CN118648122A - Impurity diffusion composition and method for manufacturing solar cell using the same - Google Patents
Impurity diffusion composition and method for manufacturing solar cell using the same Download PDFInfo
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- CN118648122A CN118648122A CN202380015392.6A CN202380015392A CN118648122A CN 118648122 A CN118648122 A CN 118648122A CN 202380015392 A CN202380015392 A CN 202380015392A CN 118648122 A CN118648122 A CN 118648122A
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- Prior art keywords
- impurity diffusion
- diffusion composition
- compound
- composition
- mass
- Prior art date
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- 239000012535 impurity Substances 0.000 title claims abstract description 246
- 238000009792 diffusion process Methods 0.000 title claims abstract description 240
- 239000000203 mixture Substances 0.000 title claims abstract description 156
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 32
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 22
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 77
- 239000004065 semiconductor Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 12
- 238000007127 saponification reaction Methods 0.000 claims description 12
- -1 silanol compound Chemical class 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- 229920002050 silicone resin Polymers 0.000 claims description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 5
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- 230000009467 reduction Effects 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 73
- 238000002360 preparation method Methods 0.000 description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 238000002156 mixing Methods 0.000 description 25
- 239000012298 atmosphere Substances 0.000 description 19
- 238000007650 screen-printing Methods 0.000 description 16
- 238000009835 boiling Methods 0.000 description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 14
- 239000004327 boric acid Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000013008 thixotropic agent Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229940116411 terpineol Drugs 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 229940035437 1,3-propanediol Drugs 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- ZOMPBXWFMAJRRU-UHFFFAOYSA-N 3-ethyloxiran-2-one Chemical compound CCC1OC1=O ZOMPBXWFMAJRRU-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000009472 formulation 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
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- AMJFYZGCLLOKLZ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutan-1-amine Chemical compound NC(F)(F)C(F)(F)C(F)(F)C(F)(F)F AMJFYZGCLLOKLZ-UHFFFAOYSA-N 0.000 description 1
- 150000000185 1,3-diols Chemical group 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SKQUTIPQJKQFRA-UHFFFAOYSA-N 2,3-dimethylbutane-1,4-diol Chemical compound OCC(C)C(C)CO SKQUTIPQJKQFRA-UHFFFAOYSA-N 0.000 description 1
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 1
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 1
- HJIYDQCBJVTQAO-UHFFFAOYSA-N 2-butyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCCCC(CO)(CO)CO HJIYDQCBJVTQAO-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000001468 Triticum dicoccon Nutrition 0.000 description 1
- 240000000359 Triticum dicoccon Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011254 layer-forming composition Substances 0.000 description 1
- UYVXZUTYZGILQG-UHFFFAOYSA-N methoxyboronic acid Chemical compound COB(O)O UYVXZUTYZGILQG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 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
- 239000005360 phosphosilicate glass Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 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
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- DTBRTYHFHGNZFX-UHFFFAOYSA-N trioctyl borate Chemical compound CCCCCCCCOB(OCCCCCCCC)OCCCCCCCC DTBRTYHFHGNZFX-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
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
The present invention provides an impurity diffusion composition which stably forms a p++ high concentration impurity diffusion layer by a laser irradiation method and has little reduction in carrier lifetime, and a method for manufacturing a solar cell by using the composition. An impurity diffusion composition comprising (a-1) a compound represented by the general formula (1) and/or polyvinyl alcohol, (a-2) particles having an average particle diameter of 200nm or less and (a-3) a boron compound, wherein, based on 100 parts by mass of the (a-3) boron compound, 5 to 50 parts by mass of the (a-2) particles are contained (in the general formula (1), R 1～R4 may be the same or different, each represents a 1-valent organic group having 1 to 3 carbon atoms, X 1 represents a single bond or at least one organic group selected from methylene groups having 1 to 3 carbon atoms, -CH 2OCH2 -, n 1 is an integer of 2 to 4, n 2～n4 may be the same or different, each represents an integer of 0 to 2, and n 1+n2+n3+n4＝4;m1 is an integer of 1 to 3, m 2～m3 may be the same or different, each represents an integer of 0 to 2, and m 1+m2+m3 = 3.
Description
Technical Field
The present invention relates to an impurity diffusion composition and a method for manufacturing a solar cell using the same.
Background
Conventionally, in the manufacture of a solar cell having a pn junction, for example, a p-type diffusion layer is formed by diffusing a p-type impurity on an n-type semiconductor substrate such as silicon, thereby forming a pn junction.
In recent years, a solar cell having a selective emitter structure has been proposed to reduce contact resistance with an electrode and to suppress recombination of carriers (non-patent document 1). For example, in a solar cell having a selective emitter structure in which an n-type silicon substrate is used as a base, a high-concentration p-type diffusion layer (p++ layer) is formed immediately below an electrode in a p-type diffusion layer on the light receiving surface side, and a low-concentration to medium-concentration p-type diffusion layer (p+ layer) is formed on the light receiving surface other than immediately below the electrode. It is known that a complex process of combining multiple diffusion and partial etching by masking is required to form a selective emitter structure (patent document 1). In recent years, in order to simplify the process, there has been proposed a method of applying an impurity diffusion composition onto a substrate by screen printing or the like, and selectively forming a high concentration diffusion layer by treatment with a heating furnace or laser irradiation (patent documents 2 to 4). In particular, laser irradiation is expected as a useful method because energy can be uniformly applied to the substrate surface (patent document 5).
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2004-193350
Patent document 2 International publication No. 2015/2132
Patent document 3 Japanese patent application laid-open No. 2013-77804
Patent document 4 Japanese patent application laid-open No. 2010-514585
Patent document 5 Japanese patent application laid-open No. 2018-508976
Non-patent literature
Non-patent literature 1:E.Lee et.al.、"Exceeding 19％efficient 6inch screen printed crystalline silicon solar cells with selective emitter"、Renewable Energy、Volume 42(June 2012)、p.95-99
Disclosure of Invention
Problems to be solved by the invention
However, since high energy is required for forming the p-type diffusion layer, when the layer formed by applying the impurity diffusion composition to the substrate surface is irradiated with laser light, there is a problem that if the output power is low, diffusion of impurities does not proceed, if the output power is high, the silicon substrate is damaged, the defect density increases, and the carrier lifetime becomes small, and a p++ layer of high concentration cannot be stably formed. Further, inorganic particles contained in the impurity diffusion composition, organic substances that become carbide by laser irradiation, and the like remain in a trace amount even after the stripping step after irradiation, and there is a problem that the carrier lifetime is reduced.
The present invention has been made in view of the above-described conventional problems, and an object of the present invention is to provide an impurity diffusion composition capable of stably forming a p++ high-concentration impurity diffusion layer by a method using laser irradiation and having a small reduction in carrier lifetime, and a method for manufacturing a solar cell using the composition.
Means for solving the problems
In order to solve the foregoing problems, the impurity diffusion composition of the present invention has the following structure.
[1] An impurity diffusion composition comprising:
(a-1) a compound represented by the general formula (1) and/or polyvinyl alcohol,
(A-2) particles having an average particle diameter of 200nm or less and containing an inorganic oxide as a main component, and
(A-3) a boron compound,
And (a-2) 5 to 50 parts by mass of particles per 100 parts by mass of (a-3) the boron compound,
In the general formula (1), R 1～R4 may be the same or different and each represents a 1-valent organic group having 1 to 3 carbon atoms, and X 1 represents a single bond or at least one organic group selected from methylene groups having 1 to 3 carbon atoms and a-CH 2OCH2 -group; n 1 is an integer of 2 to 4, n 2～n4 each may be the same or different and represents an integer of 0 to 2, and n 1+n2+n3+n4＝4;m1 is an integer of 1 to 3, m 2～m3 each may be the same or different and represents an integer of 0 to 2, and m 1+m2+m3 =3.
[2] The impurity diffusion composition according to [1], wherein the compound represented by the general formula (1) contains a trimethylol compound.
[3] The impurity diffusion composition of [1] or [2], wherein the inorganic oxide is silicon oxide.
[4] The impurity diffusion composition according to any one of [1] to [3], wherein the (a-1) contains polyvinyl alcohol, and the saponification degree of the polyvinyl alcohol is 30 to 70%.
[5] The impurity diffusion composition according to [2], which comprises trimethylolpropane, trimethylolethane and/or di (trimethylolpropane) as the trimethylol compound.
[6] The impurity diffusion composition according to any one of claims [1] to [5], wherein the particles (a-2) have particle surfaces subjected to hydrophobic treatment.
[7] The impurity diffusion composition according to any one of claims 1 to 6, which does not contain an alkoxysilane compound, a silanol compound and a silicone resin, or has a content of 10 mass% or less.
[8] A method for manufacturing a solar cell, wherein an impurity diffusion layer (c) is formed on a semiconductor substrate, comprising the steps of:
A step of forming an impurity diffusion composition film (b) by applying the impurity diffusion composition (a) of any one of [1] to [7] to the semiconductor substrate, and
And (c) irradiating the impurity diffusion composition film (b) with a laser beam to form the impurity diffusion layer (c).
Effects of the invention
According to the present invention, an impurity diffusion composition in which a p++ high-concentration impurity diffusion layer is stably formed by a laser irradiation method and in which the carrier lifetime is reduced little, and a method for manufacturing a solar cell using the composition can be provided.
Drawings
Fig. 1 is a process cross-sectional view showing an example of a method for manufacturing a solar cell according to the present invention.
Fig. 2 is a process cross-sectional view showing another example of the method for manufacturing a solar cell according to the present invention.
Fig. 3 is a diagram showing a screen printing pattern used in the embodiment of the present invention.
Fig. 4 is an enlarged view of the in-plane pattern portion of the substrate of fig. 3.
Detailed Description
Next, a method for manufacturing a solar cell according to the present invention will be described with reference to the drawings. The following embodiments are examples, and the present invention is not limited to these embodiments.
Impurity diffusion composition (a) >)
The impurity diffusion composition (a) comprises:
(a-1) Compounds represented by the general formula (1) and/or polyvinyl alcohol (sometimes referred to simply as "(a-1) Compounds" in the present specification.)
(A-2) particles (in this specification, may be simply referred to as "(a-2) particles") having an average particle diameter of 200nm or less and containing an inorganic oxide as a main component
(A-3) boron compound.
[ (A-1) Compound ]
In the general formula (1), R 1～R4 may be the same or different and each represents a 1-valent organic group having 1 to 3 carbon atoms. From the viewpoint of forming a stable complex with the boron compound, preferable organic groups include saturated hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, and the like.
X 1 represents a single bond or at least one organic group selected from the group consisting of a methylene group having 1 to 3 carbon atoms and a-CH 2OCH2 -group. From the viewpoint of forming a stable complex with the boron compound, X 1 is preferably at least one organic group selected from the group consisting of single bonds, -CH 2OCH2 -groups.
N 1 is an integer of 2 to 4, and n 2～n4 may be the same or different and each represents an integer of 0 to 2. Wherein n 1+n2+n3+n4 = 4. From the viewpoint of forming a stable complex with the boron compound, n 1 is preferably an integer of 2 to 4, more preferably an integer of 3 to 4. m 1 is an integer of 1 to 3, and m 2～m3 may be the same or different and each represents an integer of 0 to 2. Wherein m 1+m2+m3 = 3. From the viewpoint of forming a stable complex with the boron compound, m 1 is preferably 2 to 3, more preferably 3.
Preferable specific examples of the general formula (1) include dimethylol compounds such as dimethylolethane, dimethylol propane and dimethylol butane, trimethylol compounds such as trimethylol methane, trimethylol butane, trimethylol pentane, trimethylol propane, trimethylol ethane and di (trimethylol propane), and tetramethylol compounds such as pentaerythritol. Among them, from the viewpoint of being able to easily form an impurity region of higher concentration and further suppressing a decrease in carrier lifetime, a trimethylol compound is more preferably contained, trimethylol propane, trimethylol ethane and/or di (trimethylol propane) are more preferably contained, and trimethylol ethane is most preferably contained.
In addition, the saponification degree of the polyvinyl alcohol (hereinafter, sometimes referred to as "PVA") is preferably 30 to 70% from the viewpoint that an impurity region of higher concentration can be easily formed and the reduction in carrier lifetime can be further suppressed. By forming a strong complex with the boron compound at a saponification degree of 30% or more, an impurity region having a higher concentration can be easily formed, and a decrease in carrier lifetime can be further suppressed. The saponification degree is more preferably 40% or more. On the other hand, when the saponification degree is 70% or less, the complex with the boron compound is stabilized in the solvent, and thus an impurity region having a higher concentration can be easily formed, and the reduction in carrier lifetime can be further suppressed. The saponification degree is more preferably 50% or less.
The average degree of polymerization of PVA is preferably 150 to 1000 in terms of solubility and stability of complex. In the present invention, the average polymerization degree and the saponification degree are both values measured in accordance with JIS K6726 (1994). The saponification degree is a value measured by a back titration method in the method described in the JIS.
The compound represented by the general formula (1) and/or PVA, wherein the 1, 3-diol moiety contained in the structure forms a stable complex with the (a-3) boron compound, thereby forming a good impurity diffusion layer. This enables formation of an impurity diffusion layer having high stability and high concentration of the complex during laser irradiation, and also enables efficient removal of residues in the lift-off step, thereby suppressing a decrease in carrier lifetime.
The amount of the compound (a-1) in the impurity diffusion composition is preferably 1 to 30% by mass from the viewpoint that an impurity region of higher concentration can be easily formed and the reduction in carrier lifetime can be further suppressed. By setting the content of the compound (a-1) to 1 mass% or more, an impurity region having a higher concentration can be easily formed. The content of the compound (a-1) is more preferably 5% by mass or more. On the other hand, by the content of the compound (a-1) being 30 mass% or less, the carrier lifetime can be further suppressed from decreasing. The content of the compound (a-1) is more preferably 20% by mass or less.
Regarding the carrier lifetime, after manufacturing a solar cell, using a solar simulator having a spectral distribution of AM1.5, simulated sunlight was irradiated at 25 ℃ with an energy density of 100mW/cm 2, and an open circuit voltage V OC (Voltage Open Circuit) was measured, whereby the carrier lifetime was estimated, and it can be said that the higher V OC, the longer the carrier lifetime.
[ (A-2) particles ]
The average particle diameter of the particles (a-2) is 200nm or less. By having an average particle diameter of 200nm or less, diffusion of boron from the (a-3) boron compound can be promoted by laser irradiation, and the impurity diffusion layer (c) having a high concentration can be stably formed. The average particle diameter of the particles (a-2) is preferably 50nm or less.
The average particle diameter of the particles is the median diameter (d 50) in the particle size distribution, and can be estimated by subjecting the particles to ultrasonic treatment with an aqueous solution or the like for 10 to 30 minutes to deagglomerate and then using a laser diffraction/scattering type particle size distribution measuring apparatus.
The particles (a-2) are mainly composed of an inorganic oxide, and preferable specific examples thereof include oxides of silicon, titanium, zirconium, aluminum, germanium, gallium, bismuth, and barium, but are not limited thereto.
From the viewpoint of further suppressing the reduction of the carrier lifetime, the particles (a-2) preferably contain silicon oxide as a main component. The main component is a component containing 70 parts by mass or more based on 100 parts by mass of the entire particle. The content of silicon oxide as a main component in the particles (a-2) is preferably 80 parts by mass or more, more preferably 90 parts by mass or more.
The content of silica in the particles can be distinguished by subjecting the particles to stepwise acid dissolution treatment and estimated using ICP-AES (inductively coupled plasma emission spectrometry).
In order to suppress the influence of trace residues after the stripping step and further suppress the reduction of the carrier lifetime, it is preferable that the particles (a-2) themselves do not contain a boron component.
The particles of (a-2) preferably have a particle surface which has been hydrophobically treated. By providing the particle surface subjected to the hydrophobic treatment, promotion of boron diffusion at the time of laser irradiation can be suppressed by bonding and granulating the particles (a-2), and an impurity diffusion layer having a higher concentration can be formed. The term "hydrophobic treatment" as used herein refers to a treatment of reducing the concentration of hydrophilic functional groups on the particle surface by forming covalent bonds on the surface using a silane coupling agent such as trimethylsilane or hexamethylenedisilazane, or by forming ionic bonds using a fluoroalkylamine such as nonafluorobutylamine. Whether or not the particles (a-2) have a particle surface subjected to a hydrophobic treatment can be determined by adding the particles (a-2) to water at a concentration of 4 mass%, stirring, and dispersing.
The amount of the particles (a-2) is 5 to 50 parts by mass per 100 parts by mass of the boron compound (a-3). By setting the particle (a-2) to 5 parts by mass or more, a higher concentration impurity region can be easily formed. The particles (a-2) are more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. On the other hand, when the amount of the particles (a-2) is 50 parts by mass or less, the carrier lifetime can be further suppressed from decreasing. The particles (a-2) are more preferably 30 parts by mass or less.
[ (A-3) boron Compound ]
The (a-3) boron compound is a component for forming a p-type impurity diffusion layer in a semiconductor substrate.
Examples of the boron compound include boric acid, diboron trioxide, methyl boric acid, phenyl boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trioctyl borate, and triphenyl borate. Among them, boric acid and diboron trioxide are more preferable from the viewpoint of doping.
From the viewpoint of stabilization of the complex at the time of laser irradiation, the amount of the (a-3) boron compound contained in the impurity diffusion composition is preferably 1 to 30% by mass based on 100% by mass of the entire impurity diffusion composition.
Further, from the viewpoint of uniformity of diffusion, the mass ratio of the (a-1) compound to the (a-3) boron compound is preferably 1:1 to 20:1, more preferably 1:1 to 10:1.
[ Alkoxysilane Compound, silanol Compound and Silicone resin ]
In the impurity diffusion composition, it is preferable that the alkoxysilane compound, the silanol compound, and the silicone resin are not contained, or their content is 10 mass% or less. By setting the content of the alkoxysilane compound, silanol compound, and siloxane resin to 10 mass% or less, promotion of boron diffusion during laser irradiation can be suppressed by bonding granulation between particles, and a higher concentration impurity diffusion layer can be formed. The content of the alkoxysilane compound, silanol compound and silicone resin is preferably 5 mass% or less, more preferably 1 mass% or less, and most preferably 0.1 mass% or less. Here, the content of the alkoxysilane compound, silanol compound, and siloxane resin in the impurity diffusion composition refers to their mass fraction relative to the total mass of the impurity diffusion composition. The content of any one of the alkoxysilane compound, silanol compound, and silicone resin is referred to as the content thereof, and the total content thereof is referred to as the total content thereof when two or more of the alkoxysilane compound, silanol compound, and silicone resin are contained.
The concentration of the impurity diffusion layer can be estimated by measuring the surface resistance of the semiconductor substrate after impurity diffusion by a four-probe type surface resistance measuring device RT-70V (manufactured by nalclan corporation), and it can be said that the lower the resistance value, the higher the concentration of diffusion.
[ Solvent ]
The impurity diffusion composition preferably further comprises a solvent. In particular, from the viewpoint of further improving printability by screen printing, spin coating, or the like, a solvent having a boiling point of 100 ℃ or higher is preferable. When the boiling point is 100 ℃ or higher, for example, when the impurity diffusion composition is printed on a printing plate used in a screen printing method, the impurity diffusion composition is easily prevented from drying and sticking on the printing plate.
The content of the solvent having a boiling point of 100 ℃ or higher is preferably 20 mass% or higher relative to the total amount of the solvent. Examples of the solvent having a boiling point of 100℃or higher include ethyl lactate (boiling point 155 ℃), diacetone alcohol (boiling point 169 ℃), propylene glycol monomethyl ether acetate (boiling point 145 ℃), propylene glycol monomethyl ether (boiling point 120 ℃), 3-methoxy-3-methyl-1-butanol (boiling point 174 ℃), gamma-butyrolactone (boiling point 204 ℃), N-methyl-2-pyrrolidone (boiling point 204 ℃), N-dimethylimidazolidone (boiling point 226 ℃), terpineol (boiling point 219 ℃) and 1, 3-propanediol (boiling point 214 ℃).
As a preferable solvent, 1, 3-propanediol is more preferably contained. By containing 1, 3-propanediol, the stability of the complex of the (a-1) compound and the (a-3) boron compound is further improved, contributing to the formation of a higher concentration of impurity region upon laser irradiation.
[ Surfactant ]
The impurity diffusion composition may comprise a surfactant. By containing the surfactant, coating unevenness can be improved, and a uniform coating film can be obtained. As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferably used.
The content of the surfactant is preferably 0.0001 to 1% by mass in the impurity diffusion composition.
[ Thickening agent ]
The impurity diffusion composition may include a thickener to adjust viscosity. This allows the coating to be performed in a more precise pattern by a printing method such as screen printing.
From the viewpoints of dense film formation and residue reduction, the thickener preferably has a 90% thermal decomposition temperature of 400 ℃ or less. Specifically, polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, and various acrylate resins are preferable, and among them, polyethylene oxide, polypropylene oxide, and acrylate resins are preferable. From the viewpoint of storage stability, an acrylic resin is particularly preferable. Here, the 90% thermal decomposition temperature refers to a temperature at which the weight of the thickener is reduced by 90% by thermal decomposition. The thermal decomposition temperature of 90% can be measured using a thermogravimetric analysis apparatus (TGA) or the like.
[ Thixotropic agent ]
From the viewpoint of screen printability, the impurity diffusion composition may contain a thixotropic agent imparting thixotropic properties. Here, imparting thixotropic properties means increasing the ratio (. Eta.1/eta.2) of the viscosity (. Eta.1) at low shear stress to the viscosity (. Eta.2) at high shear stress. By containing the thixotropic agent, the pattern accuracy of screen printing can be improved. This is presumed to be due to the following reasons. That is, it is presumed that the thixotropic agent-containing impurity diffusion composition (a) is low in viscosity at high shear stress, and therefore clogging of the screen is less likely to occur at screen printing, and that bleeding out and thickening of pattern line width immediately after printing are less likely to occur due to high viscosity at low shear stress.
Examples of the thixotropic agent include cellulose derivatives, polysaccharides, hydrogenated castor oil-based oxidized polyethylene-based, fatty acid-based polycarboxylic acids, and phosphate-based surfactants. The thixotropic agent may be used alone, but 2 or more thixotropic agents may be combined. In addition, it is more preferable to use the thickener in combination, so that a higher effect can be obtained.
The solid content concentration of the impurity diffusion composition is not particularly limited, but is preferably in the range of 1 mass% or more and 90 mass% or less. If the concentration is lower than the present concentration range, the coating film thickness may be too thin, and desired doping property and masking property may be difficult to obtain, and if the concentration is higher than the present concentration range, storage stability may be lowered.
< Method for producing solar cell >
The method for manufacturing a solar cell according to the present invention is a method for manufacturing a solar cell in which an impurity diffusion layer (c) is formed on a semiconductor substrate, comprising: and forming the impurity diffusion layer (c) by applying the impurity diffusion composition (a) to the semiconductor substrate to form an impurity diffusion composition film (b), and irradiating the impurity diffusion composition film (b) with laser light.
As the semiconductor substrate, an n-type substrate can be exemplified. Specifically, a crystalline silicon substrate obtained by mixing single crystal silicon, polycrystalline silicon, and other elements such as germanium and carbon, each having an impurity concentration of 10 15～1016 atoms/cm 3, is exemplified.
The semiconductor substrate is preferably a substantially quadrangular shape having a thickness of 50 to 300 μm and an outer shape of 100 to 250mm on one side. In order to remove the dicing damage and the natural oxide film, the surface of the semiconductor substrate is preferably etched in advance with a hydrofluoric acid solution, an alkali solution, or the like. At this time, innumerable uneven textures having a typical width of 40 to 100 μm and a depth of 3 to 4 μm are formed on the surface of the semiconductor substrate.
In the case of forming the selective emitter structure, the impurity diffusion layer is formed with different impurity concentrations at 2 or more levels of the high concentration p-type diffusion layer (p++ layer), the low concentration to medium concentration p-type diffusion layer (p+ layer). The different impurity concentrations herein mean that the difference in impurity concentration is 1×10 17 atoms/cm 3 or more, and the difference in sheet resistance value of the substrate surface of the portion where the impurity diffusion layer is formed is 10Ω/≡or more.
< Step of Forming impurity diffusion composition film (b)
First, as shown in fig. 1 (i), an impurity diffusion composition (a) is applied to a semiconductor substrate 1 to form an impurity diffusion composition film (b). Fig. 1 shows a case where the pattern 2 of the impurity diffusion composition film (b) is formed by a method described later.
Examples of the method for applying the impurity diffusion composition (a) include spin coating, screen printing, ink jet printing, slit coating, spray coating, relief printing, and gravure printing. When the pattern of the impurity diffusion composition film (b) is to be obtained, for example, a method of screen printing or spray coating with a mask having a desired pattern opening interposed therebetween, a method of moving a nozzle in accordance with a pattern layout and directly drawing a pattern by inkjet printing, a method of forming a film on the entire surface of a substrate by spin coating, forming a pattern with a photoresist, etching an opening, and then stripping the photoresist pattern, and a method of leaving a portion covered with the photoresist as a pattern may be used for patterning.
After the impurity diffusion composition (a) is applied by these methods, the semiconductor substrate 1 coated with the impurity diffusion composition (a) is preferably dried for 30 seconds to 30 minutes at 50 to 300 ℃ using a hot plate, an oven, or the like, to form the pattern 2 of the impurity diffusion composition film (b).
The film thickness of the dried impurity diffusion composition film (b) is preferably 100nm or more from the viewpoint of the diffusivity of impurities, and preferably 10 μm or less from the viewpoint of the residue after etching.
< Laser irradiation Process >)
Next, as shown in fig. 1 (ii), laser irradiation is performed on the pattern 2 of the impurity diffusion composition film (b) to form an impurity diffusion layer (c).
The laser irradiation is not particularly limited, and known ones can be used. For example, as the laser light, a fundamental wave (1064 nm) of Nd YAG laser light or Nd YVO 4 laser light, a 2-fold wave (532 nm), a 3-fold wave (355 nm), a XeCl excimer laser light (308 nm), a KrF excimer laser light (248 nm), an ArF excimer laser light (198 nm), or the like can be used. The material is irradiated at a vibration frequency of 5-100 kHz and a pulse width of 10-200 nsec, and heated to a temperature within the beam diameter of 800-1000 ℃, thereby forming a diffusion layer with a surface impurity concentration of 10 19～1021 atoms/cm 3.
When the impurity diffusion composition film (b) is not patterned, the impurity diffusion layer (c) having a desired pattern shape can be formed by laser irradiation in a desired pattern from above the impurity diffusion composition film (b).
Further, the impurity diffusion of the impurity diffusion layer (c) may be performed by additionally performing a heat treatment after the laser irradiation.
The laser irradiation atmosphere is not particularly limited, and may be performed in the atmosphere, or an inert gas such as nitrogen or argon may be used to appropriately control the amount of oxygen in the atmosphere.
When the impurity diffusion layer (c) is formed at 2 or more levels of different impurity concentrations, it is preferable to include a step of diffusing the impurity into an area where the impurity diffusion composition film (b) is not formed, using the impurity diffusion composition film (b) as a mask. Specifically, as shown in fig. 1 (iii), an impurity diffusion layer (d) having the same type of conductivity as that of the impurity diffusion layer (c) and having a different impurity concentration is formed on the unpatterned portion using the pattern 2 of the impurity diffusion composition film (b) as a mask.
The step of diffusing the impurity into the portion of the impurity diffusion composition film (b) not formed (the step of forming the impurity diffusion layer (d)) using the impurity diffusion composition film (b) as a mask may be performed after forming the impurity diffusion layer (c) by diffusing the impurity into the semiconductor substrate 1 by irradiating the impurity diffusion composition film (b) with laser light.
Specific examples of the method for diffusing the impurity into the non-formed portion of the impurity diffusion composition film (b) include: a method of implanting ions containing an impurity diffusion component into a semiconductor substrate 1 having a pattern 2 of an impurity diffusion composition film (b) and then annealing the same, a method of heating a semiconductor substrate 1 having a pattern 2 of an impurity diffusion composition film (b) in an atmosphere containing an impurity diffusion component, a method of applying another impurity diffusion composition having the same conductivity and different impurity concentrations to an unformed portion of an impurity diffusion composition film (b) on a semiconductor substrate 1 having a pattern 2 of an impurity diffusion composition film (b), and then performing electric heating, infrared heating, microwave heating, and the like.
Among them, the step of diffusing the impurity into the portion of the impurity diffusion composition film (b) where the impurity is not formed is preferably a step of heating in an atmosphere containing an impurity diffusion component.
When heating is performed in an atmosphere containing an impurity diffusion component, for example, in the case of p-type, boron bromide (BBr 3) may be bubbled, N 2 may be flowed to change the atmosphere to an atmosphere containing an impurity diffusion component, and the semiconductor substrate 1 with the pattern 2 of the impurity diffusion composition film (b) may be heated at 800 to 1000 ℃ under the atmosphere to form the impurity diffusion layer (d). By setting the gas pressure and the heating conditions, the impurity concentration of the impurity diffusion layer (d) can be set to be different from the impurity concentration of the impurity diffusion layer (c).
As shown in fig. 2, the method of forming the impurity diffusion layer (c) at2 or more levels of different impurity concentrations may be a step of forming the impurity diffusion layer (e) on the entire surface of one side of the semiconductor substrate and forming the impurity diffusion layer (f) at a concentration different from (e) on the irradiated portion by laser irradiation. The present embodiment will be described in detail below.
First, as shown in fig. 2 (i), an impurity diffusion layer (e) is formed on a semiconductor substrate 1.
Examples of the forming method include a method of implanting ions containing an impurity diffusion component and then annealing, and a method of heating in an atmosphere containing an impurity diffusion component.
Among them, a preferable method of forming is, for example, a method of bubbling boron bromide (BBr 3) in the case of p-type and flowing N 2 therethrough to prepare an atmosphere containing an impurity diffusion component, and heating the semiconductor substrate at 800 to 1000 ℃.
Next, as shown in fig. 2 (ii), the impurity diffusion composition (a) is coated on the impurity diffusion layer (e), and a pattern 2 of the impurity diffusion composition film (b) is formed. The method of applying the impurity diffusion composition (a) and the method of forming the pattern 2 of the impurity diffusion composition film (b) are as described above.
Next, as shown in fig. 2 (iii), laser irradiation is performed on the pattern 2 to form an impurity diffusion layer (f). The laser irradiation method is as described above.
< Stripping procedure >)
After the step of forming the impurity diffusion layer at 2 or more levels of different impurity concentrations in this way, as shown in fig. 1 (iV) and 2 (iV), pattern 2 of the impurity diffusion composition film (b) is removed.
The removal of the pattern 2 of the impurity diffusion composition film (b) can be performed by a known etching method. The material used for etching is not particularly limited, and for example, it is preferable to contain at least one of hydrogen fluoride, ammonium, phosphoric acid, sulfuric acid, and nitric acid as an etching component, and water, an organic solvent, and the like are preferably contained as other components.
< Back surface Forming Process >
The method for manufacturing a solar cell according to the present invention may include a back surface forming step.
For example, when a p-type impurity diffusion layer is formed on the surface of a semiconductor substrate at 2 or more levels of different impurity concentrations and an n-type impurity diffusion layer is formed on the back surface, the surface is protected with a SiO 2 film or the like to prevent n-type impurities from wrapping around the surface. The film thickness is preferably 100 to 1000nm to obtain the protective effect, and is preferably formed by plasma CVD having a high film formation rate at a low temperature in order to suppress the influence of the p-type diffusion layer on the surface of the semiconductor substrate. More specifically, the film is formed under the conditions that the flow rate ratio of the mixed gas SiH 4/N2 O is 0.01 to 5.0, the pressure of the reaction chamber is 0.1 to 4Torr, and the temperature at the time of film formation is 300 to 550 ℃.
Then, phosphorus oxychloride (POCl 3) was bubbled through the back surface, and N 2 was flowed to form an atmosphere containing impurity diffusion components, and the semiconductor substrate was heated at 800 to 900 ℃. At this time, an n-type impurity diffusion layer is formed on the back surface of the semiconductor substrate, and a silicon oxide-containing layer such as a phosphosilicate glass layer is formed on the outermost portion of the back surface by oxidation.
Then, the inorganic film on the front surface and the silicon oxide-containing layer on the back surface of the semiconductor substrate are removed by etching. A preferred specific example of etching is the same as that of forming the impurity diffusion layer at 2 or more levels of different impurity concentrations.
< Passivation procedure >)
In the method for manufacturing a solar cell of the present invention, it is preferable that a passivation film for suppressing recombination of surfaces and preventing reflection of light is provided on the front and back surfaces of the semiconductor substrate after the back surface forming step in the case where the back surface forming step is provided after the peeling step. For example, as a passivation film of the p-type diffusion layer, siO 2 obtained by heat treatment in a high-temperature oxygen atmosphere at 700 ℃ or higher and a silicon nitride film for protecting the film may be provided. In addition, only SiNx film may be formed. In this case, the material may be formed by a plasma CVD method using a mixed gas of SiH 4 and NH 3 as a raw material. At this time, hydrogen diffuses into the crystal, and dangling bonds, which are orbitals not contributing to the bonding of silicon atoms, bond with hydrogen, and deactivate the defect (hydrogen passivation). More specifically, the reaction mixture is formed under the conditions that the flow rate ratio NH 3/SiH4 is 0.05-5.0, the pressure in the reaction chamber is 0.1-4 Torr, and the temperature at the time of film formation is 300-550 ℃.
< Electrode Forming Process >
Next, a metal paste was printed by screen printing from above the passivation film onto the high concentration impurity diffusion layer out of the 2 horizontal impurity diffusion layers, and dried to form an electrode. The metal paste for an electrode contains metal particles and glass particles as essential components, and if necessary, a resin binder, other additives, and the like. The metal particles used in this case are preferably Ag or Al.
< Electrode firing Process >
Then, the electrode is heat-treated (fired) to complete the solar cell. After heat treatment (firing) at 600 to 900 ℃ for several seconds to several minutes, glass particles contained in the electrode metal paste are melted as an antireflection film of an insulating film on the light-receiving surface side, and further, the silicon surface is partially melted, and metal particles (for example, silver particles) in the paste form contact portions with the semiconductor substrate and solidify. The light-receiving surface electrode thus formed is electrically connected to the semiconductor substrate. This is called fuse-cut (access and a ya group.
The light-receiving surface electrode is generally composed of a bus electrode and a finger electrode intersecting the bus electrode. Such a light-receiving surface electrode can be formed by a method such as screen printing of the metal paste, plating of an electrode material, or vapor deposition of an electrode material heated by an electron beam in a high vacuum. The bus bar electrode and the finger electrode may be formed by a known method.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
(Blending example 1)
Preparation of p-type impurity diffusion composition
3.0G of boric acid (Fuji film and polyvinyl alcohol (manufactured by Wako pure chemical industries, ltd.) having a saponification degree of 49% (hereinafter referred to as polyvinyl alcohol (49)) 13.5g, fine particle silica (manufactured by Wako pure chemical industries, ltd.; average 1 st particle diameter < 20nm, hydrophilicity due to surface treatment) 5.0g, gamma-butyrolactone (manufactured by Tokyo) 32.9g, and terpineol (manufactured by Tokyo) 45.0g were mixed and sufficiently stirred to be uniform, thereby obtaining p-type impurity diffusion composition A1.
(Blending example 2)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A2 was obtained in the same manner as in blend example 1, except that polyvinyl alcohol (hereinafter referred to as polyvinyl alcohol (80)) having a saponification degree of 80% was used instead of polyvinyl alcohol (49).
(Blending example 3)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A3 was obtained in the same manner as in blend example 1, except that polyvinyl alcohol (hereinafter referred to as polyvinyl alcohol (10)) having a saponification degree of 10% was used instead of polyvinyl alcohol (49).
(Blending example 4)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A4 was obtained in the same manner as in blend example 1, except that a higher layer VPNKC130,130 (manufactured by the product of the company a. D.: average 1 particle size < 20nm, surface hydrophobicity treated product) was used instead of the higher layer # 200.
(Blending example 5)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A5 was obtained in the same manner as in preparation example 1, except that trimethylolpropane (manufactured by tokyo chemical Co., ltd.) was used instead of polyvinyl alcohol (49).
(Blending example 6)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A6 was obtained in the same manner as in blend example 1, except that trimethylolpropane was used instead of polyvinyl alcohol (49) and an emergency control unit was used instead of emergency control unit VPNKC and emergency control unit # 200.
(Blending example 7)
Preparation of p-type impurity diffusion composition
12.5G of boric acid (Fuji film and Wako pure chemical industries, ltd.), 12.5g of trimethylolpropane, 2.6g of high-grade conveyor oil VPNKC g, 25.0g of 1, 3-propanediol (Tokyo chemical Co., ltd.), and 45.0g of terpineol (Tokyo chemical Co., ltd.) were mixed and stirred well to obtain a p-type impurity diffusion composition A7.
(Blending example 8)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A8 was obtained in the same manner as in formulation example 7, except that bis (trimethylol propane) was used instead of trimethylol propane.
(Blending example 9)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A9 was obtained in the same manner as in formulation example 7, except that trimethylolethane was used instead of trimethylolpropane.
(Blending example 10)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A10 was obtained in the same manner as in preparation example 2, except that 15.0g of methyltriethoxysilane (KBM-13, manufactured by Xinyue chemical Co., ltd.) was added.
(Blending example 11)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition a11 was obtained in the same manner as in preparation example 2, except that nano silicon (Aldrich) having an average 1-order particle diameter of 100nm and being hydrophilic due to surface treatment was used instead of the high-level zeolite # 200.
(Blending example 12)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A12 was obtained in the same manner as in preparation example 2, except that SO-E2 (from Emmer) as silicon oxide, having an average particle size of 400nm at 1 st order and being hydrophilic due to surface treatment, was used instead of the diethyl ether # 200.
(Blending example 13)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition a13 was obtained in the same manner as in blend example 2, except that polyvinyl alcohol (80) was not added.
(Blending example 14)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition a14 was obtained in the same manner as in blend example 2, except that the a-type impurity was not added to the mixture # 200.
(Blending example 15)
Preparation of p-type impurity diffusion composition
7.1G of boric acid, 13.5g of polyvinyl alcohol (80), 5.0g of alpha-butyrolactone #200, 32.9g of gamma-butyrolactone and 45.0g of terpineol were mixed and sufficiently stirred uniformly to obtain a p-type impurity diffusion composition A15.
(Blending example 16)
Preparation of p-type impurity diffusion composition
3.7G of boric acid, 12.5g of trimethylolpropane, 2.6g of alpha-butyrolactone #200, 25.0g of gamma-butyrolactone and 45.0g of terpineol were mixed and sufficiently stirred uniformly to obtain a p-type impurity diffusion composition A16.
(Blending example 17)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A17 was obtained in the same manner as in preparation example 15, except that 11.1g of boric acid was used.
(Blending example 18)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A18 was obtained in the same manner as in preparation example 15, except that 11.1g of boric acid and 16.1g of methyltriethoxysilane were added.
(Blending example 19)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A19 was obtained in the same manner as in preparation example 15, except that 11.1g of boric acid and 9.3g of methyltriethoxysilane were added.
(Blending example 20)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition A20 was obtained in the same manner as in preparation example 15, except that 11.1g of boric acid was used and polyvinyl alcohol (80) was changed to polyvinyl alcohol (10).
(Blending example 21)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition a21 was obtained in the same manner as in example 16, except that 5.8g of boric acid was used, trimethylolpropane was changed to pentaerythritol, and the diethyl ether #200 was changed to diethyl ether VPNKC.
(Blending example 22)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition a22 was obtained in the same manner as in preparation example 15, except that 11.1g of boric acid was used, polyvinyl alcohol (80) was used as the polyvinyl alcohol (10), and the diethyl ether was used as the diethyl ether in the form of diethyl ether #200 (VPNKC).
(Blending example 23)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition a23 was obtained in the same manner as in preparation example 15, except that 11.1g of boric acid was used, polyvinyl alcohol (80) was changed to polyvinyl alcohol (65), and the diethyl ether #200 was changed to diethyl ether VPNKC.
(Blending example 24)
Preparation of p-type impurity diffusion composition
A p-type impurity diffusion composition a24 was obtained in the same manner as in preparation example 15, except that 11.1g of boric acid was used, polyvinyl alcohol (80) was changed to polyvinyl alcohol (30), and the diethyl ether #200 was changed to diethyl ether VPNKC.
Evaluation of high concentration diffusion region Forming ability (resistance value measurement) >)
In order to evaluate the high concentration diffusion region forming ability of the solar cell obtained in examples and comparative examples, a substrate for evaluating the high concentration diffusion region forming ability was produced as follows.
As a substrate, a semiconductor substrate made of n-type single crystal silicon having a side length of 156mm was prepared, and both surfaces were alkali etched to remove slicing damage and native oxide. At this time, countless uneven textures having a typical width of 40 to 100 μm and a typical depth of 3 to 4 μm are formed on both surfaces of the semiconductor substrate, and the substrate is defined as a substrate.
Next, a p-type impurity diffusion composition A1 (model TM-750 of the block type) was printed on the entire surface of one surface of the substrate by screen printing, and a screen mask (manufactured by SUS (strain), 400 mesh, wire diameter 23 μm)) was used.
After screen printing the p-type impurity diffusion composition, the substrate was heated with a hot plate at 140℃for 5 minutes in air and then heated in an oven at 230℃for 30 minutes, thereby forming a pattern having a thickness of about 1.5. Mu.m.
Then, the entire surface of one surface of the substrate is irradiated with laser light. The irradiation was performed using 2 times higher harmonic (532 nm) of Nd-YAG laser with a pulse width of 100nsec, an oscillation frequency of 10kHz, an output of 5W, and a beam diameterThe time was appropriately adjusted so that the temperature of the irradiated portion reached 980 ℃.
The irradiated substrate was immersed in a 5% hydrofluoric acid solution for 5 minutes, the p-type impurity diffusion composition remaining on the surface was removed, and then washed with water and dried to obtain a substrate for evaluating the high concentration diffusion region forming ability.
The obtained substrate was measured for 15 points of surface resistance at equal intervals in one direction including the center of the substrate by using a four-probe type surface resistance measuring device RT-70V (manufactured by nark corporation), and an average value was calculated. Similarly, p-type impurity diffusion compositions A2 to a24 were also evaluated. The lower the value, the higher the concentration of the impurity diffusion layer formed in the solar cell obtained in examples and comparative examples can be said to be.
Evaluation of Carrier lifetime (V OC measurement) >)
The solar cells (B1 to B24) obtained in the examples and the comparative examples were excellent in characteristics as the open circuit voltage V OC(Voltage Open Circuit).VOC was measured to be higher by using a solar simulator having a spectral distribution of AM1.5 and irradiating simulated sunlight at 25 ℃ with an energy density of 100mW/cm 2.
< Evaluation of stability with time of Properties >
The p-type impurity diffusion compositions (A1 to A24) after being left at room temperature (23 ℃) for 14 days were similarly formed into solar cells (B1 to B24), and the resistance values of A1 to A24 and the V OC of B1 to B24 after being left for 14 days were measured in the same manner as described above.
Example 1
As a substrate, a semiconductor substrate made of n-type single crystal silicon having a side length of 156mm was prepared, and alignment marks for alignment were laser-processed. Then, to remove the slice damage (SLICE DAMAGE) and native oxide, both surfaces are alkali etched. At this time, innumerable uneven textures having a typical width of 40 to 100 μm and a depth of 3 to 4 μm are formed on both surfaces of the semiconductor substrate, and the uneven textures are used as substrates.
The substrate was placed in a diffusion furnace (product) and a photovoltaic device was fabricated, boron bromide (BBr 3) was bubbled in under an atmosphere of nitrogen gas 19L/min and oxygen gas 0.6L/min by nitrogen gas 0.06L/min, thereby forming an atmosphere containing a p-type impurity diffusion component in the furnace, and the atmosphere was maintained at 930 ℃ for 30 minutes, thereby forming an impurity diffusion layer on the entire surface of the substrate.
Next, p-type impurity diffusion composition a17 was printed on the substrate by screen printing. The print pattern is a pattern corresponding to a screen mask (made of SUS (strain), 400 mesh, wire diameter 23 μm) of a screen printer (a silk-screen printer (strain) TM-750) in alignment in the arrangement shown in fig. 3 and 4.
After screen printing the p-type impurity diffusion composition, the substrate was heated with a hot plate at 140℃for 5 minutes in air and then heated in an oven at 230℃for 30 minutes, thereby forming a pattern having a thickness of about 1.5. Mu.m.
Next, the substrate was irradiated with laser light so as to overlap with the pattern of the p-type impurity diffusion composition shown in fig. 3 and 4. The irradiation was performed using a 2-fold harmonic (532 nm) of a Nd-YAG laser with a pulse width of 100nsec, an oscillation frequency of 10kHz, an output of 5W, and a beam diameter of 40 μm phi, and the time was adjusted so that the temperature of the irradiated portion reached 980 ℃.
The irradiated substrate was immersed in a 5% hydrofluoric acid solution for 5 minutes, and after removing the p-type impurity diffusion composition remaining on the surface, the substrate was washed with water and dried.
Next, in order to form an n-type impurity diffusion layer on the back surface, the substrate surface was placed in a plasma CVD apparatus at a substrate temperature of 400 ℃, RF power of 180W, gas flow rate: siH 4＝35scc、N2 o=1500 scc, and a pressure of 2.5torr forms a silicon oxide layer having a thickness of 500nm on the p-type impurity diffusion layer.
Next, the substrate was placed in a diffusion furnace (product) and nitrogen 19L/min, oxygen 0.6L/min, and phosphorus oxychloride (POCl 3) were bubbled in through nitrogen 0.06L/min, whereby an atmosphere containing an n-type impurity diffusion component was formed in the furnace, and the atmosphere was maintained at 850 ℃ for 20 minutes, and n-type impurity diffusion was performed on the side surface opposite to the p-type impurity diffusion surface. After the diffusion, the substrate was immersed in a 5% hydrofluoric acid solution for 10 minutes, and after the silicon oxide-containing layers on both sides of the substrate were removed, the substrate was washed with water and dried.
Next, the substrate was placed in a plasma CVD apparatus at a substrate temperature of 400 ℃, an RF power of 180W, and a gas flow rate: n 2＝750scc、SiH4＝35scc、NH3 =90 scc, and a passivation film made of silicon nitride having a thickness of 80nm was formed on both surfaces at a pressure of 2.0 torr.
Next, commercial Ag electrode pastes were printed on both sides of the substrate by screen printing. The alignment is performed using the alignment mark (ALIGNMENT MARK) such that the printed pattern of the electrode overlaps with the pattern of the p-type impurity diffusion composition film.
Next, the substrate with the electrode pattern was placed in a diffusion furnace (product of a diffusion furnace) and treated at 750 ℃ for 3 minutes in an atmosphere of 16L/min and 4L/min of oxygen to turn on the electrode and the p-type impurity diffusion layer, thereby forming a solar cell B17.
Examples 2 to 11 and comparative examples 1 to 13
Solar cells B1 to B16 and B18 to B24 were produced in the same manner as in example 1, except that p-type impurity diffusion layer-forming compositions A1 to a16 and a18 to a24 were used.
The evaluation results are shown in Table 1.
Description of the drawings
1 Semiconductor substrate
2 Pattern of impurity diffusion composition film (b)
3 Laser irradiation
4 Gas containing impurity diffusion component
5 Outermost Zhou Tuan of impurity diffusion layers
6 In-plane pattern of impurity diffusion layer (vertical 5 and horizontal 121)
(C) Impurity diffusion layers of (d), (e) and (f)
(G) Pattern part in substrate surface
(H) Width of impurity diffusion layer pattern
(J) Spacing of impurity diffusion layer patterns
Claims (8)
1. An impurity diffusion composition comprising a metal oxide and a metal oxide, which is an impurity diffusion composition (a) containing:
(a-1) a compound represented by the general formula (1) and/or polyvinyl alcohol,
(A-2) particles having an average particle diameter of 200nm or less and containing an inorganic oxide as a main component, and
(A-3) a boron compound,
And (a-2) 5 to 50 parts by mass of particles per 100 parts by mass of (a-3) the boron compound,
In the general formula (1), R 1～R4 may be the same or different and each represents a 1-valent organic group having 1 to 3 carbon atoms, and X 1 represents a single bond or at least one organic group selected from methylene groups having 1 to 3 carbon atoms and a-CH 2OCH2 -group; n 1 is an integer of 2 to 4, n 2～n4 each may be the same or different and represents an integer of 0 to 2, and n 1+n2+n3+n4＝4;m1 is an integer of 1 to 3, m 2～m3 each may be the same or different and represents an integer of 0 to 2, and m 1+m2+m3 =3.
2. The impurity diffusion composition according to claim 1, wherein the compound represented by the general formula (1) contains a trimethylol compound.
3. The impurity diffusion composition according to claim 1 or 2, wherein the inorganic oxide is silicon oxide.
4. The impurity diffusion composition according to claim 1 or 2, wherein (a-1) contains polyvinyl alcohol, and the saponification degree of the polyvinyl alcohol is 30 to 70%.
5. The impurity diffusion composition according to claim 2, comprising as the trimethylol compound trimethylol propane, trimethylol ethane and/or di (trimethylol propane).
6. The impurity diffusion composition according to claim 1 or 2, wherein the (a-2) particles have particle surfaces which are hydrophobically treated.
7. The impurity diffusion composition according to claim 1 or 2, which does not contain an alkoxysilane compound, a silanol compound and a silicone resin, or whose content is 10 mass% or less.
8. A method for manufacturing a solar cell, wherein an impurity diffusion layer (c) is formed on a semiconductor substrate, comprises the steps of:
A step of forming an impurity diffusion composition film (b) by applying the impurity diffusion composition (a) according to claim 1 or 2 to the semiconductor substrate, and
And (c) irradiating the impurity diffusion composition film (b) with a laser beam to form the impurity diffusion layer (c).
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| JP2012138568A (en) * | 2010-12-08 | 2012-07-19 | Nippon Synthetic Chem Ind Co Ltd:The | Coating liquid for impurity diffusion |
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| WO2013125252A1 (en) * | 2012-02-23 | 2013-08-29 | 日立化成株式会社 | Impurity diffusion layer forming composition, method of manufacturing semiconductor substrate having impurity diffusion layer, and method of manufacturing solar cell element |
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