CN114380507A - Glass powder for thick film silver paste suitable for crystalline silicon p + layer contact and preparation method thereof - Google Patents
Glass powder for thick film silver paste suitable for crystalline silicon p + layer contact and preparation method thereof Download PDFInfo
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- CN114380507A CN114380507A CN202111669051.XA CN202111669051A CN114380507A CN 114380507 A CN114380507 A CN 114380507A CN 202111669051 A CN202111669051 A CN 202111669051A CN 114380507 A CN114380507 A CN 114380507A
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- Prior art keywords
- oxide
- glass powder
- crystalline silicon
- layer
- contact
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- 239000011521 glass Substances 0.000 title claims abstract description 89
- 239000000843 powder Substances 0.000 title claims abstract description 63
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 29
- 239000004332 silver Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910003438 thallium oxide Inorganic materials 0.000 claims description 8
- 229910052810 boron oxide Inorganic materials 0.000 claims description 7
- 229910000464 lead oxide Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 230000003044 adaptive effect Effects 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- -1 silver-aluminum Chemical compound 0.000 abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000005215 recombination Methods 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 238000011049 filling Methods 0.000 abstract description 4
- 239000013081 microcrystal Substances 0.000 abstract description 4
- 230000003628 erosive effect Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 238000003723 Smelting Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 238000009736 wetting Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009837 dry grinding Methods 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 3
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 3
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000013082 photovoltaic technology Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000004348 Glyceryl diacetate Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 235000019443 glyceryl diacetate Nutrition 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Glass Compositions (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to C03C, in particular to glass powder for thick film silver paste suitable for a crystalline silicon p + layer contact and a preparation method thereof. The raw materials for preparing the glass powder comprise metal oxide and non-metal oxide. The invention provides glass powder for thick film silver paste suitable for a crystalline silicon p + layer contact, and the glass powder is introduced into the thick film silver paste, so that the metal-semiconductor contact resistance and the metal induced recombination speed can be reduced. By controlling the granularity and the using amount of the glass powder, the rapid formation of silver microcrystals in silver paste sintering can be promoted, the erosion to a doped layer and the formation of aluminum pinning are reduced, and the open-circuit voltage and the filling factor of the battery are improved. The glass powder provided by the invention can be used in TOPCon cell silver-aluminum paste, the metal-semiconductor contact performance of the silver-aluminum paste and a crystalline silicon solar cell P + layer is optimized, the metal induced recombination is reduced, the open-circuit voltage of the solar cell is improved, and the photoelectric conversion efficiency of an N-type or P-type TOPCon crystalline silicon solar cell is improved.
Description
Technical Field
The invention relates to C03C, in particular to the field of functional glass powder materials, which can be used as a raw material for preparing thick film silver paste, and the related thick film silver paste can be applied to the surface of a p + layer of an N-type crystalline silicon solar cell to realize ohmic contact between an electrode and the p + layer.
Background
The solar cell power generation technology is one of the most promising energy utilization technologies in the future world as a novel power generation technology which is clean, environment-friendly, safe, reliable, rich in resources and wide in application field. At present, the mainstream photovoltaic technology is mainly a P-type back passivation local contact battery (PERC battery), the industrialization efficiency is 22.5-23.3%, but the highest industrialization conversion efficiency of the PERC battery technology is about 24.5%, and the development of related products can meet the obvious bottleneck problem of continuous development; the highest efficiency of the N-TOPCon/P-TOPCon battery industrialization is expected to be 27.0%, which becomes one of the cores of the future photovoltaic technology development.
The TOPCon crystalline silicon solar cell has the characteristics of relatively simple preparation process, high conversion efficiency, low temperature coefficient, small light attenuation and the like, and the efficiency reaches the level of 24.2-24.5% in 2021 years. The development level of silver paste related to the TOPCon crystal silicon battery determines the development speed of the TOPCon battery technology. Aiming at the p + layer structure of the TOPCon battery, the surface concentration of the TOPCon battery is low, and special silver-aluminum paste of the TOPCon battery, which is different from the positive silver paste of the PERC battery, is required to be used. At present, aluminum-containing powder is often added on high-conductivity silver powder, ohmic contact is improved by utilizing the aluminum powder, but the high-activity aluminum powder can be sputtered out of a surface alumina shell under high-temperature sintering, a p + doped layer at the bottom of a silicon sediment is quickly dissolved, an obvious aluminum nailing effect is formed, high metal induction is caused, the recombination speed of a photon-generated carrier is too high, the open-circuit voltage and the filling factor of a battery are obviously reduced, the conversion efficiency of the solar battery is obviously reduced, and the electrical performance of the solar battery is influenced. To balance this property, the glass frit of the silver-aluminum paste needs to be specially optimized to effectively balance the metal-induced recombination velocity and the metal-semiconductor contact resistance.
In the patent CN 108701504A disclosed by Nippon Nameishi, Al, Zn, Cu, Ni, Au, Zn or Sn alloy powder is added, the glass powder is designed by adopting at least one raw material of PbO/SiO2/ZnO/Bi2O3/Al2O3/B2O3, the PbO weight ratio is only defined to be 50-97%, the use range of other oxides is not clearly defined, and the softening point is 200-700 ℃. The glass powder adopting the glass system is difficult to realize the effect of effectively reducing the aluminum pinning effect, the metal induced recombination speed is higher, and the contact resistivity and the open-circuit voltage cannot be effectively balanced in the TOPCon crystalline silicon solar cell.
The glass powder for silver-aluminum paste developed by Korean patent No. 10-2015-0142235, which is published by Phoenix corporation, comprises 60-80% of PbO, 15-25% of ZnO, 1-10% of B2O3, 1-5% of SiO2 and 0.1-1.0% of WO3 by mass, and the prepared N-type battery has the efficiency of 22.12% and the contact resistivity of less than 1.8m omega cm2. The glass has higher softening temperature, and the applicable sheet source with higher concentration of a p + layer and lower sheet resistance can not meet the current high sheet resistance system.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides a glass powder for adapting to a crystalline silicon p + layer contact, the composition of the glass powder comprises metal oxides and non-metal oxides, the metal oxides comprise lead oxide, zinc oxide, aluminum oxide and thallium oxide, and the non-metal oxides comprise silicon oxide and boron oxide.
In a preferred embodiment of the present invention, the glass frit is prepared from metal or nonmetal oxides, nitrates, carbonates, or crystals of two or more thereof, and is not particularly limited, wherein the final content of each component in the glass frit can be determined by ICP-OES/XRF/EDS or the like.
As a preferable technical scheme of the invention, the glass powder comprises the following components in percentage by weight: 20 to 80 wt% of lead oxide, 1 to 15 wt% of zinc oxide, 2 to 25 wt% of boron oxide, 0.5 to 8 wt% of aluminum oxide, 0.1 to 20 wt% of thallium oxide, and 0.2 to 18 wt% of silicon oxide.
Lead oxide is used as main oxide, and has the functions of lowering smelting temperature, lowering glass softening point, raising silver dissolving capacity, widening glass temperature window,The silver powder and the silicon wafer are in ohmic contact at the moment, but the pollution is increased due to the large using amount of the silver powder and the silicon wafer, and the inventor finds that the content of the lead can be reduced, the ohmic contact is promoted, the resistance is reduced, and the photoelectric conversion efficiency is improved by adding other metal or nonmetal oxides. The proportion of the lead oxide in the glass powder is 20-80 wt%, preferably 40-70 wt%, and more preferably 50-65 wt%, calculated by weight ratio. Examples of the lead oxide include lead monoxide (PbO) and lead tetraoxide (Pb)3O4) Lead nitrate (Pb (NO))3)2) One or more of the above-mentioned materials are introduced.
The invention selects the oxide with lower softening point, which can promote the sliding of the glass powder in the slurry sintering, but also causes the problem that the wettability of the silver powder is reduced along with the increase of the temperature in the glass powder sintering process, and partial exposure exists. Acidic silicon oxides, e.g. SiO, in weight ratio2The proportion of the glass powder is 0.2-18 wt%, preferably 1-10 wt%, and more preferably 3-8 wt%.
Boron oxide has a sudden change in different glass designs, mainly the transformation of its tetrahedron and trihedron. Introducing a certain amount of B2O3The glass softening temperature can be effectively reduced, the leveling property is improved, the wetting capacity of glass to the substrate is enhanced, the contact area with a silicon substrate is increased, and the ohmic contact resistance is reduced, but an even melt is difficult to form between silicon compounds and boron compounds, so that the formation of silver microcrystals can be influenced while the wetting of silver powder is influenced, and the open-circuit voltage and the filling factor are reduced. By weight ratio, boron oxides, e.g. B2O3The proportion of the glass powder is 2-25 wt%, preferably 5-15 wt%, and more preferably 8-15 wt%.
By adding alkaline earth zinc oxide, the acid resistance and the water resistance of the glass powder are improved by utilizing the stronger chemical stability of the alkaline earth zinc oxide, and the octahedral structure is also beneficial to improving the wetting of the glass powder with lower conversion temperature at high temperature and the wetting of the glass powder with the silicon substrate, and is also beneficial to promoting the transformation of partial boron oxide box tetrahedra, thereby promoting the silicon and boron compounds to form uniform melt. And zinc oxide, such as ZnO belongs to semiconductor oxide, is suitable for forming better ohmic contact with a silicon substrate, but the addition amount of zinc cannot be too much, otherwise, the wetting of silver powder and the reduction of screen printing holes are not facilitated. The proportion of zinc oxide in the glass powder is 1-15 wt%, preferably 3-10 wt%, more preferably 3-8 wt% calculated by weight ratio.
Thallium oxide belongs to an oxide with strong oxidizability, can effectively promote silver dissolution, promote the formation of silver microcrystals at a silver-silicon interface, and reduce ohmic contact resistance between an electrode and a silicon substrate. Thallium oxide has a very low melting point, can effectively reduce the glass softening temperature, increase the softening and wetting time of glass powder, further reduce ohmic contact resistance, and promote the uniform melting of metal and nonmetal and the wrapping of silver powder by adding thallium oxide. Thallium oxide, e.g. Tl, in weight ratios2O3The proportion of the glass powder is 0.5-10 wt%, preferably 2-10 wt%, and more preferably 4-8 wt%.
A small amount of amphoteric alumina is added into the glass powder, and the amphoteric alumina and other components of the glass powder are ground to form a structure related to aluminum, other metals and nonmetal, so that the amphoteric glass powder is beneficial to reducing sputtering of aluminum-containing powder and avoiding formation of aluminum pinning when being subsequently added into silver paste and printed and sintered, and further improves conversion efficiency2O3The proportion of the glass powder is 0.2-8 wt%, preferably 1-6 wt%, and more preferably 2-4 wt%.
The glass powder for thick-film silver paste in contact with the p + layer of the crystalline silicon can be adapted to the thick-film silver paste, the auxiliary oxide can be added, the high-temperature leveling property, the wettability, the glass transition temperature, the adhesiveness, the redox characteristic, the acid-base resistance, the reliability and the like of the glass powder can be adjusted in a targeted manner by introducing different oxides, and the inventor finds that the metal and nonmetal oxides can be used as main components, can be adapted to various different auxiliary oxides, can form a uniform system to promote the silver powder to contact with the p + layer of the crystalline silicon, and can form a uniform system to promote the silver powderThe coating and the bonding to the silicon substrate of (1) can reduce the formation of silicate even for calcium oxide and the like which can form silicate with silicon dioxide and the like, and obtain higher photoelectric conversion efficiency and silver microcrystalline structure. As a preferred technical solution of the present invention, the composition of the glass frit in the metal oxide further includes an auxiliary oxide, and elements in the auxiliary oxide include: oxides comprising at least one of bismuth, calcium, barium, lithium, sodium, titanium, vanadium, zirconium, niobium, yttrium, tungsten, germanium, gallium, antimony, tellurium, cerium, neodymium, or erbium, may be oxides, nitrates, carbonates of these elements, or crystals of two or more thereof, including, but not limited to, bismuth trioxide (Bi)2O3) Calcium oxide (CaO), barium oxide (BaO), lithium oxide (Li)2O), sodium oxide (Na)2O), titanium oxide (TiO)2) Vanadium pentoxide (V)2O5) Zirconium oxide (ZrO), niobium pentoxide (Nb)2O5) No yttrium oxide (Y)2O5) Tungsten oxide (WO)3) Germanium oxide (GeO)2) Gallium sesquioxide (Ga)2O3) Antimony trioxide (Sb)2O3) Tellurium dioxide (TeO)2) Cerium oxide (CeO)2) Neodymium oxide (Nd)2O3) Erbium (Er) oxide2O3) The proportion of the auxiliary oxide in the glass powder is 0-8.0 wt%, preferably 0.5-3 wt%, and more preferably 1-2 wt%, calculated by weight ratio.
As a preferred technical scheme of the invention, the glass transition temperature (differential thermal analysis test) of the glass powder is 250-500 ℃, preferably 300-450 ℃, and more preferably 330-400 ℃.
As a preferable technical scheme, the particle size D50 (measured by a laser particle size distribution instrument) of the glass powder is 0.5-4 μm, preferably 1.0-3.0 μm, and more preferably 1.5-2.5 μm; the specific surface area (BET specific surface area test method) of the glass powder is 0.5-3.0 m2A ratio of 0.8 to 2.0 m/g is preferred2A more preferable range is 1.0 to 1.5 m/g2The concentration of silver powder is selected according to the particle size of silver powder in the silver paste, and is not particularly limited.
The second aspect of the invention provides a preparation method of the glass powder suitable for the contact of the crystalline silicon p + layer, which comprises the following steps: the glass powder is prepared by blending and grinding the raw materials for preparing the glass powder at high temperature, wherein the specific method comprises but is not limited to one of a smelting ball-milling method, a sol-gel sintering ball-milling method and a smelting dry-milling method. The smelting ball milling method comprises the steps of weighing, mixing, smelting, quenching, drying, ball milling and drying raw materials required by preparation to obtain the glass powder, wherein the smelting temperature is 800-1300 ℃, the quenching process can be selected from but not limited to water quenching and dry quenching, and the ball milling process can be selected from but not limited to water milling and solvent milling. The sol-gel sintering ball milling method is to prepare the elements related to the raw materials into gel, and to obtain the glass powder after high-temperature sintering ball milling. The smelting dry-grinding method is to obtain the glass powder after weighing, mixing, smelting, quenching, drying and dry-grinding raw materials required by preparation, wherein the dry-grinding comprises but is not limited to zirconium bead grinding and jet milling.
The third aspect of the invention provides application of the glass powder suitable for the contact of the crystalline silicon p + layer in thick film silver paste.
According to a preferable technical scheme, the mass percentage of the glass powder in the thick film silver paste is 0.5-10 wt%, the silver-aluminum paste is prepared above a p + layer of the TOPCon battery through a screen printing technology, and an electrode with good ohmic contact is formed after high-temperature sintering at 720-820 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides glass powder for thick film silver paste suitable for a crystalline silicon p + layer contact, and the glass powder is introduced into the thick film silver paste, so that the metal-semiconductor contact resistance and the metal induced recombination speed can be reduced.
(2) By controlling the granularity and the using amount of the glass powder, the rapid formation of silver microcrystals in silver paste sintering can be promoted, the erosion to a doped layer and the formation of aluminum pinning are reduced, and the open-circuit voltage and the filling factor of the battery are improved.
(3) The glass powder provided by the invention can be used in TOPCon cell silver-aluminum paste, the metal-semiconductor contact performance of the silver-aluminum paste and a crystalline silicon solar cell P + layer is optimized, the metal induced recombination is reduced, the open-circuit voltage of the solar cell is improved, and the photoelectric conversion efficiency of an N-type or P-type TOPCon crystalline silicon solar cell is improved.
(4) By selecting proper metal or nonmetal oxide as a main component, a uniform system can be promoted to be formed, the wetting of silver powder and the bonding of the silver powder to a silicon substrate can be promoted in the subsequent silver paste sintering process, bubbles in a thick film are reduced, and the contact resistivity is reduced.
(5) The glass powder of the main component provided by the invention can act with various other pro-oxides to further adjust the performance of the glass powder, and has good system adaptability.
Detailed Description
Examples
Reference examples 1-2 and examples 1-18 provide glass frits prepared from the following raw materials in weight percent as shown in table 1:
TABLE 1
Evaluation of Performance
The glass powder provided in examples 1-18 and reference examples 1-2 was applied to TOPCon cell silver-aluminum paste, the corresponding silver-aluminum paste was printed on a p + layer of an N-type TOPCon crystalline silicon substrate, dried to obtain a film thickness of 15 μm, and subjected to sintering at 750-760 ℃ to obtain a cell sheet, which was subjected to current-voltage performance test, wherein the data includes open-circuit voltage (Voc), series resistance (Rs), Fill Factor (FF) and conversion efficiency (Eta), and the results are shown in Table 2. The glass frits provided in examples 1 to 18 and reference examples 1 to 2 were measured for transition temperature by differential thermal analysis (DSC) and contact resistivity of TOPCon solar cell electrodes by TLM equipment, and the results are shown in table 2.
The formula of the silver-aluminum paste comprises the following components in percentage by weight: 87% of silver powder, 2% of aluminum powder, 3% of glass powder, 5% of diethylene glycol monobutyl ether acetate, 1% of cellulose acetate butyrate CAB, 0.5% of ethyl cellulose EC 1%, 0.5% of diacetin and 0.5% of dimethyl adipate.
TABLE 2
According to the test result, the glass powder provided by the invention can be used in silver-aluminum paste, the aluminum pinning effect caused by adding aluminum is obviously improved, the metal induced recombination speed is reduced, the open-circuit voltage is improved, the metal semiconductor contact is improved, the series resistance and the contact resistivity are reduced, and the crystalline silicon solar cell with high conversion efficiency is obtained, and the silver-aluminum paste provided by the embodiment can be applied to a silicon wafer with the surface doped sheet resistance of more than 75 omega/□.
Claims (10)
1. The glass powder for adapting the contact of the crystalline silicon p + layer is characterized in that the components of the glass powder comprise metal oxides and non-metal oxides, wherein the metal oxides comprise lead oxide, zinc oxide, aluminum oxide and thallium oxide, and the non-metal oxides comprise silicon oxide and boron oxide.
2. The glass frit for contact of an accommodating crystalline silicon p + layer as claimed in claim 1, wherein the proportion of the lead oxide in the glass frit is 20 to 80 wt%, preferably 40 to 70 wt%, more preferably 50 to 65 wt% calculated by weight ratio.
3. The glass frit for contact of an accommodating crystalline silicon p + layer as claimed in claim 1, wherein the proportion of the silicon oxide in the glass frit is 0.2 to 18 wt%, preferably 1 to 10 wt%, more preferably 3 to 8 wt% calculated by weight ratio.
4. The glass frit for contact of an accommodating crystalline silicon p + layer as claimed in claim 1, wherein the proportion of boron oxide in the glass frit is 2-25 wt%, preferably 5-15 wt%, more preferably 8-15 wt%, calculated as weight ratio.
5. The glass frit for contact of an accommodating crystalline silicon p + layer as claimed in claim 1, wherein the proportion of zinc oxide in the glass frit is 1-15 wt%, preferably 3-10 wt%, more preferably 3-8 wt%;
the weight ratio of the thallium oxide in the glass powder is 0.1-20 wt%, preferably 2-10 wt%, and more preferably 4-8 wt%.
6. The glass frit for contact of an accommodating crystalline silicon p + layer as claimed in claim 1, wherein the proportion of the alumina in the glass frit is 0.2 to 8 wt%, preferably 1 to 6 wt%, more preferably 2 to 4 wt%, calculated as weight ratio.
7. The glass frit in contact with the p + layer of the accommodating crystalline silicon as claimed in any one of claims 1 to 6, wherein the composition of the glass frit further comprises an auxiliary oxide, and the auxiliary oxide comprises at least one oxide of bismuth, calcium, barium, lithium, sodium, titanium, vanadium, zirconium, niobium, yttrium, tungsten, germanium, gallium, antimony, tellurium, cerium, neodymium or erbium, and the proportion of the auxiliary oxide in the glass frit is 0 to 8.0 wt%, preferably 0.5 to 3 wt%, and more preferably 1 to 2 wt%, calculated by weight ratio.
8. The glass frit for contact of an accommodating crystalline silicon p + layer as claimed in claim 1, wherein the glass frit has a glass transition temperature of 250 to 500 ℃, preferably 300 to 450 ℃, more preferably 330 to 400 ℃.
9. The method for preparing the glass powder in contact with the adaptive crystalline silicon p + layer according to any one of claims 1 to 8, characterized by comprising the following steps: the glass powder is prepared by blending the preparation raw materials of the glass powder at high temperature and grinding.
10. The application of the glass powder for accommodating p + layer contact of crystalline silicon according to any one of claims 1 to 8 in thick film silver paste.
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| CN202111669051.XA CN114380507A (en) | 2021-12-31 | 2021-12-31 | Glass powder for thick film silver paste suitable for crystalline silicon p + layer contact and preparation method thereof |
| PCT/CN2022/128496 WO2023124495A1 (en) | 2021-12-31 | 2022-10-31 | Glass powder for thick film silver paste adapting to crystalline silicon p+ layer contact and preparation method therefor |
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| WO2023124495A1 (en) * | 2021-12-31 | 2023-07-06 | 广东南海启明光大科技有限公司 | Glass powder for thick film silver paste adapting to crystalline silicon p+ layer contact and preparation method therefor |
| WO2024050765A1 (en) * | 2022-09-08 | 2024-03-14 | 深圳市首骋新材料科技有限公司 | Frit and preparation method, and conductive paste and preparation method |
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| KR20210111912A (en) * | 2020-03-02 | 2021-09-14 | 창저우 퓨전 뉴 머티리얼 씨오. 엘티디. | Composition for forming solar cell electrode and solar cell electrode prepared using the same |
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| CN114822909B (en) * | 2022-04-29 | 2024-03-26 | 广东南海启明光大科技有限公司 | Silver-aluminum paste for low-temperature sintering crystalline silicon solar cell, preparation method and application |
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