+i=2之條件之整數]。
作為烷氧矽烷(iii)之具體例,例如可列舉甲基二甲氧基矽烷、甲基甲氧基乙氧基矽烷、甲基二乙氧基矽烷、甲基甲氧基丙氧基矽烷、甲基甲氧基戊基氧基矽烷、甲基甲氧基苯基氧基矽烷、乙基二丙氧基矽烷、乙基甲氧基丙氧基矽烷、乙基二戊基氧基矽烷、乙基二苯基氧基矽烷、丙基二甲氧基矽烷、丙基甲氧基乙氧基矽烷、丙基乙氧基丙氧基矽烷、丙基二乙氧基矽烷、丙基二戊基氧基矽烷、丙基二苯基氧基矽烷、丁基二甲氧基矽烷、丁基甲氧基乙氧基矽烷、丁基二乙氧基矽烷、丁基乙氧基丙氧基矽烷、丁基二丙氧基矽烷、丁基甲基二戊基氧基矽烷、丁基甲基二苯基氧基矽烷、二甲基二甲氧基矽烷、二甲基甲氧基乙氧基矽烷、二甲基二乙氧基矽烷、二甲基二戊基氧基矽烷、二甲基二苯基氧基矽烷、二甲基乙氧基丙氧基矽烷、二甲基二丙氧基矽烷、二乙基二甲氧基矽烷、二乙基甲氧基丙氧基矽烷、二乙基二乙氧基矽烷、二乙基乙氧基丙氧基矽烷、二丙基二甲氧基矽烷、二丙基二乙氧基矽烷、二丙基二戊基氧基矽烷、二丙基二苯基氧基矽烷、二丁基二甲氧基矽烷、二丁基二乙氧基矽烷、二丁基二丙氧基矽烷、二丁基甲氧基戊基氧基矽烷、二丁基甲氧基苯基氧基矽烷、甲基乙基二甲氧基矽烷、甲基乙基二乙氧基矽烷、甲基乙基二丙氧基矽烷、甲基乙基二戊基氧基矽烷、甲基乙基二苯基氧基矽烷、甲基丙基二甲氧基矽烷、甲基丙基二乙氧基矽烷、甲基丁基二甲氧基矽烷、甲基丁基二乙氧基矽烷、甲基丁基二丙氧基矽烷、甲基乙基乙氧基丙
氧基矽烷、乙基丙基二甲氧基矽烷、乙基丙基甲氧基乙氧基矽烷、二丙基二甲氧基矽烷、二丙基甲氧基乙氧基矽烷、丙基丁基二甲氧基矽烷、丙基丁基二乙氧基矽烷、二丁基甲氧基乙氧基矽烷、二丁基甲氧基丙氧基矽烷、二丁基乙氧基丙氧基矽烷、苯基二甲氧基矽烷、苯基甲氧基乙氧基矽烷、苯基二乙氧基矽烷、苯基甲氧基丙氧基矽烷、苯基甲氧基戊基氧基矽烷、苯基甲氧基苯基氧基矽烷等,其中以甲基二甲氧基矽烷、甲基二乙氧基矽烷為佳。
在烷氧矽烷化合物(C)之反應生成物(C1),例如可將從上述烷氧矽烷(i)~(iii)之中選出1種或2種以上,於酸觸媒、水、有機溶劑的存在下,以水解之方法來調製。
如上所述,於烷氧矽烷之水解反應雖使用水,但於關於本實施形態之P型擴散劑組成物,係以將組成物全體作為基準水之含量為1質量%以下為佳,以0.5質量%以下較佳,以實質上不包含水更佳。藉此可更提高P型擴散劑組成物的保存安定性。
酸觸媒可使用有機酸、無機酸之任何一種。作為無機酸,可使用硫酸、磷酸、硝酸、鹽酸等,其中以磷酸、硝酸為佳。作為有機酸,可使用蟻酸、草酸、福馬酸、順丁烯二酸、冰乙酸、乙酸酐、丙酸、n-酪酸等之羧酸、及具有含硫黃之酸殘基之有機酸。作為具有含硫黃之酸殘基之有機酸,可列舉有機磺酸等,作為該等之酯化物,可列舉有機硫酸酯、有機亞硫酸酯等。該等之中,特
別是有機磺酸,例如以下述一般式(7)所示之化合物為佳。
R13-X (7)[一般式(7)中,R13為可具有取代基之烴基,X為磺酸基]。
上述一般式(7)中,作為R13之烴基以碳原子數1~20之烴基為佳。此烴基可為飽和物亦可為不飽和物,可為直鏈狀、分枝狀、環狀之任一種。R13之烴基為環狀時,例如以苯基、萘基、蒽基等之芳香族烴基為佳,其中以苯基為佳。此芳香族烴基之芳香環,作為取代基之碳原子數1~20之烴基可結合1個或複數個。該芳香環上之取代基之烴基可為飽和物亦可為不飽和物,可為直鏈狀、分枝狀、環狀之任一種。又,作為R13之烴基可具有1個或複數個之取代基,作為此取代基,例如可列舉氟原子等之鹵素原子、磺酸基、羧基、羥基、胺基、氰基等。
上述酸觸媒在水的存在下水解烷氧矽烷時用作為觸媒,使用酸觸媒的量為水解反應之反應系中之濃度為1~1000ppm,特別是以成為5~800ppm的範圍來調製者為佳。水之添加量為藉由此改變矽氧烷聚合物之水解率依所得之水解率來決定。
水解反應之反應系的有機溶劑,例如可列舉甲醇、乙醇、丙醇、異丙醇(IPA)、n-丁醇般之一價的醇類、甲基-3-甲氧基丙酸酯、乙基-3-乙氧基丙酸酯般之
烷基羧酸酯、乙二醇、二乙二醇、丙二醇、丙三醇、三羥甲丙烷、己烷三醇等之多元醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等之多元醇的單醚類或是該等之單乙酸酯類、乙酸甲酯、乙酸乙酯、乙酸丁酯般之酯類、丙酮、甲基乙基酮、甲基異戊基酮般之酮類、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基醚、乙二醇二丁基醚、丙二醇二甲基醚、丙二醇二乙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚般之多元醇之羥基全部烷基醚化後之多元醇醚類等。該等之有機溶劑可單獨使用亦可組合2種以上使用。
藉由此般反應系使烷氧矽烷進行水解反應得到烷氧矽烷化合物(C)。該水解反應通常進行1~100小時左右,縮短反應時間以不超過80℃之溫度範圍進行加熱為佳。
反應結束後得到所合成之烷氧矽烷化合物(C)與使用於反應包含有機溶劑之反應溶液。烷氧矽烷化合物(C)藉由以往周知的方法來分離有機溶劑以乾燥後之固體狀態或視情況需要以取代溶劑後之溶液狀態由上述的方法得到者。
又,作為烷氧矽烷化合物(C),可取代反應生成物(C1),或可連同反應生成物(C1)使用下述一
般式(8)所示之矽氧烷聚合物(C2)。
一般式(8)中,R01為含有乙烯性不飽和雙鍵之基,R0為碳原子數1~9之伸烷基,可具有不同R0時,R02為烷基、烷氧基、芳基或氫原子,可具有不同R02時,m:p為1:99~100:0之範圍,較佳為10:90~90:10的範圍。m:p可考慮Si含有率或調整膜厚等來適宜地設定。
一般式(8)中,作為於R01含有乙烯性不飽和雙鍵之基,以於末端具有乙烯性不飽和雙鍵者為佳,特別是以丙烯醯基氧基或是甲基丙烯醯基氧基為佳。
一般式(8)中,作為於R0之碳原子數1~9的伸烷基,可列舉直鏈狀或是支鏈狀的伸烷基。較佳為碳原子數1~7,更佳為碳原子數1~5之直鏈狀的伸烷基,特佳為亞甲基、伸乙基、n-伸丙基。
一般式(8)中,作為於R02之烷基,可列舉碳原子數1~10之烷基,例如可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等之直鏈狀的烷基;1-甲基乙基、1-甲基丙基、2-甲基丙基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1-乙基丁基、2-乙基丁基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基等之支鏈狀的烷基;環戊基、環己基、金剛烷基、降冰片
基、異莰基、三環癸基等之環狀的烷基。較佳為碳原子數1~5之烷基,更佳為碳原子數1~3之烷基,特佳為甲基。
一般式(8)中,作為於R02之烷氧基,可列舉碳原子數1~5之烷氧基,例如可列舉甲氧基、乙氧基、丙氧基、丁氧基、戊基氧基。較佳為碳原子數1~3之烷氧基,更佳為甲氧基或是乙氧基。
一般式(8)中,作為於R02之芳基,例如可列舉苯基、雙苯基(biphenyl)、茀(fluorenyl)基、萘基、蒽(anthryl)基、菲基等。較佳為苯基。又,R02之芳基亦可具有烷基等之取代基。
作為一般式(8)所示之矽氧烷聚合物(C2),特佳可列舉下述式(9)所示之矽氧烷聚合物(C2-1)、下述式(10)所示之矽氧烷聚合物(C2-2)、或下述式(11)所示之矽氧烷聚合物(C2-3)。式中,m及p與前述相同。又s+t=p、u+v=p。烷氧矽烷化合物(C)之質量平均分子量(Mw)沒有特別限定,較佳為500~30000,特佳為1000~10000。
烷氧矽烷化合物(C)之含量,相對於組成物全體(以SiO2換算含量)以1~50質量%的範圍者為佳,以1.5~35質量的範圍者更佳,以2~20質量%者特佳。藉由將烷氧矽烷化合物(C)之含量成為1質量%以上,使擴散劑組成物的擴散選擇性變為良好,並藉由將該含量成為50質量%以下,可與包含於擴散劑組成物之其他成分的含量平衡變為良好。
P型擴散劑組成物係含有作為任意成分之有機溶劑(D)。有機溶劑(D)為多元醇(B)以外之有機溶劑。作為有機溶劑(D),例如可列舉甲醇、乙醇、異丙醇、丁醇等之醇類、丙酮、二乙基酮、甲基乙基酮等之酮類、乙酸甲酯、乙酸乙酯、乙酸丁酯等之酯類、丙二醇、丙三醇、二丙二醇等之多元醇、二丙二醇二甲基醚、乙二醇二
甲基醚、乙二醇二乙基醚、丙二醇二甲基醚、丙二醇二乙基醚等之醚類、乙二醇單甲基醚、乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、二丙二醇單甲基醚等之單醚系二醇類、四氫呋喃、二噁烷等之環狀醚類、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等之醚系酯類。
P型擴散劑組成物可含有作為其他成分的一般性界面活性劑或消泡劑等。例如藉由包含界面活性劑,可改善塗佈性、平坦化性、展開性,可減少塗佈後所形成擴散劑組成物層之塗佈不均勻的發生。此般界面活性劑可使用以往周知者,以聚矽氧系之界面活性劑為佳。又,界面活性劑相對於擴散劑組成物全體,以包含500~3000質量ppm為佳,特別是600~2500質量ppm的範圍為佳。進而為2000質量ppm以下時,因擴散處理後之擴散劑組成物層之剝離性優異,故更佳。界面活性劑可單獨使用亦可以組合使用者。尚且,在後述之擴散劑層形成步驟,於網板印刷法形成P型擴散劑組成物之圖形時,P型擴散劑組成物為了進一步改善印刷性或印刷圖形的精度,可含有微粒子(E)。微粒子(E)可考慮增黏性或觸變性適宜地使用以往周知者。作為微粒子(E)例如可列舉二氧化矽微粒子或氧化鋁微粒子。
P型擴散劑組成物中所包含之金屬雜質(包含於上述硼酸酯、多元醇(B)及烷氧矽烷化合物(C)之金屬成分除外)之濃度以500ppb以下者為佳。藉由此可抑制由包含金屬雜質所產生光引發電力效果之效率低下。
N型擴散劑組成物為含有N型(第2導電型)之雜質擴散成分(A2)與烷氧矽烷化合物(C)。又,N型擴散劑組成物係含有作為任意成分之有機溶劑(D)。以下詳細地說明N型擴散劑組成物的各成分。
N型的雜質擴散成分(A2)一般而言包含作為摻雜劑使用於太陽能電池的製造之V族(15族)元素的化合物。N型的雜質擴散成分(A2)可在P型的半導體基板內形成N型的雜質擴散層(雜質擴散區域),在N型的半導體基板內形成N+型(高濃度N型)之雜質擴散層。作為V族元素的化合物,例如可列舉包含P2O5、Bi2O3、Sb(OCH2CH3)3、SbCl3、As(OC4H9)3、磷酸單甲基、磷酸二甲基、磷酸單乙基、磷酸二乙基、磷酸三乙基、磷酸單丙基、磷酸二丙基、磷酸單丁基、磷酸二丁酯、磷酸三丁基等之磷酸酯等,於N型之雜質擴散成分(A2)包含1種以上該等化合物。本實施之形態中N型的雜質擴散成分(A2)為含有磷之化合物。N型擴散劑組成物中N型之雜質擴散成分(A2)的含量,因應於半導體基板所形成之雜質擴散層的層厚等來適當的調整。例如N型的雜質擴散成分(A2)相對於N型擴散劑組成物之全質量以包含5~60質量%為佳,以包含10~40質量%較佳,以包含15~
30質量%者更佳。
烷氧矽烷化合物(C)及有機溶劑(D)與上述之P型擴散劑組成物所包含烷氧矽烷化合物(C)及有機溶劑(D)相同。又,與P型擴散劑組成物同樣地N型擴散劑組成物作為其他成分一般而言亦可以包含界面活性劑或消泡劑等。尚且各導電型之擴散劑組成物的組成不限於上述者,例如P型擴散劑組成物所包含之P型的雜質擴散成分(A1)為硼酸酯以外,亦可為一般而言作為摻雜劑使用於太陽能電池的製造之III族(13族)元素的化合物。此般III族元素的化合物如B2O3、Al2O3、三氯化鎵等。又,P型的雜質擴散成分(A1)亦可以包含1種以上III族元素的化合物。又亦可以不包含多元醇(B)。又,在網板印刷法形成N型擴散劑組成物之圖型時可包含N型擴散劑組成物之微粒子(E)。
P型擴散劑組成物及N型擴散劑組成物藉由上述各成分之以往周知的方法,以任意的順序,藉由混合成均勻的溶液來調製。又,因應在後述之擴散劑層形成步驟中所使用之選擇性的塗佈方法,可調整擴散劑組成物的黏度等。
如圖1(A)所示,作為半導體基板1,例如準備P型矽晶圓。半導體基板1為於一邊的表面上具有刻紋部1a之太陽能電池用基板。尚且,在半導體基板1另一邊
的表面可設置刻紋部,亦可不設置。刻紋部1a係具有連續凹凸並排的構造,於此構造間距或高度為具有規則性並排相同程度之凹凸、或間距或高度係包含隨機並排各式各樣之凹凸。凹凸的間距(從凸部的頂點到凹部的最深部面方向的距離)例如為1~10μm。凹凸的高度(從凹部的最深部至凸部頂點的高度)例如為1~10μm。藉由刻紋部1a可防止在半導體基板1的表面之光的反射。刻紋構造可使用周知的濕蝕刻法來形成。
而且,在與刻紋部1a所設置側相反側之半導體基板1的表面上,選擇性塗佈含有P型之雜質擴散成分(A1)之P型擴散劑組成物,形成P型擴散劑層2(第1擴散劑層)。對半導體基板1之P型擴散劑組成物的選擇性塗佈,例如由噴墨印刷法、網板印刷法、噴塗佈法、輥塗佈印刷法、凸版印刷法、凹版印刷法、平板印刷法等來實施。形成特定圖型之P型擴散劑層2之後,搭載半導體基板1於加熱板,例如在200℃下施以0.5分鐘的烘烤處理,使P型擴散劑層2乾燥。
其次,如圖1(B)所示,將設置P型擴散劑層2之半導體基板1投入加熱爐200。加熱爐200例如為以往周知的縱型擴散爐,係具備基部201、與外筒202、與載置台204、支持構件206、與氣體供應管路208、氣體排出管路210、加熱器212。
外筒202係軸方向以與垂直方向成為平行的方式組附在基部201,於基部201與外筒202形成爐室203。載置台204以平面視圓型配置於爐室203的中央。支持構件206以柱體狀於載置台204之外緣部於圓周方向以一定的間隔設置複數個。於各支持構件206的側面在軸方向以一定的間隔設置複數個溝。半導體基板1係藉由以外緣部銜接於支持構件206的溝,藉由支持構件206來支持。氣體供給路208為在爐室203供給環境氣體之管路,連結於一端為環境氣體槽(未圖示)、另一端為外筒202的開口202a。氣體排出路210為排出爐室203內之氣體的管路,連結於一端為外筒202的開口202b。加熱器212係設置於外筒202的外周圍,加熱爐室203內。
於爐室203內設置複數之半導體基板1,於從氣體供給路208至爐室203內,供給例如氮氣(N2)作為環境氣體。然後於N2氣體環境下加熱半導體基板1,燒成P型擴散劑層2。作為前述環境氣體,除了N2氣體以外,可使用氧氣或氮氣與氧氣之混合氣體等。藉由燒成,精燒成P型擴散劑層2。於燒成之P型擴散劑層2的加熱溫度,亦即燒成溫度較佳為500℃以上且900℃以下。藉由燒成溫度定為500℃以上可更確實地燒成P型擴散劑層2。又,藉由燒成溫度成為900℃以下,可更確實地抑制從P型擴散劑層2之P型之雜質擴散成分(A1)的外部擴散。燒成時間較佳為10分鐘以上60分鐘以下。
其次,如圖1(C)所示,將半導體基板1從加熱爐200取出冷卻之後,於排除形成P型擴散劑層2部分之半導體基板1的表面上,選擇性地塗佈含有N型之雜質擴散成分(A2)之N型擴散劑組成物,而形成N型擴散劑層3(第2擴散劑層)。對半導體基板1之N型擴散劑組成物的選擇性塗佈,例如藉由噴墨印刷法、網板印刷法、噴塗佈法、輥塗佈印刷法、凸版印刷法、凹版印刷法、平板印刷法等實施。形成特定圖型之N型擴散劑層3之後,將半導體基板1搭載於加熱板上,在200℃下施以0.5分鐘的烘烤處理,使N型擴散劑層3乾燥。於本實施之形態,在半導體基板1同一面形成P型擴散劑層2及N型擴散劑層3。
其次,如圖2(A)所示,將設置P型擴散劑層2及N型擴散劑層3之半導體基板1投入加熱爐200。於爐室203內設置複數之半導體基板1,於從氣體供給路208至爐室203內,例如供給氮氣(N2)作為環境氣體。而且,在N2氣體環境下,以較燒成溫度更高的溫度加熱半導體基板1,使P型的雜質擴散成分(A1)及N型的雜質擴散成分(A2)擴散於半導體基板1。半導體基板1之加熱溫度,亦即,熱擴散溫度較佳為950℃以上且1100℃以下。
藉由熱擴散溫度成為950℃以上,可更確實地熱擴散雜質擴散成分。又,藉由熱擴散溫度形成1100℃以下,可確實地防止使雜質擴散成分超過所期望的擴散區域擴散於半導體基板1內、及半導體基板1受到由熱造成的損害。擴散時間較佳為10分鐘以上且60分鐘以下。尚且,取代擴散爐,藉由慣用之雷射的照射亦可加熱半導體基板1。
然後,從加熱爐200取出半導體基板1浸漬於氫氟酸等之剥離液,去除P型擴散劑層2及N型擴散劑層3。藉由以上的步驟,如圖2(B)所示,可得到P型雜質擴散層4(第1雜質擴散層)及N型雜質擴散層5(第2雜質擴散層)形成於表面之半導體基板1。
其次,如圖2(C)所示,使用周知的化學氣相成長法(CVD法),例如電漿CVD法等,於形成半導體基板1之P型雜質擴散層4及N型雜質擴散層5側的表面上,形成由氮化矽膜(SiN膜)所成之鈍化層6。此鈍化層6具有抗反射膜之機能。又,於刻紋部1a的表面上形成由氮化矽膜所成之抗反射膜7。
其次,如圖2(D)所示藉由周知之光微影步驟法及蝕刻法選擇性地去除鈍化層6形成露出特定區域之P型雜質擴散層4及N型雜質擴散層5之接觸孔6a。而且,例如藉由使用電鍍法及無電鍍法、或使用金屬糊料之網板印刷等,於P型雜質擴散層4上所設置之接觸孔6a
填充金屬,形成與P型雜質擴散層4電連接之電極8(第1電極)。又,以同樣的方式於N型雜質擴散層5上所設置之接觸孔6a,形成與N型雜質擴散層5電連接之電極9(第2電極)。藉由以上的步驟,可製造本實施形態之太陽能電池10。尚且,關於本實施形態之雜質擴散成分的擴散方法,在形成太陽能電池以外的用途所使用之半導體基板時亦可以採用。
如以上說明所示,關於本實施形態之雜質擴散成分的擴散方法,係於半導體基板1的表面上形成P型擴散劑層2,並於燒成之後形成N型擴散劑層3,實施硼及磷之同時擴散。無法燒成P型擴散劑層2時,藉由以同時擴散步驟之加熱,使來自P型擴散劑層2之P型之雜質擴散成分(A1)擴散於外部,於N型擴散劑層3吸收此雜質擴散成分(A1),在半導體基板1之區域應擴散N型之雜質擴散成分(A2),恐有已擴散雜質擴散成分(A1)之虞。又,藉由以同時擴散步驟之加熱,P型擴散劑層2已吸收從N型擴散劑層3擴散至外部之雜質擴散成分(A2),雜質擴散成分(A1)於應擴散之半導體基板1的區域,恐有已擴散雜質擴散成分(A2)之虞。對此,於本實施形態,在同時擴散步驟之前,為了因燒結P型擴散劑層2,可抑制從P型擴散劑層2之P型之雜質擴散成分擴散至外部。又,可抑制P型擴散劑層2已吸收從N型擴散劑層3擴散至外部之雜質擴散成分(A2)。
亦即,根據本實施形態,藉由燒固預先燒成
含有一者之摻雜劑之擴散劑層,在之後的同時擴散步驟中,可抑制形成逆轉之元素的擴散(逆摻雜Counter doping)。因此根據本實施形態,可抑制外擴散的發生,其結果,可使更高精度相異之導電型的雜質擴散成分選擇性地且同時地擴散於半導體基板1。又,藉由使用此雜質擴散成分之擴散方法製造太陽能電池,可改善太陽能電池的性能。
又,在本實施形態,於一側之擴散劑層、另一側之擴散劑層形成前燒成。2個擴散劑層形成後,在同時擴散步驟之前,於兩擴散層實施燒成處理時,不經過燒成步驟於造成同時擴散時,可引發與上述污染相同的情況。亦即,藉由於燒成步驟之加熱,來自P型擴散劑層及N型擴散劑層之雜質擴散成分(A1)、(A2),以較同時擴散更少量往外部擴散,雜質擴散成分(A1)與雜質擴散成分(A2)分別吸收至N型擴散劑層及P型擴散劑層。對於此,於本實施形態,因為係於燒成先塗佈之一側的擴散劑層之後,而形成於另一側之擴散劑層,故可抑制此般污染的發生。
又,於本實施形態,藉由擴散劑層的燒成抑制外擴散的發生。因此,相較於外擴散防止用之遮罩覆蓋於半導體基板1之方法,不妨礙半導體製造的高產能化,且可抑制外擴散的發生。又,擴散劑層之燒成係以使雜質擴散成分熱擴散時之加熱溫度更低溫來實施。因此,於燒成步驟所需時間係比擴散步驟所需時間更短。據此,藉由
於燒成後進行同時擴散,與分別實施時相比較,可縮短P型之雜質擴散成分(A1)的熱擴散與N型的雜質擴散成分(A2)的熱擴散之製造時間,改善製造產能。又,於本實施的形態,係由印刷將擴散劑組成物塗佈於半導體基板1。因此,相較於使用以往之旋轉塗佈法可減少使用組成物量,可意圖降低製造製程之成本。
又,於本實施的形態,實施燒成處理之P型擴散劑層2係包含烷氧矽烷化合物(C)。因此,藉由燒成處理,可更確實地燒成固定P型擴散劑層2。又,於本實施之形態,於燒成包含硼之P型擴散劑層2之後,形成包含磷之N型擴散劑層3(亦即第1導電型為硼,第2導電型為磷)。磷相較於硼容易揮發,且容易外部擴散。因此,藉由於包含硼之P型擴散劑層2施以燒成處理,相較於包含磷之N型擴散劑層3實施燒成處理時,可降低燒成步驟中外部擴散之雜質擴散成分的量。
亦即,P型擴散劑層2及N型擴散劑層3該施以何種燒成處理,換而言之何者先在半導體基板1上形成,決定於分別包含雜質擴散成分的擴散容易程度為佳。亦即,以優先形成包含相對不易擴散的雜質擴散成分之擴散劑層為佳。例如於上述之硼與磷,因為硼的部分不易擴散,故以優先形成包含硼之P型擴散劑層2為佳。又,於硼與銻因為銻擴散不易,故以優先形成包含銻之N型擴散劑層3為佳。尚且,即使於燒成包含磷之N型擴散劑層3之後,形成包含硼之P型擴散劑層2(亦即第1導電型為
磷、第2導電型為硼),相較於不經過燒成步驟使其同時擴散之以往的方法,可抑制外擴散的發生。
本發明並不限於上述實施的形態,基於本發明領域具有通常知識者的知識可施以各種設計變更等之變形,此般所施加的變形也包含於本發明之實施形態的範圍。藉由上述實施形態與以下之變形例之組合所產生之新實施的形態,具有組合實施形態及變形例分別之效果。
於上述之實施形態,於P型矽晶圓形成雜質擴散層,亦可於N型矽晶圓形成雜質擴散層。又,於上述之實施形態,加熱爐200為縱型擴散爐亦可為以往周知之橫型擴散爐者。
以下雖說明本發明之實施例,但該等實施例沒有超過合理地說明本發明之例示,不限定於本發明。
依表1所示之成分組成及含量,均勻混合各成分,以0.45μm之膜濾器進行過濾,調製P型擴散劑組成物I~III及N型擴散劑組成物。尚且,使用硼酸三乙酯(TEB)作為P型雜質擴散成分(A1),使用磷酸二丁酯作為N型雜質擴散成分(A2)。又,各擴散劑組成物使用作為界面活性劑之聚矽氧系界面活性劑(SF8421EG:Dow Corning Toray股份有限公司製)。又,使用作為有機溶劑(D)
之二丙二醇單甲基醚(MFDG),該含量為將擴散劑組成物之全質量成為100wt%時,將各成分之含量從100wt%減去剩餘的量為全部溶劑的含量。
表1中之簡稱表示以下之化合物。
TEB:硼酸三乙酯(硼酸三乙酯)
MFDG:二丙二醇單甲基醚
又,表1中之構造C-1為將四乙氧矽烷(Si(OC2H5)4)作為縮合生成物之起始原料。又,構造C-2為下述一般式(12)表示之縮合生成物。
在6寸之P型鏡像矽晶圓(CZ-P<100>/5~15Ω.cm)之特定區域,使用噴墨排氣機(MID-500C:武藏工程公司製)藉由噴墨印刷法選擇性塗佈P型擴散劑組成物I,形成P型擴散劑圖型。其次,於加熱板上200℃下施以P型擴散劑圖型0.5分鐘之烘乾處理。烘乾處理後之P型擴
散劑圖型的膜厚為1.2μm。而且,P型擴散劑圖型係將設置之矽晶圓配置於加熱爐內,在650℃下加熱30分鐘並燒成。之後,在此矽晶圓的特定區域藉由噴墨印刷法,選擇性塗佈N型擴散劑組成物,而形成N型擴散劑圖型。其次,於加熱板上將N型擴散劑圖型在200℃下施以0.5分鐘之烘乾處理。烘乾處理後之N型擴散劑圖型的膜厚為1μm。
圖3(A)表示為晶圓上形成P型擴散劑圖型及N型擴散劑圖型之示意平面圖。如圖3(A)所示,於晶圓100形成2個帶狀的P型擴散劑圖型102a、102b與2個帶狀的N型擴散劑圖型103a、103b。P型擴散劑圖型102a、102b及N型擴散劑圖型103a、103b以個別長邊成為平行的方式,使P型與N型交互地配列。亦即,依P型擴散劑圖型102a、N型擴散劑圖型103a、P型擴散劑圖型102b、N型擴散劑圖型103b的順序來配置。各帶狀圖型之長邊的長度為100mm、短邊的長度為8mm,相鄰帶狀圖型的間隔為2mm。
將N型擴散劑圖型與燒成之P型擴散劑圖型所形成之矽晶圓配置於加熱爐內,在980℃下加熱20分鐘,將P型擴散劑圖型內之硼及N型擴散劑圖型內之磷同時地熱擴散,於矽晶圓內形成P型雜質擴散層及N型雜質擴散層。然後,將各擴散劑圖型浸漬於5%之氫氟酸溶液10分鐘而去除。藉由以上的步驟得到實施例1之晶圓。圖3(B)為表示去除P型擴散劑圖型及N型擴散劑
圖型狀態之晶圓示意平面圖。如圖3(B)所示,經過擴散步驟之晶圓100,在設置P型擴散劑圖型102a之區域,形成帶狀雜質擴散層104a。同樣地,在設置N型擴散劑圖型103a之晶圓區域、設置P型擴散劑圖型102b之晶圓區域、設置N型擴散劑圖型103b之晶圓區域,分別形成帶狀的雜質擴散層104b、雜質擴散層104c、雜質擴散層104d。
除了燒成溫度成為750℃、燒成時間為60分鐘之外,其他與實施例1以相同的方式製作實施例2的晶圓100。
除了將燒成溫度成為850℃之外,其他與實施例1以相同的方式製作實施例3之晶圓100。
除了將燒成溫度成為900℃之外,其他與實施例1以相同的方式製作實施例4之晶圓100。
除了取代P型擴散劑組成物I改使用P型擴散劑組成物II,將燒成溫度成為850℃,烘乾處理後之P型擴散劑圖型102a,102b的膜厚為0.9mm之外,其他與實施例1
以相同的方式製作實施例5之晶圓100。
除了烘乾處理後之P型擴散劑圖型102a,102b之膜厚為0.5mm之外,其他與實施例5以相同的方式製作實施例6之晶圓100。
除了取代P型擴散劑組成物I改使用P型擴散劑組成物III,將燒成溫度成為850℃,烘乾處理後之P型擴散劑圖型102a,102b之膜厚為0.1mm之外,其他與實施例1以相同的方式製作實施例7之晶圓100。
除了將N型擴散劑圖型103a,103b較P型擴散劑圖型102a,102b更早形成之外,其他與實施例1以相同的方式製作實施例8之晶圓100。
除了烘乾處理後之P型擴散劑圖型102a,102b的膜厚為1.2mm之外,其他與實施例5以相同的方式製作實施例9之晶圓100。
除了將燒成溫度成為500℃以外,其他與實施例1以相同的方式製作實施例10之晶圓100。
除了使N型擴散劑圖型103a,103b較P型擴散劑圖型102a,102b先形成,且未實施燒成步驟之外,其他與實施例1以相同的方式製作比較例1之晶圓100。
除了未實施燒成步驟之外,其他與實施例1以相同的方式製作比較例2之晶圓100。
各實施例及比較例使用之P型擴散劑組成物的種類、圖型的形成順序、圖型的膜厚、燒成條件表示於表2。
關於各實施例及比較例之晶圓100,將對應P型擴散劑圖型102a,102b之雜質擴散層104a及雜質擴散層104c之導電型、對應N型擴散劑圖型103a,103b之雜質擴散層104b及雜質擴散層104d之導電型分別作為P型圖型下區域之導電型、N型圖型下區域之導電型使用P/N判定機(PN/12α:Napson股份有限公司製)進行判定。結果表示於表3。
關於各實施例及比較例之晶圓100,雜質擴散層104a~104d之薄片電阻值Rs(Ω/sq),使用薄片電阻測定器
(VR-70:國際電器股份有限公司製)藉由四探針法來測定。計算雜質擴散層104a及雜質擴散層104c之薄片電阻值的平均值,將此值作為P型圖型下區域薄片電阻值。又,計算雜質擴散層104b及雜質擴散層104d之薄片電阻值的平均值,此值作為N型圖型下區域之薄片電阻值。結果表示於表3。
又,分別關於P型圖型下區域及N型圖型下區域以各雜質擴散層的長邊方向中央部,測定於短邊方向以1mm的間隔並排5點之薄片電阻值,計算標準偏差(σ)(Rs分散)。Rs分散一般而言值越小越好,未滿10時為「A」、10以上時為「B」。結果表示於表3。
雜質擴散層104c之中心部的硼原子濃度(atm/cc)及磷原子濃度(atm/cc)使用SIMS分析裝置(CAMECAIMS-7f)來進行測定。測定時採用測定深度0.01μm之值。然後將對於磷原子濃度之硼原子濃度的比率(B/P)於P型圖型下區域中計算作為原子濃度比者。又以相同的方式測定於雜質擴散層104b之中心部的硼原子濃度(atm/cc)及磷原子濃度(atm/cc)將對於硼原子濃度之磷原子濃度的比率(P/B)於N型圖型下區域計算作為原子濃度比。原子濃度比一般以大者為佳,100以上時為「A」,10以上未滿100時為「B」、未滿10成為「C」。結果表示於表3。尚且,比較例1、2不測定原子
濃度比。
如表3所示,在比較例1、2,N型圖型下區域之導電型為N型。然而,P型圖型下區域之導電型,本來應該為P型,但為N型。此被認為是因為N型擴散劑圖型103a、103b中的磷被外部擴散之P型擴散劑圖型102a、102b所吸收,而擴散至雜質擴散層104a及雜質擴散層104c。另一方面,於在實施例1~10,N型圖型下區域的導電型為N型,P型圖型下區域的導電型為P型。由此,燒成一側之導電型的擴散劑圖型後,於另一側形成導電型的擴散劑圖型藉由進行同時擴散,確認可抑制外擴散並使雜質擴散成分之高精度的選擇性擴散為可能。
又,先形成P型擴散劑圖型之實施例1~7、
9、10,與先形成N型擴散劑圖型之實施例8相比較,P型圖型下區域中Rs分散較小。據此,確認出包含磷之N型擴散劑圖型較包含硼之P型擴散劑圖型先形成,藉由燒成此P型擴散劑圖型形成較更良好的雜質擴散層。又,從比較不同的P型擴散劑圖型的膜厚之實施例5、6、9,確認得到膜厚越厚,則越好的原子濃度、又得到較小的薄片電阻值。
例如關於實施的形態由以下的組合包含於本發明之範圍。
一種雜質擴散成分之擴散方法,其特徵為包含:在半導體基板的表面上形成包含第1導電型之雜質擴散成分之第1擴散劑層之步驟、燒成前述第1擴散劑層之步驟、在排除前述第1擴散劑層所形成區域之前述半導體基板的表面上,形成包含第2導電型之雜質擴散成分的第2擴散劑層之步驟、將前述半導體基板以較燒成溫度更高的溫度加熱,在前述半導體基板使第1導電型之雜質擴散成分及第2導電型之雜質擴散成分擴散之步驟。
如項目1之雜質擴散成分之擴散方法,其中前述第1擴散劑層包含烷氧矽烷化合物。
如項目1或項目2之雜質擴散成分之擴散方法,其中前述第1導電型為硼,前述第2導電型為磷。
如項目1~3中任一項之雜質擴散成分之擴散方法,其中前述第1擴散劑層及前述第2擴散劑層係形成於前述半導體基板的同一面上。
如項目1~4中任一項之雜質擴散成分之擴散方法,其中前述燒成中,前述第1擴散劑層以500℃以上、900℃以下的溫度加熱。
一種太陽能電池之製造方法,其特徵為包含:使用項目1~5中任一項記載之雜質擴散成分之擴散方法,在半導體基板使第1導電型之雜質擴散成分及第2導電型之雜質擴散成分擴散,在前述半導體基板的表面上,形成第1導電型之第1雜質擴散層及第2導電型之第2雜質擴散層之步驟、在前述半導體基板的前述表面上設置第1電極及第2電極,電連接該第1電極與前述第1雜質擴散層,電連接該第2電極與前述第2雜質擴散層之步驟。
Claims (6)
- 一種雜質擴散成分之擴散方法,其特徵為包含:在半導體基板的表面上形成包含第1導電型之雜質擴散成分之第1擴散劑層之步驟、以在半導體基板的表面上形成有前述第1擴散劑層且未形成包含第2導電型之雜質擴散成分之第2擴散劑層之狀態下來燒成前述第1擴散劑層之步驟、在排除前述第1擴散劑層所形成區域之前述半導體基板的表面上,形成前述第2擴散劑層之步驟、將前述半導體基板以較燒成溫度更高的溫度加熱,在前述半導體基板使第1導電型之雜質擴散成分及第2導電型之雜質擴散成分擴散之步驟。
- 如請求項1之雜質擴散成分之擴散方法,其中,前述第1擴散劑層包含烷氧矽烷化合物。
- 如請求項1之雜質擴散成分之擴散方法,其中,前述第1導電型為硼,前述第2導電型為磷。
- 如請求項1之雜質擴散成分之擴散方法,其中,前述第1擴散劑層及前述第2擴散劑層係形成於前述半導體基板的同一面上。
- 如請求項1之雜質擴散成分之擴散方法,其中,在前述燒成,前述第1擴散劑層以500℃以上、900℃以下的溫度加熱。
- 一種太陽能電池之製造方法,其特徵係使用雜質擴散成分之擴散方法,包含: 在半導體基板使第1導電型之雜質擴散成分及第2導電型之雜質擴散成分擴散,在前述半導體基板的表面上,形成第1導電型之第1雜質擴散層及第2導電型之第2雜質擴散層之步驟、與在前述半導體基板的前述表面上設置第1電極及第2電極,電連接該第1電極與前述第1雜質擴散層,電連接該第2電極與前述第2雜質擴散層之步驟;前述雜質擴散成分之擴散方法為包含:在半導體基板的表面上形成包含第1導電型之雜質擴散成分之第1擴散劑層之步驟、以在半導體基板的表面上形成有前述第1擴散劑層且未形成包含第2導電型之雜質擴散成分之第2擴散劑層之狀態下來燒成前述第1擴散劑層之步驟、在排除前述第1擴散劑層所形成區域之前述半導體基板的表面上,形成前述第2擴散劑層之步驟、將前述半導體基板以較燒成溫度更高的溫度加熱,在前述半導體基板使第1導電型之雜質擴散成分及第2導電型之雜質擴散成分擴散之步驟。
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