CN103545016B - Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof - Google Patents
Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof Download PDFInfo
- Publication number
- CN103545016B CN103545016B CN201310495909.4A CN201310495909A CN103545016B CN 103545016 B CN103545016 B CN 103545016B CN 201310495909 A CN201310495909 A CN 201310495909A CN 103545016 B CN103545016 B CN 103545016B
- Authority
- CN
- China
- Prior art keywords
- oxide
- glass dust
- crystal silicon
- silicon solar
- metal powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 182
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000010703 silicon Substances 0.000 title claims abstract description 168
- 239000013078 crystal Substances 0.000 title claims abstract description 132
- 239000002002 slurry Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 81
- 238000007613 slurry method Methods 0.000 title abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 254
- 239000000428 dust Substances 0.000 claims abstract description 249
- 239000000843 powder Substances 0.000 claims abstract description 212
- 150000001875 compounds Chemical class 0.000 claims abstract description 182
- 238000005530 etching Methods 0.000 claims abstract description 177
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 175
- 230000007797 corrosion Effects 0.000 claims abstract description 175
- 238000005260 corrosion Methods 0.000 claims abstract description 174
- 229910052751 metal Inorganic materials 0.000 claims abstract description 130
- 239000002184 metal Substances 0.000 claims abstract description 130
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 230000008018 melting Effects 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 124
- 239000000203 mixture Substances 0.000 claims description 116
- 229910052714 tellurium Inorganic materials 0.000 claims description 115
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 108
- 229910052709 silver Inorganic materials 0.000 claims description 107
- 239000011701 zinc Substances 0.000 claims description 107
- 239000010936 titanium Substances 0.000 claims description 104
- 229910052725 zinc Inorganic materials 0.000 claims description 102
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 101
- 239000011734 sodium Substances 0.000 claims description 96
- 239000012298 atmosphere Substances 0.000 claims description 94
- 238000010438 heat treatment Methods 0.000 claims description 90
- 239000004332 silver Substances 0.000 claims description 87
- 229910052719 titanium Inorganic materials 0.000 claims description 87
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 86
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 85
- 239000011777 magnesium Substances 0.000 claims description 85
- 229910052802 copper Inorganic materials 0.000 claims description 73
- 239000010949 copper Substances 0.000 claims description 73
- 229910052804 chromium Inorganic materials 0.000 claims description 70
- 239000011651 chromium Substances 0.000 claims description 70
- 229910052744 lithium Inorganic materials 0.000 claims description 70
- 229910052797 bismuth Inorganic materials 0.000 claims description 69
- 229910052796 boron Inorganic materials 0.000 claims description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 68
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 66
- 238000002156 mixing Methods 0.000 claims description 65
- 229910052759 nickel Inorganic materials 0.000 claims description 65
- 229910052782 aluminium Inorganic materials 0.000 claims description 63
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 58
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 58
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 55
- 229910052788 barium Inorganic materials 0.000 claims description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 53
- 229910052749 magnesium Inorganic materials 0.000 claims description 51
- 229910052706 scandium Inorganic materials 0.000 claims description 51
- 229910052726 zirconium Inorganic materials 0.000 claims description 51
- 229910052791 calcium Inorganic materials 0.000 claims description 49
- 239000011575 calcium Substances 0.000 claims description 49
- 229910017052 cobalt Inorganic materials 0.000 claims description 49
- 239000010941 cobalt Substances 0.000 claims description 49
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 49
- 229910052700 potassium Inorganic materials 0.000 claims description 49
- 229910052708 sodium Inorganic materials 0.000 claims description 49
- 229910052712 strontium Inorganic materials 0.000 claims description 49
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 47
- 229910052760 oxygen Inorganic materials 0.000 claims description 46
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 45
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims description 44
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 43
- 229910052720 vanadium Inorganic materials 0.000 claims description 43
- 239000010955 niobium Substances 0.000 claims description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 40
- 239000010937 tungsten Substances 0.000 claims description 40
- 229910052721 tungsten Inorganic materials 0.000 claims description 34
- 229910052715 tantalum Inorganic materials 0.000 claims description 33
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 33
- 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 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 32
- 239000011574 phosphorus Substances 0.000 claims description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 30
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 30
- 239000011572 manganese Substances 0.000 claims description 30
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 30
- 239000011135 tin Substances 0.000 claims description 30
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 30
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 30
- 229910052733 gallium Inorganic materials 0.000 claims description 29
- 229910052746 lanthanum Inorganic materials 0.000 claims description 29
- 229910052758 niobium Inorganic materials 0.000 claims description 29
- 229910052727 yttrium Inorganic materials 0.000 claims description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 28
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 28
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 28
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 28
- 229910052785 arsenic Inorganic materials 0.000 claims description 28
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 28
- 238000005253 cladding Methods 0.000 claims description 28
- 229910052732 germanium Inorganic materials 0.000 claims description 28
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 28
- 229910052735 hafnium Inorganic materials 0.000 claims description 28
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 28
- 229910052738 indium Inorganic materials 0.000 claims description 28
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 28
- 239000011591 potassium Substances 0.000 claims description 28
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 28
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 27
- 229910052748 manganese Inorganic materials 0.000 claims description 25
- 239000010944 silver (metal) Substances 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052718 tin Inorganic materials 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229910014142 Na—O Inorganic materials 0.000 claims description 15
- 229910018557 Si O Inorganic materials 0.000 claims description 15
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- 229910007367 Li2TeO3 Inorganic materials 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- 229910016336 Bi—Te—O Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229940046892 lead acetate Drugs 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000005280 amorphization Methods 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 claims description 2
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 claims description 2
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 claims description 2
- SITVSCPRJNYAGV-UHFFFAOYSA-N tellurous acid Chemical compound O[Te](O)=O SITVSCPRJNYAGV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008676 import Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 17
- 230000004888 barrier function Effects 0.000 abstract description 8
- 230000003667 anti-reflective effect Effects 0.000 abstract description 6
- 230000000149 penetrating effect Effects 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract description 2
- -1 tellurium boron oxide compound Chemical class 0.000 description 58
- 238000002441 X-ray diffraction Methods 0.000 description 49
- 239000008187 granular material Substances 0.000 description 45
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 40
- 239000012071 phase Substances 0.000 description 39
- 238000000498 ball milling Methods 0.000 description 37
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 32
- 230000008859 change Effects 0.000 description 32
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 29
- 229910052799 carbon Inorganic materials 0.000 description 24
- 238000010298 pulverizing process Methods 0.000 description 23
- 229910003069 TeO2 Inorganic materials 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 18
- 229910052810 boron oxide Inorganic materials 0.000 description 15
- 229910000416 bismuth oxide Inorganic materials 0.000 description 13
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000007689 inspection Methods 0.000 description 9
- 238000010791 quenching Methods 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000013528 metallic particle Substances 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910006715 Li—O Inorganic materials 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910004273 TeO3 Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 5
- 229910001936 tantalum oxide Inorganic materials 0.000 description 5
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 5
- 229910003077 Ti−O Inorganic materials 0.000 description 4
- 229910007541 Zn O Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000005355 lead glass Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- 150000003497 tellurium Chemical class 0.000 description 4
- 239000013008 thixotropic agent Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 238000009617 vacuum fusion Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001006 Constantan Inorganic materials 0.000 description 2
- 229910008291 Li—B—O Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 239000006123 lithium glass Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- UCMJLSDIXYLIDJ-UHFFFAOYSA-N tellanylidenebarium Chemical compound [Ba]=[Te] UCMJLSDIXYLIDJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-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
- 241001465754 Metazoa Species 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 229910020222 Pb—Si Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CCXYPVYRAOXCHB-UHFFFAOYSA-N bismuth silver Chemical compound [Ag].[Bi] CCXYPVYRAOXCHB-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910000743 fusible alloy Inorganic materials 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
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.This crystal silicon solar batteries front electrode electrocondution slurry is formed by corroding etching agent, metal powder, organic carrier and glass dust；Described corrosion etching agent is one or more crystalline compounds, and its melting temperature is 250 DEG C～760 DEG C；Described glass dust is non-crystal structure.In the process of electrode conductive paste sintering, described corrosion etching agent is directly become liquid by solid, so as to easily flow；Itself and the glass dust coordinative role softened, thus being prone to etching and penetrating the antireflective insulating barrier in crystal silicon solar energy battery front, conductive metal powder and crystal silicon solar energy battery is made to form good Ohmic contact, and energy moistening conductive metal powder, contact between reinforcement metal powder, forms the crystal silicon solar batteries front electrode that electric conductivity is excellent.
Description
Technical field
The invention belongs to technical field of solar batteries, more particularly to a kind of crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
Background technology
Solar energy is a kind of inexhaustible clean type energy, along with the exhaustion day by day of the non-renewable energy resources such as coal, oil, develops, utilizes solar energy to become big focus, and solaode is exactly a kind of important means utilizing solar energy.Wherein, the crystal silicon solar batteries having been carried out industrialized production is exactly the one in solaode.
As the ingredient of crystal silicon solar batteries core the most, cell piece is in order to by the electric current collection produced under illumination and derive, it is necessary to make an electrode on front and the back side respectively.The method manufacturing electrode is a lot, and silk screen printing and altogether burning are presently the most general a kind of production technology.
Crystal silicon solar batteries conductive slurry for front electrode and backplate electrocondution slurry, aluminum back surface field slurry are the same, are all that the mode adopting silk screen printing is coated on silicon chip, and form front electrode by co-sintering at front side of silicon wafer.Crystal silicon solar batteries electrode after co-sintering adhesion-tight, the ash that do not fall, silicon chip must be unlikely to deform, and be prone to welding, it is simple to the electric current collection that illumination produced with wire also derives.Compared with the electrode electrocondution slurry of silicon solar cell back face, silicon solar cell conductive slurry for front electrode must possess the ability penetrating silicon nitride anti-reflecting film.
Traditional crystal silicon solar batteries front side conductive slurry is made up of argentum powder, glass dust, additive and organic carrier, and its electrocondution slurry is generally printed on crystal silicon solar batteries front or plane of illumination, and then sintering forms front electrode.In sintering process, glass dust in electrocondution slurry etches and penetrates antireflective insulating barrier such as silicon nitride, titanium oxide, aluminium oxide, silicon oxide or the silicon/titanium of crystal silicon solar batteries front or plane of illumination, make argentum powder and crystal silicon solar batteries substrate contact, form front electrode.Usual glass dust has following effect in the slurry: 1. moistening metal powder, promotes the sintering of metal powder；2. etching antireflection layer, and promote contacting and ensureing cementation between the two of metal and silicon face.Glass dust progressively softens in sintering process, in of short duration process cycle, is generally 1～2 minute, and during softening, segment glass powder rests in metal powder and flows, and the softening of another part glass dust is reacted to bottom with antireflection layer.
In order to make metal powder and silicon face form good Ohmic contact, then require that antireflection layer must be possible to determine when the sample has been completely etched, PN junction area can not be penetrated again simultaneously.When selecting glass dust, the composition of glass dust, softening point, thermal coefficient of expansion, wettability, consumption etc. all can affect the physicochemical change in sintering process, and then affect the various performances of solaode.If glass dust content is less, then it cannot be guaranteed that itself and antireflection layer are fully contacted and complete reaction；To ensure that antireflection layer is pierced completely, then need to add the glass dust of q.s；But if the addition of glass dust is more high, then the relative amount of conductive gold symbolic animal of the birth year is more low, and the contact probability between metallic particles is more few, it will cause that electrical property deteriorates；If glass dust softening point temperature is too high, sintering can be caused to be difficult to control to；If glass dust softening point temperature is too low, the interconnected pore between metal-powder can be blocked, hinder effective discharge of organic carrier.The glass dust that traditional crystal silicon solar batteries front side conductive slurry uses is amorphous material, in heating process, whole solid deliquescing first occurs, not having fixing fusing point, and simply soften in a certain temperature range, this scope is called softened zone, start to occur the temperature of softening to be called softening temperature, softening temperature is an eigenvalue of glass dust, and different glass has different softening temperatures, relevant with its material composition and composition.Atomic arrangement within glass dust is unordered, XRD(X-rayDiffiractionPattern) test will reveal whether the bulge that a very wide intensity is relatively low, unlike crystalline compounds, there is sharp-pointed diffractive features peak.Oxide is usually heated to melted by glass dust, quenches or is quenched and makes.Such as, crystal silicon solar batteries front side conductive slurry disclosed in US Patent No. 2011/0308595, employ plumbous tellurium oxide (Pb-Te-O) glass dust, its preparation method is: lead oxides and tellurium oxide are mixed, it is heated to molten condition under air atmosphere or oxygen atmosphere, then, the mixture of molten condition is quenched, grind and obtain its plumbous tellurium oxide (Pb-Te-O) glass dust.And for example, crystal silicon solar batteries front side conductive slurry disclosed in PCT Patent WO2012/129554, employ plumbous tellurium oxide glass powder, its preparation method is traditional method for glass preparation: lead oxides and tellurium oxide are mixed, it is heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its plumbous tellurium oxide glass powder.As described in PCT Patent WO2012/129554, the interior atoms arrangement of their glass dust is unordered, and XRD test will reveal whether the bulge that a very wide intensity is relatively low, unlike crystalline compounds, has sharp-pointed diffractive features peak.And for example, crystal silicon solar batteries front side conductive slurry disclosed in US Patent No. 2011/0232747, employ plumbous tellurium oxidate for lithium glass dust, its preparation method is: by TeO2, PbO, and Li2CO3 mixing, be heated to 900 DEG C and melt, it is incubated one hour, is then quenched and makes plumbous tellurium oxidate for lithium glass dust.And for example, crystal silicon solar batteries front side conductive slurry disclosed in US Patent No. 2011/0232746, employ plumbous tellurium boron oxide compound glass dust, its preparation method is by the mixture of plumbous tellurium boron, being heated to 800-1200 DEG C to melt, be then quenched by the mixture of fusing and make plumbous tellurium boron oxide compound glass dust, its glass dust is noncrystal, only softening temperature, it does not have specific melting temperature.
At present, Pb-Si glass system generally selected by the glass dust of front electrode slurry, also occurs in that Pb-Te glass system simultaneously.
But regardless of glass dust system, it is subject to the physical property constraint of glass dust itself, all there are the problems referred to above so that suitable glass dust and the manufacture difficulty of slurry are big, use process window narrow.
Summary of the invention
It is an object of the present invention to provide a kind of adhesion-tight, Ohmic contact is good, can improve the front electrode electrocondution slurry of crystal silicon solar batteries combination property, is 100 parts of calculating according to gross weight, including the component of following formula proportion:
Corrosion etching agent and 0.5～10 part of glass dust,
Wherein, described corrosion etching agent is 5/95～95/5 with the weight ratio of glass dust；Described corrosion etching agent is the crystalline compounds of the oxide formation of plumbous, tellurium and/or addition element, and melting temperature is 250 DEG C～760 DEG C；Described glass dust is amorphization compound；
Metal powder 70～93 parts；
Organic carrier 5～25 parts；
Described metal powder, glass dust and corrosion etching agent are randomly dispersed among organic carrier.
It is a further object to provide the crystal silicon solar batteries front electrode electrocondution slurry preparation method that a kind of technique is simple, condition is easily-controllable, production cost is low, comprise the steps:
Prepare described corrosion etching agent；
Prepare described glass dust；
Prepare described organic carrier；Described corrosion etching agent, glass dust, metal powder and organic carrier is weighed according to the formula of above-mentioned crystal silicon solar batteries front electrode electrocondution slurry；
Described corrosion etching agent, glass dust, metal powder and organic carrier are mixed, grinds, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
The preparation method that it is a further object of the present invention to provide a kind of high performance crystal silicon solar batteries front electrode, comprises the steps:
Thering is provided the crystal silicon semiconductor element that a kind of upper face has dielectric film, wherein, described dielectric film is superimposed layer at least one in silicon nitride, titanium oxide, aluminium oxide, silicon oxide；
The electrocondution slurry that the preparation method of 1～9 arbitrary described crystal silicon solar batteries front electrode electrocondution slurry or 10～18 arbitrary described crystal silicon solar batteries front electrode electrocondution slurry obtains is printed on described dielectric film；
Sintering, the step of described sintering is: is dried at 180 DEG C～260 DEG C by the described electrocondution slurry being printed on dielectric film, is heated to 700 DEG C～950 DEG C sintering；
Cooling, obtains described crystal silicon solar batteries front electrode.
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention is at least one crystal structure by adopting corrosion etching agent and glass dust, this corrosion etching agent simultaneously, and it has special internal structure and atomic arrangement；Glass dust is then at least one non-crystal structure.When co-sintering, organic carrier is removed by volatilization, described corrosion etching agent is directly become liquid by solid, become the runny liquid of appearance, itself and the glass dust coordinative role softened, thus being prone to corrosion and penetrating the antireflective insulating barrier in crystal silicon solar energy battery front, conductive metal powder and crystal silicon solar energy battery is made to form good Ohmic contact, and energy moistening conductive metal powder, contact between reinforcement metal powder, form the crystal silicon solar batteries front electrode that electric conductivity is excellent, than the glass dust that is used alone in traditional handicraft, there is more excellent characteristic
Crystal silicon solar batteries front electrode of the present invention, owing to have employed above-mentioned electrocondution slurry, has Stability Analysis of Structures, an excellent combination property such as Ohmic contact is good, conduct electricity very well.
Accompanying drawing explanation
Fig. 1 is the method process flow diagram that the present invention prepares crystal silicon solar batteries front electrode electrocondution slurry；
Fig. 2 is the method process flow diagram using electrocondution slurry of the present invention to prepare crystal silicon solar batteries front electrode；
Fig. 3 is the partial structurtes schematic diagram having printed the crystal silicon solar batteries of electrocondution slurry before sintering；
Fig. 4 is the crystal silicon solar batteries partial structurtes schematic diagram after sintering having printed electrocondution slurry；
Cooling chart when Fig. 5 is to prepare corrosion etching agent crystalline compounds；
Fig. 6 a is the exemplary measurement figure of XRD of a Pb-Te-Li-O system crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Fig. 6 b is the exemplary measurement figure of XRD of a Pb-Te-Li-O system glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak；
Fig. 7 a is the exemplary measurement figure of XRD of a Pb-Te-Si-O system crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Fig. 7 b is the exemplary measurement figure of XRD of a Pb-Te-Si-O system glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak；
Fig. 8 a is the exemplary measurement figure of XRD of a Pb-Te-Ba-O system crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Fig. 8 b is the exemplary measurement figure of XRD of a Pb-Te-Ba-O glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak；
Fig. 9 a is the exemplary measurement figure of XRD of a Pb-Te-Bi-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Fig. 9 b is the exemplary measurement figure of XRD of a Pb-Te-Bi-O glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak；
Figure 10 a is the exemplary measurement figure of XRD of a Pb-Te-Bi-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Figure 10 b is the exemplary measurement figure of XRD of a Pb-Te-Bi-O glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak；
Figure 11 a is the exemplary measurement figure of XRD of a Pb-Te-Bi-Li-B-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Figure 11 b is the exemplary measurement figure of XRD of a Pb-Te-Bi-Li-B-O glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak；
Figure 12 a is the exemplary measurement figure of XRD of a Pb-Te-Bi-B-Ti-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Figure 12 b is the exemplary measurement figure of XRD of a Pb-Te-Bi-B-Ti-O glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak.
Figure 13 a is the exemplary measurement figure of XRD of a Pb-Te-Bi-Ti-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Figure 13 b is the exemplary measurement figure of XRD of a Pb-Te-Bi-Ti-O glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak
Figure 14 a is the exemplary measurement figure of XRD of a Bi-Te-B-Li-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval；
Figure 14 b is the exemplary measurement figure of XRD of a Bi-Te-B-Li-O glass dust, demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low, it does not have sharp-pointed diffractive features peak
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Embodiments provide a kind of crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof, and use the method that this electrocondution slurry prepares crystal silicon solar batteries front electrode.
The crystal silicon solar batteries front electrode electrocondution slurry that the embodiment of the present invention provides, is 100 parts of calculating according to gross weight, including the component of following formula proportion:
Corrosion etching agent and 0.5～10 part of glass dust,
Wherein, described corrosion etching agent is 5/95～95/5 with the weight ratio of glass dust；Described corrosion etching agent is the crystalline compounds of the oxide formation of plumbous, tellurium and/or addition element, and melting temperature is 250 DEG C～760 DEG C；Described glass dust is amorphization compound；
Metal powder 70～93 parts；
Organic carrier 5～25 parts；
Described metal powder, glass dust and corrosion etching agent are randomly dispersed among organic carrier.
Fig. 1 is the method process flow diagram that the embodiment of the present invention prepares crystal silicon solar batteries front electrode electrocondution slurry, comprises the steps:
S01A, prepares described corrosion etching agent；
S01B, prepares described glass dust；
S01C, prepares described organic carrier；
S02, weighs described corrosion etching agent, glass dust, metal powder and organic carrier according to the formula of above-mentioned crystal silicon solar batteries front electrode electrocondution slurry；
S03, mixes described corrosion etching agent, glass dust, metal powder and organic carrier, grinds, obtains described crystal silicon solar batteries front electrode electrocondution slurry.
Specifically, in step S01, preparation corrosion etching agent can adopt one of following method: liquid-phase chemical reaction method, chemical vapour deposition, melted control cooling method and vacuum fusion control cooling method.
It is preferable to carry out in case at one, the preparation method of above-mentioned corrosion etching agent is: by the mixing of the lead acetate solution of telluric acid solution, tellurous acid solution, tellurate solution or tellurite solution and/or 0.1～10mol/l that the temperature of 0.1～6mol/l is 60-90 DEG C, is subsequently adding in lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium the saline solution of at least one addition element；When mixed solution only comprising tellurium and being plumbous, tellurium is 0.1/10～10/0.1 with plumbous mol ratio, it is preferably 1/5 5/1 to be stirred at 50 DEG C～250 DEG C by the solution of mixing again, maintain mixing speed within the scope of 1000～1500r/min, response time is 2～5hrs, generate precipitation, it is preferred to stir 3 hours with the speed of 1000r/min at 80 DEG C；Then being sequentially carried out solid-liquid separation, washing, until filtrate PH is 5～7；Regather solid, at 150 DEG C, dry 2～3hrs, obtain above-mentioned corrosion etching agent crystalline compounds, then pulverize, after milled processed, obtain described corrosion etching agent crystalline compounds granule.
Being preferable to carry out in case at another, the preparation method of above-mentioned corrosion etching agent is: be continuously introduced in the reative cell containing oxygen atmosphere by plumbous and/or tellurium steam by a certain percentage with the steam at least one addition element in lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium；Only comprising tellurium in gas with time plumbous when mixing, tellurium is 0.1/10～10/0.1 with plumbous mol ratio, it is preferred to 1/5 5/1；When comprising tellurium, lead and addition element in mixed solution, plumbous, the summation of tellurium is 9,0/2 80/20 with the mol ratio of the summation of addition element, it is preferred to 9,5/5 85/15；It is made to react 1～4 hour at 1000～3000 DEG C, it is preferred to react 2 hours at 1000～2000 DEG C；Above-mentioned corrosion etching agent crystalline compounds is obtained after naturally cooling to 25 DEG C；Then pulverize, after milled processed, obtain above-mentioned corrosion etching agent crystalline compounds granule.
In another case study on implementation, the preparation method of described corrosion etching agent is: mixed with the oxide of at least one addition element in lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium by the oxide of the oxide of tellurium and/or lead；When only comprising tellurium in mixture and being plumbous, tellurium is 0.1/10～10/0.1 with plumbous mol ratio, it is preferred to 2/5-5/2；When comprising tellurium, lead and addition element in mixture, the mol ratio of plumbous, tellurium element summation and addition element summation is 9,8/2 80/20, it is preferred to 9,5/5 85/15；Then in non-reducing atmosphere (including oxygen atmosphere, air atmosphere, nitrogen atmosphere, argon gas atmosphere etc.), it is heated to 700～1200 DEG C so that it is react 30～120 minutes in the molten state, it is preferred at 800-1100 DEG C 2 hours；Naturally cool to 25 DEG C or cool to 25 DEG C with the furnace, then pulverizing, after milled processed, obtaining described corrosion etching agent crystalline compounds granule.
In another case study on implementation, the preparation method of described corrosion etching agent is: by the oxide mixing of at least one addition element in the oxide of the oxide of tellurium and/or lead and lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium；When only comprising tellurium and plumbous oxide in mixture, tellurium is 0.1/10～10/0.1 with plumbous mol ratio, it is preferred to 2/5-5/2；When comprising the oxide of tellurium, lead and addition element in mixture, the mol ratio of plumbous, tellurium element summation and addition element summation is 9,8/2 80/20, it is preferred to 9,5/5 85/15.；Then in the atmosphere of vacuum, 700～1200 DEG C it are heated to so that it is react 30～120 minutes in the molten state, it is preferred at 1000 DEG C 2 hours；Naturally cool to 25 DEG C or cool to 25 DEG C with the furnace, then pulverizing, after milled processed, obtaining above-mentioned corrosion etching agent crystalline compounds granule.
Further, above-mentioned corrosion etching agent is crystalline compounds, for spherical, class is spherical, at least one in lamellar, graininess, colloid particle, is of a size of 0.1～10.0 μm.
Specifically, the method that in step S03, the step of mixing can take substep mixing:
In one embodiment, above-mentioned corrosion etching agent, glass dust and metal powder are pre-mixed, then this is pre-mixed thing mixes with organic carrier, be then ground processing, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, by above-mentioned, corrosion etching agent, glass dust and organic carrier are pre-mixed, then in this mixture, add metal powder, be then ground processing, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, metal powder and organic carrier are pre-mixed, then are pre-mixed in thing and add corrosion etching agent, glass dust at this, be then ground processing, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, 20-60 part by weight of metal powder and 20-60 weight portion organic carrier are pre-mixed, again 40-80 weight portion is corroded etching agent, glass dust and part organic carrier to be pre-mixed, then two kinds are pre-mixed thing mixing again, milled processed, obtains described crystal silicon solar batteries front electrode electrocondution slurry.
Fig. 2 is the method process flow diagram using above-mentioned electrocondution slurry to prepare crystal silicon solar batteries front electrode.The preparation method of the high-performance crystal silicon solar batteries front electrode that the embodiment of the present invention provides, comprises the steps:
S04, it is provided that a kind of upper face has the crystal silicon semiconductor element of dielectric film, wherein, described dielectric film is superimposed layer at least one in silicon nitride, titanium oxide, aluminium oxide, silicon oxide；
S05, is printed on above-mentioned crystal silicon solar batteries front electrode electrocondution slurry on the dielectric film of step S04；
S06, sintering；The step of this sintering is: dried at 180 DEG C～260 DEG C by the described electrocondution slurry being printed on dielectric film, it is heated to 720 DEG C～900 DEG C sintering, in sintering engineering, described corrosion etching agent becomes liquid, it is easy to flowing, the glass dust coordinative role of it and softening, corrode and penetrate the antireflective insulating barrier in crystal silicon solar energy battery front, moistening conductive metal powder, urges into the combination between metal powder, makes conductive metal powder and crystal silicon solar energy battery form good Ohmic contact；Cooling, obtains described crystal silicon solar batteries front electrode.
Fig. 3 is the partial structurtes schematic diagram having printed the crystal silicon solar batteries of described electrocondution slurry before sintering.It is worthy of note, this figure is an example, and it should as the use scope of the restriction present invention.As shown in Figure 3, crystal silicon solar batteries is made up of semiconductor chip 100, emitter stage 102 and insulating barrier 110, P/N interface is between semiconductor chip 100 and emitter stage 102, and electrode conductive paste 120 is employed screen printing technique and is optionally printed on the surface 121 of insulating barrier 110 local.Electrode conductive paste contains metal dust 122, corrosion etching agent 126, glass dust 124 and the organic carrier 128. needs according to solar cell design and application, the printing width of electrode conductive paste 120 is 30 μm-～2mm, the printing width of its thin gate electrode is 30～70 μm, and the printing width of primary gate electrode is 1～2mm.
Fig. 4 is the partial structurtes schematic diagram having printed the crystal silicon solar batteries of described electrocondution slurry after sintering.It is worthy of note, this figure is an example, and it should as the use scope of the restriction present invention.As shown in Figure 4, electrocondution slurry, through oversintering, is transformed into electrode 200.Sintering is to be heated to 180 DEG C-260 DEG C drying from 25 DEG C, is then heated to 700 DEG C-950 DEG C sintering, then cools down, and forms electrode 200.In sintering process, along with temperature raises, organic carrier in electrocondution slurry is removed, and corrosion etching agent is molten into liquid 210, flows to surface of insulating layer 110, along with temperature raises further, glass dust softening (as indicated by 230), the corrosion etching agent 210 of fusing and the glass dust 230 phase same-action of softening, corrode and penetrate the dielectric film 110 of crystal silicon semiconductor element surface, make metal powder directly contact with the matrix of crystal silicon semiconductor element, form ohm layer 240.The corrosion etching agent of fusing and the glass dust of softening corrosion and penetrate crystal silicon semiconductor element surface dielectric film 110 while, also effective moistening conductive metal powder, strengthen the contact between metal powder, form the metal powder coalition 220 that electric conductivity is excellent, it forms Ohmic contact by ohm layer 240 and quasiconductor 102, forms the crystal silicon solar batteries front electrode 200 that electric conductivity is excellent.
Further, in front electrode 200 of the present invention containing corrosion etching agent and glass dust sintering after mixture. above-mentioned corrosion etching agent be lead, tellurium and/or addition element (as: lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, at least one in germanium) the crystalline compounds that formed of oxide, its melting temperature is 250 DEG C～760 DEG C, above-mentioned glass dust is Pb-Si-O, Bi-Si-O, Pb-B-O, Bi-B-O, Pb-Te-O, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O, at least one in V-P-Ba-O system glass dust, wherein, described glass dust contains Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, at least one in the oxide of P or Bi；This glass dust is non-crystal structure, and its softening temperature is 250 DEG C～650 DEG C.
Further, being preferable to carry out in case at one, the metal powder being coated with containing the non-silver through oversintering in front electrode 200 of the present invention, including at least one in silver, gold, platinum, copper, ferrum, nickel, zinc, titanium, cobalt, chromium, manganese, palladium, rhodium.
In another one case study on implementation, the metal powder being coated with containing the silver through oversintering in front electrode 200 of the present invention, including at least one in the copper of silver cladding, ferrum, nickel, aluminum, zinc, titanium, cobalt, chromium, manganese, wherein, the thickness of silver coating is 10～2000nm.
In another one case study on implementation, mixture containing metal powder be coated with through the above-mentioned non-silver of oversintering and the metal powder of silver cladding in front electrode 200 of the present invention, the weight ratio of the metal powder that the metal powder of wherein said non-silver cladding is coated with silver is 5/95～95/5.
Start to discuss in detail each component of crystal silicon solar batteries front electrode electrocondution slurry provided by the present invention, preparation method, and use herein below.
I. etching agent is corroded
Corrosion etching agent of the present invention is crystalline compounds, has fusing point, is different from glass dust.Described corrosion etching agent be plumbous, tellurium and/or addition element (as: in lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium at least one) the crystalline compounds that formed of oxide, its melting temperature is 250 DEG C～760 DEG C.
Corrosion etching agent of the present invention includes the one or more kinds of mixture in following crystalline compounds: PbTe4O9、PbTeO3、PbTeO4、PbTe3O7、PbTe5O11、Pb2TeO4、Pb2Te3O7、Pb2Te3O8、Pb3TeO5、Pb3TeO6、Pb4Te1.5O7、Pb5TeO7、Pb5TeO7、PbTe2O5、Li2TeO3、Bi6B10O24、Na2B8O13、Bi4TeO8、Pb6Bi4O18、PbBi6Te10、Bi2TeO5、PbBi6TeO12、BiTe0.5Pb0.5SrNb2O9、Pb0.25SrBi1.5Te0.25Nb2O9、Pb3Te2Br2O6、Pb3TeBr2O4、Pb2CaTeO6、Pb2TeCoO6、PbTe2CuO6、PbTeCu3O7、Pb3Te2Fe2O12、Pb(Te0.33Fe0.67)O3、Pb2(Hf1.5Te0.5)O6.5、Pb2Te(Li0.5Al0.5)O6、Pb2Te(Li0.5Bi0.5)O6、Pb2TeLi0.5Fe0.5O6、PbTeLiFeO6、Pb2Te(Li0.5La0.5)O6、Pb2(Ti1.5Te0.5)O6.5、Pb2(Ti1.5Te0.5)O6.5、Pb2(Li0.5Sc0.5)TeO6、Pb2Li0.5Y0.5TeO6、Li0.5Pb2Yb0.5TeO6、Pb2MgTeO6、Pb11Si3O17、Ba(Fe0.5Mg0.5)PbTa0.5Te0.5O6、PbBaMgTeO6、Pb0.5BaNbTe2O9、BaTeO5、BaTe4O9、Pb2MgTeO6、Pb2Mg0.5Fe0.5(Ta0.5Te0.5)O6、Pb2MgSrTeO6、Pb2Mg(W0.9Te0.1)O6、Pb2Mg(W0.7Te0.3)O6、Pb2Mg(W0.5Te0.5)O6、Pb2Mg(W0.4Te0.6)O6、Pb2Mg(W0.4Te0.6)O6、PbMnTeO6、Pb(Mn0.5Te0.5)O3、Pb2MnTeO6、PbMn2Ni6Te3O18、Pb(Na0.4Te0.6)O3、Pb2(Na0.5Bi0.5)TeO6、Na0.5Pb2Fe0.5TeO6、Pb2(Na0.5La0.5)TeO6、Pb2Na0.5Sc0.5TeO6、Na0.5Pb2Yb0.5TeO6、Na0.5Pb2Y0.5TeO6、Pb4Te6Nb10O41、Pb3Ni4.5Te2.5O15、Pb2NiTeO6、PbSc0.5Ti0.25Te0.25O3、Pb2Sn1.5Te0.5O6.5、Pb2(Sn1.5Te0.5)O6.5、Pb2SrTeO6、Pb2ZnTeO6、Pb3Zn3TeAs2O14、Pb2(Zr1.5Te0.5)O6.5、PbTe5O11、Pb3(Te2O6)Cl2、Pb2ZnTeO6In at least one.Described corrosion etching agent is all crystalline compounds, there is typical crystal characteristic, when being heated to its melting temperature, crystal starts fusing, becomes liquid, it does not have softening temperature, physical aspects change in its heating process is: directly become liquid from solid-state, and glass dust is non-crystalline compounds, the physical aspects change in heating process is: first becomes softening state from solid-state, then becomes-liquid again.
Corrosion etching agent of the present invention is different from glass dust can be passed through X-ray diffraction (XRD) and measure and be distinguish between.Each crystalline compounds of described corrosion etching agent, when XRD measures, all can demonstrate sharp-pointed diffractive features peak in specific angle of diffraction, and glass dust is noncrystal, only demonstrates one in low-angle interval and is distributed the bulge that very wide intensity is relatively low.
The dramatically different transmission electron microscope (TEM) that can also pass through of corrosion etching agent of the present invention and glass dust is distinguish between.When any crystalline compounds in corrosion etching agent of the present invention is detected by transmission electron microscope, it will show orderly atomic arrangement face, and glass dust will show that unordered atomic arrangement face.
Corrosion etching agent of the present invention be spherical, class is spherical, lamellar, strip, at least one in dendritic, graininess, colloid particle, its size is not particularly limited.In a case study on implementation, it is smaller in size than 15 μm；In another case study on implementation, it is of a size of 0.1-10 μm；In another case study on implementation, it is of a size of 0.1～7.0 μm.
Described corrosion etching agent is prepared by one of following method: liquid-phase chemical reaction method, chemical vapour deposition, melted control cooling method and vacuum fusion control cooling method.
Corrosion etching agent of the present invention can be prepared by liquid-phase chemical reaction method, and its preparation process is: by tellurium saline solution, lead salt solution stirs mixing at 80 DEG C～250 DEG C, is then respectively adding lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the salt compound of at least one addition element in germanium, maintains mixing speed within the scope of 1500r/min, reacts 2～5hrs, generate precipitation, then solid-liquid separation, washing successively, regather solid, dry 1～3hrs for 150 DEG C, obtain a kind of or two or more containing plumbous and tellurium and lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the crystalline compounds that in germanium, at least one addition element and oxygen are formed.
In a case study on implementation, by tellurium salt (such as Na2TeO3) solution and lead salt be (such as lead acetate Pb (CH3COO)2) solution stirs mixing at 80 DEG C～250 DEG C, is subsequently adding lithium salts such as (LiCl or LiNO3Deng), maintain mixing speed within the scope of 1500r/min, react 2～5hrs, generate precipitation, then solid-liquid separation successively, washing, regather solid, dry 1～3hrs for 150 DEG C, obtain plumbous tellurium system crystalline compounds and the mixture such as PbT of lithium tellurium system crystalline compoundseO3And Li2TeO3The one or more kinds of mixture of crystalline compounds.
In another one case study on implementation, by tellurium salt (such as Na2TeO3) solution and lead acetate (Pb (CH3COO)2) solution stirs mixing at 80 DEG C～250 DEG C, is subsequently adding barium salt such as BaCl2With magnesium salt such as MgSO4, maintain mixing speed within the scope of 1500r/min, react 2～5hrs, generate the mixture that precipitation obtains containing lead tellurium system crystalline compounds and barium tellurium system crystalline compounds after stopping heating and cooling down with room temperature, such as PbTeO3、PbBaMgTeO6And Pb2MgTeO6Its mixture one or more kinds of of crystalline compounds.
In another one case study on implementation, by tellurium salt (such as Na2TeO3) solution and lead acetate (Pb (CH3COO)2) solution stirs mixing at 80 DEG C～120 DEG C, is subsequently adding lithium salts such as LiCl, barium salt BaCl2With bismuth saline solution such as Bi(NO3)2Solution, maintain mixing speed within the scope of 1500r/min, reaction 2～5hrs, stops generating after heating cools down with room temperature precipitation and obtains the mixture of plumbous tellurium system crystalline compounds, barium tellurium system crystalline compounds, bismuth tellurium system's crystalline compounds and lithium tellurium system crystalline compounds, for instance PbTeO3、Li2TeO3、Pb5Bi4O18、PbBi6TeO12、Bi2TeO5One or more kinds of mixture Deng crystalline compounds.
In another one case study on implementation, by tellurium salt (such as Na2TeO3) solution and lead acetate (Pb (CH3COO)2) solution stirs mixing at 80 DEG C～250 DEG C, is subsequently adding lithium salts such as LiCl or LiNO3With iron salt such as Fe (OH)3Maintain mixing speed within the scope of 1500r/min, reaction 2～5hrs, precipitation is generated after stopping heating and cooling down with room temperature, then solid-liquid separation, washing successively, regathers solid, dry 1～3hrs for 150 DEG C, obtain the mixture such as PbTeO of the multiple crystalline compounds formed containing plumbous and tellurium and lithium, ferrum and oxygen3、Li2TeO3、Li0.5Pb2Fe0.5TeO6One or more kinds of mixture Deng crystalline compounds.
Change the chemical reaction condition of above case study on implementation, comprise variation chemical composition or reaction temperature time, it is possible to obtain the crystalline compounds that performance is similar or close.
Corrosion etching agent of the present invention can also be used with the melted cooling method that controls to be prepared, and its preparation process is: is mixed with plumbous oxide by the oxide of tellurium, is then optionally separately added into lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the oxide of a kind of or two or more addition element in germanium, further Homogeneous phase mixing, it is subsequently placed in crucible, puts into heating furnace non-reducing atmosphere at 800 DEG C～1200 DEG C and (include oxygen atmosphere, air atmosphere, nitrogen atmosphere, the mixing of argon gas atmosphere or above gas) in, bring it about reaction in molten condition, then take out from heating furnace, be positioned in air atmosphere (or reducing atmosphere includes oxygen atmosphere, air atmosphere, nitrogen atmosphere, the mixing of argon gas atmosphere or above gas), naturally cool to 25 DEG C or cool to 25 DEG C with the furnace, pulverizing, after milled processed, obtaining one or more by plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the crystalline compounds that at least one and oxygen in germanium is formed, its melting temperature is 250 DEG C～760 DEG C.
Crystalline compounds of the present invention includes the one in following crystalline compounds or two or more: PbTe4O9、PbTeO3、PbTe4O9、PbTeO3、PbTeO4、PbTe3O7、PbTe5O11、Pb2TeO4、Pb2Te3O7、Pb2Te3O8、Pb3TeO5、Pb3TeO6、Pb4Te1.5O7、Pb5TeO7、Pb5TeO7、PbTe2O5、Li2TeO3、Bi6B10O24、Na2B8O13、Bi4TeO8、Pb6Bi4O18、PbBi6Te10、Bi2TeO5、PbBi6TeO12、BiTe0.5Pb0.5SrNb2O9、Pb0.25SrBi1.5Te0.25Nb2O9、Pb3Te2Br2O6、Pb3TeBr2O4、Pb2CaTeO6、Pb2TeCoO6、PbTe2CuO6、PbTeCu3O7、Pb3Te2Fe2O12、Pb(Te0.33Fe0.67)O3、Pb2(Hf1.5Te0.5)O6.5、Pb2Te(Li0.5Al0.5)O6、Pb2Te(Li0.5Bi0.5)O6、Pb2TeLi0.5Fe0.5O6、PbTeLiFeO6、Pb2Te(Li0.5La0.5)O6、Pb2(Ti1.5Te0.5)O6.5、Pb2(Ti1.5Te0.5)O6.5、Pb2(Li0.5Sc0.5)TeO6、Pb2Li0.5Y0.5TeO6、Li0.5Pb2Yb0.5TeO6、Pb2MgTeO6、Pb11Si3O17、Ba(Fe0.5Mg0.5)PbTa0.5Te0.5O6、PbBaMgTeO6、Pb0.5BaNbTe2O9、BaTeO5、BaTe4O9、Pb2MgTeO6、Pb2Mg0.5Fe0.5(Ta0.5Te0.5)O6、Pb2MgSrTeO6、Pb2Mg(W0.9Te0.1)O6、Pb2Mg(W0.7Te0.3)O6、Pb2Mg(W0.5Te0.5)O6、Pb2Mg(W0.4Te0.6)O6、Pb2Mg(W0.4Te0.6)O6、PbMnTeO6、Pb(Mn0.5Te0.5)O3、Pb2MnTeO6、PbMn2Ni6Te3O18、Pb(Na0.4Te0.6)O3、Pb2(Na0.5Bi0.5)TeO6、Na0.5Pb2Fe0.5TeO6、Pb2(Na0.5La0.5)TeO6、Pb2Na0.5Sc0.5TeO6、Na0.5Pb2Yb0.5TeO6、Na0.5Pb2Y0.5TeO6、Pb4Te6Nb10O41、Pb3Ni4.5Te2.5O15、Pb2NiTeO6、PbSc0.5Ti0.25Te0.25O3、Pb2Sn1.5Te0.5O6.5、Pb2(Sn1.5Te0.5)O6.5、Pb2SrTeO6、Pb2ZnTeO6、Pb3Zn3TeAs2O14、Pb2(Zr1.5Te0.5)O6.5、PbTe5O11、Pb3(Te2O6)Cl2、Pb2ZnTeO6In at least one.Described crystalline compounds be additionally included in small region memory two yuan or low-melting alloy crystal (Eutectic) more than two yuan small as plumbous tellurium bismuth (Pb-Te-Bi), plumbous tellurium lithium (Pb-Te-Li), such as plumbous tellurium silver bismuth (Pb-Te-Ag-Bi) alloy etc..
Change the condition of above case study on implementation, it is possible to obtain the crystalline compounds that performance is similar.Such as, reaction can below 700 DEG C or after the temperature of more than 1200 DEG C carries out melting, it is possible to use the protective gas not heated of flowing is (such as N2, CO2, Ar2Deng) flow through its molten mass surface, accelerate rate of cooling, or use the protective gas heated (such as N2、CO2、Ar2Deng) flow through its molten mass surface, slow down rate of cooling, obtains its crystalline compounds.
In a case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2O or Li2CO3Further Homogeneous phase mixing, it is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, make it react in the molten state, then take out from heating furnace, it is positioned in air atmosphere, naturally cools to 25 DEG C or cool to 25 DEG C with the furnace, pulverizing, after milled processed, obtain multiple two yuan or more than the two yuan mixture containing plumbous, tellurium and the crystalline compounds of lithium and oxygen formation.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2O or Li2CO3, boron oxide B2O3With the oxide of bismuth such as Bi2O3Further Homogeneous phase mixing, it is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, make it react in the molten state, then take out from heating furnace, it is positioned in air atmosphere, naturally cools to 25 DEG C, pulverize, after milled processed, obtain the mixture of multiple two yuan or more than the two yuan crystalline compounds formed containing lead, tellurium, lithium, boron and bismuth and oxygen.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2With the oxide of barium such as BaO, further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium and barium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, barium the oxide such as Na of oxide such as BaO, sodium2O, and aluminium oxide such as Al2O3Further Homogeneous phase mixing, it is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C-1200 DEG C or in oxygen atmosphere, make it react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, it is positioned in air atmosphere, naturally cools to 25 DEG C, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, aluminum, sodium and barium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, barium the oxide such as WO of oxide such as BaO, tungsten3Further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten and barium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, barium the oxide such as WO of oxide such as BaO, tungsten3, tantalum oxide such as Ta2O5Further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten, tantalum and barium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, barium the oxide such as WO of oxide such as BaO, tungsten3, tantalum oxide such as Ta2O5With the oxide of chromium such as Cr2O3Further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten, tantalum, chromium and barium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, silicon oxide such as SiO2, the oxide of boron such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, barium the oxide such as WO of oxide such as BaO, tungsten3, tantalum oxide such as Ta2O5With the oxide of chromium such as Cr2O3Further Homogeneous phase mixing, it is subsequently placed in crucible, put in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, it is positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten, tantalum, silicon, chromium and barium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, the oxide such as WO of the oxide of zinc such as ZnO, tungsten3, tantalum oxide such as Ta2O5With the oxide of chromium such as Cr2O3Further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten, tantalum, zinc and chromium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, the oxide such as Nb of the oxide of zinc such as ZnO, niobium2O5, magnesium the oxide such as WO of oxide such as MgO, tungsten3, tantalum oxide such as Ta2O5With the oxide of chromium such as Cr2O3Further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, niobium, magnesium, tungsten, tantalum, zinc and chromium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, barium the oxide such as Y of oxide such as BaO, yttrium2O3, zirconium oxide such as ZrO2With the oxide of chromium such as Cr2O3Further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, zirconium, yttrium, chromium and barium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, the oxide such as La of the oxide of barium such as BaO, lanthanum2O3, scandium oxide such as Sc2O3With the oxide of chromium such as Cr2O3Further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, zirconium, lanthanum, chromium, scandium and barium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, silicon oxide such as SiO2, boron oxide such as B2O3, bismuth oxide such as Bi2O3With titanyl compound such as TiO2, further Homogeneous phase mixing, it is subsequently placed in crucible, put in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, make it react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, pulverize, after milled processed, obtain multiple two yuan or more than two yuan containing lead, tellurium, lithium, bismuth, boron, titanium, silicon the mixture of crystalline compounds.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, boron oxide such as B2O3, bismuth oxide such as Bi2O3With titanyl compound such as TiO2, further Homogeneous phase mixing, it is subsequently placed in crucible, put in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, make it react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, silicon oxide such as SiO2, boron oxide such as B2O3, bismuth oxide such as Bi2O3, titanyl compound such as TiO2, aluminum oxide such as Al2O3, further Homogeneous phase mixing, it is subsequently placed in crucible, put in heating furnace air atmosphere at 800 DEG C～1200 DEG C or in oxygen atmosphere, make it react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, silicon and aluminum.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, the oxide of silicon such as SiO2, the oxide of boron such as B2O3, the oxide of bismuth such as Bi2O3, and titanyl compound such as TiO2Further Homogeneous phase mixing, is subsequently placed in crucible, puts in heating furnace air atmosphere at 800 DEG C-1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, being positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium and silicon.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, the oxide of silicon such as SiO2, the oxide of boron such as B2O3, the oxide of bismuth such as Bi2O3, titanyl compound is TiO such as2With the oxide of copper such as CuO2 further Homogeneous phase mixing, it is subsequently placed in crucible, put in heating furnace air atmosphere at 800 DEG C-1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, it is positioned in air atmosphere, naturally cool to 25 DEG C, pulverize, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, copper and silicon.
In another one case study on implementation, first by the oxide of tellurium such as TeO2With plumbous oxide such as Pb3O4Or PbO mixes, and is subsequently adding the oxide such as Li of lithium2CO3, the oxide of silicon such as SiO2, the oxide of boron such as B2O3, the oxide of bismuth such as Bi2O3, titanyl compound is TiO such as2The oxide of ruthenium such as RuO4, with the oxide of copper such as CuO2 further Homogeneous phase mixing, it is subsequently placed in crucible, put in heating furnace air atmosphere at 800 DEG C-1200 DEG C or in oxygen atmosphere, it is made to react in the molten state, then cool to 25 DEG C with the furnace or take out from heating furnace, it is positioned in air atmosphere, naturally cools to 25 DEG C, pulverize, pulverize, after milled processed, obtain multiple two yuan or more than two yuan and contain lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of ruthenium, titanium, copper and silicon.
Corrosion etching agent of the present invention can also be used with vacuum fusion control cooling method to be prepared, and its preparation process is: is mixed with plumbous oxide by the oxide of tellurium, is then respectively adding lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the oxide of at least one addition element in germanium, further Homogeneous phase mixing, it is subsequently placed in crucible, put into vacuum furnace, at 800 DEG C～1200 DEG C, in the atmosphere of vacuum, carry out melting, then, naturally cool to 25 DEG C, pulverize again, after milled processed, obtain one or more two yuan or more than two yuan containing plumbous and tellurium and lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the crystalline compounds that the addition element such as germanium and oxygen are formed.
As is familiar to those skilled in the art, the chemical reaction condition of above case study on implementation is changed, it is possible to obtain the plumbous tellurium system crystalline compounds that performance is similar.Such as, its smelting temperature can below 700 DEG C or more than 1200 DEG C；Again such as, after melting completes, outside except with the method for natural cooling, it is also possible to use the protective gas not heated of flowing (such as N2, CO2, Ar2Deng) flow through its molten mass surface, accelerate to be cooled to 25 DEG C, or use the protective gas heated (such as N2, CO2, Ar2Deng) flow through its molten mass surface, slow down rate of cooling, is cooled to 25 DEG C.
Corrosion etching agent of the present invention can also be used with chemical vapour deposition to be prepared, its preparation process is: be continuously introduced in the reative cell of oxygen atmosphere by tellurium with plumbous gas, it is then respectively adding lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, gas at least one in germanium, it is made to react 1～3 hour at 1000～1300 DEG C, after naturally cooling to 25 DEG C, after milled processed, obtain one or more by plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the crystalline compounds that at least one and oxygen in germanium is formed, its melting temperature is 250 DEG C～760 DEG C.
Specifically, further illustrate the present invention below by exemplary case study on implementation and comparative case study on implementation and use crystalline compounds corrosion etching agent compared to traditional method uses merely glass dust have the advantage that:
Exemplary case study on implementation 1: first by 14gTeO2And 8.75gPb3O4Oxide powder mixes, and then, is sequentially added into 0.75gAl2O3And 1.5gLi2CO3Oxide powder, further Homogeneous phase mixing, it is subsequently placed in crucible, put into heating furnace, be warming up to 900 DEG C, in the air atmosphere at 900 DEG C, it is made to react 60min in the molten state, then melted mixture is taken out from stove, be placed under atmospheric environment natural cooling, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1～15 μ m, obtains its crystalline compounds.Melted mixture temperature in a furnace is 900 DEG C, and after taking out from stove, temperature drops to 732 DEG C.The mixture that Fig. 5 is melted take out from stove after cool time and the relation of temperature, record is from 732 DEG C, can be seen that, it is cooled to 593 DEG C from 732 DEG C in the 1st minute, average cooling rate is 139 DEG C/min, it is cooled to 504 DEG C from 593 DEG C in second minute, average cooling rate is 89 DEG C/min, it is cooled to 449 DEG C from 504 DEG C in the 3rd minute, average cooling rate is 55 DEG C/min, is cooled to 416.2 DEG C from 449 DEG C in the 4th minute, and average cooling rate is 32.8 DEG C/min, at this moment, molten mass has had changed into crystal.After being cooled to 25 DEG C, the block obtained is carried out pulverizing and obtains little granule, little granule is formed powder body again through ball milling.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in Figure 6 a.By Fig. 6 a it can be seen that Li2TeO3And PbTeO3The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, Al2O3But the angle of diffraction that characteristic peak is corresponding demonstrates a relatively low sharp-pointed diffractive features peak, so exemplary case study on implementation 1 obtains Li2TeO3And PbTeO3The mixture of two kinds of crystalline compounds and small Al2O3Crystal.
Comparative case study on implementation 1: first by 14gTeO2And 8.75gPb3O4Oxide powder mixes, and then, is sequentially added into 0.75gAl2O3And 1.5gLi2CO3Oxide powder, further Homogeneous phase mixing, it is subsequently placed in crucible, put into heating furnace to exist, be warming up to 900 DEG C, in the air atmosphere at 900 DEG C, it is made to react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, the powder body D of ball milling50In 0.1～15 μ m, obtain glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in Figure 6 b.By Fig. 6 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 1 and comparative case study on implementation 1, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds Li of the present invention2TeO3And PbTeO3, the physical aspects change in heating process is: solid-liquid；The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Exemplary case study on implementation 2: first by 3.5gTeO2And 6.6gPb3O4Oxide powder mixes, and then, adds 0.45gSiO2Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1000 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment and naturally cools to 25 DEG C, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in Figure 7a.By Fig. 7 a it can be seen that PbTeO3、Pb11Si3O17The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 2 obtains PbTeO3And Pb11Si3O17The mixture crystal of two kinds of crystalline compounds.
Comparative case study on implementation 2: first by 3.5gTeO2And 6.6gPb3O4Oxide powder mixes, and then, adds 0.45gSiO2Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1000 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, the powder body D of ball milling50In 0.1～15 μ m, obtain glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in Figure 7b.By Fig. 7 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 2 and comparative case study on implementation 2, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds PbTeO of the present invention3And Pb11Si3O17, the physical aspects change in heating process is: solid-liquid；The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Exemplary case study on implementation 3: first by 4.9gTeO2And 6.6gPb3O4Oxide powder mixes, and then, adds 0.24gBaO2Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 900 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment and naturally cools to 25 DEG C, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in Figure 8 a.By Fig. 8 a it can be seen that PbTeO3、BaTeO5, and BaTe4O9The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 3 obtains PbTeO3、BaTeO5And BaTe4O9, the mixture of three kinds of crystalline compounds and BaO crystal.
Comparative case study on implementation 3: first by 4.9gTeO2And 6.6gPb3O4Oxide powder mixes, and then, adds 0.24gBaO2Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 900 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, the powder body D of ball milling50In 0.1～15 μ m, obtain glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in Figure 8 b.By Fig. 8 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 3 and comparative case study on implementation 3, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds PbTeO of the present invention3、Ba11TeO5And BaTe4O9The mixture of three kinds of crystalline compounds, the physical aspects change in heating process is: solid-liquid；The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Exemplary case study on implementation 4: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1100 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment and naturally cools to 25 DEG C, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as illustrated in fig. 9.By Fig. 9 a it can be seen that Bi4TeO8And PbTeO3The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 4 obtains Bi4TeO8And PbTeO3The mixture of two kinds of crystalline compounds.
Comparative case study on implementation 4: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 900 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, the powder body D of ball milling50In 0.1～15 μ m, obtain glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in figure 9b.By Fig. 9 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 4 and comparative case study on implementation 4, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds Bi of the present invention4TeO8And PbTeO3The mixture of two kinds of crystalline compounds, the physical aspects change in heating process is: solid-liquid；The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Exemplary case study on implementation 5: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.25gBi2O3Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1100 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment and naturally cools to 25 DEG C, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1-15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in Figure 10 a.By Figure 10 a it can be seen that Bi4TeO8, Bi2TeO5, and PbTeO3The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 6 obtains Bi4TeO8, Bi2TeO5, and PbTeO3The mixture of three kinds of crystalline compounds.
Comparative case study on implementation 5: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.25gBi2O3Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1100 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, and the powder body D50 of ball milling, in 0.1-15 μ m, obtains glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in fig. lob.By Figure 10 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 5 and comparative case study on implementation 5, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds Bi of the present invention4TeO8, Bi2TeO5, and PbTeO3The mixture of three kinds of crystalline compounds, the physical aspects change in heating process is: solid-liquid.The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Exemplary case study on implementation 6: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Oxide powder, 0.05gB2O3Oxide powder and 1.25gLi2CO3Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1100 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment and naturally cools to 25 DEG C, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in fig. 11a.By Figure 11 a it can be seen that Bi24B2O39、Pb5B2O5、Pb5TeO7And Li6TeO6The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 6 obtains Bi24B2O39、Pb5B2O5、Pb5TeO7And Li6TeO6The mixture of four kinds of crystalline compounds.
Comparative case study on implementation 6: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Oxide powder, 0.05gB2O3Oxide powder and 1.25gLi2CO3Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1100 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, the powder body D of ball milling50In 0.1～15 μ m, obtain glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in figure 11b.By Figure 11 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 6 and comparative case study on implementation 6, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds Bi of the present invention24B2O39、Pb5B2O5、Pb5TeO7, and Li6TeO6The mixture of four kinds of crystalline compounds, the physical aspects change in heating process is: solid-liquid；The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Exemplary case study on implementation 7: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Oxide powder, 0.05gB2O3Oxide powder and 1.25gTiO2Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1100 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment and naturally cools to 25 DEG C, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as figure 12 a shows.By Figure 12 a it can be seen that Bi4TeO8、Pb3Bi2O6、Pb2B2O5And PbTiO3The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 7 obtains Bi4TeO8、Pb3Bi2O6、Pb2B2O5And PbTiO3The mixture of four kinds of crystalline compounds.
Comparative case study on implementation 7: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Oxide powder, 0.05gB2O3Oxide powder and 1.25gTiO2Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1100 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, the powder body D of ball milling50In 0.1～15 μ m, obtain glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in Figure 12b.By Figure 12 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 7 and comparative case study on implementation 7, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds Bi of the present invention24B2O39、Pb5B2O5、Pb5TeO7And Li6TeO6The mixture of four kinds of crystalline compounds, the physical aspects change in heating process is: solid-liquid；The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Exemplary case study on implementation 8: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Oxide powder, 0.05gB2O3Oxide powder, and 1.25gTiO2Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 1100 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment and naturally cools to 25 DEG C, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1-15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as depicted in fig. 13 a.By Figure 13 a it can be seen that Ti2TeO8, Pb2Te3O8, Pb5Bi8O17, and PbBiO6The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 8 obtains Ti2TeO8, Pb2Te3O8, Pb5Bi8O17, and Pb3BiO6The mixture of four kinds of crystalline compounds.
Comparative case study on implementation 8: first by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Oxide powder, 0.05gB2O3Oxide powder, and 1.25gTiO2Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put in heating furnace air atmosphere at 900 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, and the powder body D50 of ball milling, in 0.1-15 μ m, obtains glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as illustrated in fig. 13b.By Figure 13 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 8 and comparative case study on implementation 8, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds Ti of the present invention2TeO8, Pb2Te3O8, Pb5Bi8O17, and PbBiO6The mixture of four kinds of crystalline compounds, the physical aspects change in heating process is: solid-liquid.The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Exemplary case study on implementation 9: by 12gTeO2And 0.625gB2O3, 1.25gBi2O3, and 1.5gLi2CO3Oxide powder Homogeneous phase mixing, is subsequently placed in crucible, puts into heating furnace, it is warming up to 1100 DEG C, in the air atmosphere at 1100 DEG C, makes it react 60min in the molten state, then melted mixture is taken out from stove, be placed under atmospheric environment natural cooling, form block.The block obtained being carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, the powder body of ball milling, in 0.1-15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in figures 14a.By Figure 14 a it can be seen that Li2TeO3And Bi6B10O24The angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 9 obtains Li2TeO3And Bi6B10O24The mixture of two kinds of crystalline compounds and small Al2O3Crystal.
Comparative case study on implementation 9: by 12gTeO2And 0.625gB2O3, 1.25gBi2O3, and 1.5gLi2CO3Oxide powder Homogeneous phase mixing, is subsequently placed in crucible, puts into heating furnace, it is warming up to 1100 DEG C, in the air atmosphere at 1100 DEG C, makes it react 60min in the molten state, then melted mixture is taken out from stove, pour in the deionized water of 25 DEG C and quench, obtain block.The block obtained obtains little granule then through pulverizing, and again through ball milling, little granule is formed powder body, and the powder body D50 of ball milling, in 0.1-15 μ m, obtains glass dust.By XRD, the glass dust of preparation in above-mentioned case study on implementation having been carried out analytical control, result is as shown in fig. 14b.By Figure 14 b it can be seen that the XRD inspection of described glass dust demonstrates one and is distributed the bulge that very wide intensity is relatively low, it does not have demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 9 and comparative case study on implementation 9, prepared crystalline compounds and glass dust have identical chemical composition, but, owing to its preparation method is different, internal structure is different, atomic arrangement is different, and result in they change procedures of physical state in heating process has obvious difference.Wherein, the former is crystalline compounds Li of the present invention2TeO3And Bi6B10O24, the physical aspects change in heating process is: solid-liquid.The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid.
Electrode slurry of the present invention contains glass dust and crystalline compounds corrosion etching agent simultaneously.In slurry sintering process, when temperature reaches fusing point, its crystalline compounds corrosion etching agent physical aspect by solid-state to liquid state.It was solid before fusing point, will not be filled between metal powder granule in hole, the discharge of organic component will not be hindered, thus being prevented effectively from such as glass dust to soften the blockage problem brought in early days；After corrosion etching agent fusing, for liquid, its viscosity is low, the space between metal powder can be quickly move through and flow into bottom, can effectively corrode and penetrate the antireflective insulating barrier in crystal silicon solar energy battery front, make conductive metal powder and crystal silicon solar energy battery form good Ohmic contact, it is possible to effective moistening conductive metal powder, urge into the combination between metal powder, form the crystal silicon solar batteries front electrode that electric conductivity is excellent.The crystalline compounds corrosion etching agent of its liquid condition, it is easy to sprawl, it is possible to provide more interface, increase contact point and the tunnel-effect of conduction, make the electrode resistance of formation diminish.Inventor finds under study for action, and the content of the corrosion etching agent in above-described embodiment crystal silicon solar batteries front electrode electrocondution slurry is if greater than 10 weight portions, it is possible to burns PN junction, causes short circuit；If corrosion etching agent is less than 0.5 weight portion, hence it may becomes difficult to remove antireflection layer completely, cause the crystal silicon solar batteries penalty of preparation.Therefore, frit and corrosion etching agent gross weight ratio control within the scope of 0.5～10wt%, frit with corrosion etching agent weight ratio be 5/95～95/5.
II. glass dust and corrosion etching agent
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention, containing corrosion etching agent and glass dust, this corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 0.5-10%, and the part by weight of corrosion etching agent and glass dust can be 5/95-95/5.
The crystalline compounds that the oxide that corrosion etching agent of the present invention is plumbous, tellurium and/or addition element (in lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium at least one) is formed, its melting temperature is 250 DEG C～760 DEG C.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Crystalline compounds of the present invention includes in following crystalline compounds: PbTe4O9、PbTeO3、PbTeO4、PbTe3O7、PbTe5O11、Pb2TeO4、Pb2Te3O7、Pb2Te3O8、Pb3TeO5、Pb3TeO6、Pb4Te1.5O7、Pb5TeO7、Pb5TeO7、PbTe2O5、Li2TeO3、Bi6B10O24、Na2B8O13、Bi4TeO8、Pb6Bi4O18、PbBi6Te10、Bi2TeO5、PbBi6TeO12、BiTe0.5Pb0.5SrNb2O9、Pb0.25SrBi1.5Te0.25Nb2O9、Pb3Te2Br2O6、Pb3TeBr2O4、Pb2CaTeO6、Pb2TeCoO6、PbTe2CuO6、PbTeCu3O7、Pb3Te2Fe2O12、Pb(Te0.33Fe0.67)O3、Pb2(Hf1.5Te0.5)O6.5、Pb2Te(Li0.5Al0.5)O6、Pb2Te(Li0.5Bi0.5)O6、Pb2TeLi0.5Fe0.5O6、PbTeLiFeO6、Pb2Te(Li0.5La0.5)O6、Pb2(Ti1.5Te0.5)O6.5、Pb2(Ti1.5Te0.5)O6.5、Pb2(Li0.5Sc0.5)TeO6、Pb2Li0.5Y0.5TeO6、Li0.5Pb2Yb0.5TeO6、Pb2MgTeO6、Pb11Si3O17、Ba(Fe0.5Mg0.5)PbTa0.5Te0.5O6、PbBaMgTeO6、Pb0.5BaNbTe2O9、BaTeO5、BaTe4O9、Pb2MgTeO6、Pb2Mg0.5Fe0.5(Ta0.5Te0.5)O6、Pb2MgSrTeO6、Pb2Mg(W0.9Te0.1)O6、Pb2Mg(W0.7Te0.3)O6、Pb2Mg(W0.5Te0.5)O6、Pb2Mg(W0.4Te0.6)O6、Pb2Mg(W0.4Te0.6)O6、PbMnTeO6、Pb(Mn0.5Te0.5)O3、Pb2MnTeO6、PbMn2Ni6Te3O18、Pb(Na0.4Te0.6)O3、Pb2(Na0.5Bi0.5)TeO6、Na0.5Pb2Fe0.5TeO6、Pb2(Na0.5La0.5)TeO6、Pb2Na0.5Sc0.5TeO6、Na0.5Pb2Yb0.5TeO6、Na0.5Pb2Y0.5TeO6、Pb4Te6Nb10O41、Pb3Ni4.5Te2.5O15、Pb2NiTeO6、PbSc0.5Ti0.25Te0.25O3、Pb2Sn1.5Te0.5O6.5、Pb2(Sn1.5Te0.5)O6.5、Pb2SrTeO6、Pb2ZnTeO6、Pb3Zn3TeAs2O14、Pb2(Zr1.5Te0.5)O6.5、PbTe5O11、Pb3(Te2O6)Cl2、Pb2ZnTeO6In at least one.
Glass dust of the present invention includes lead glass powder and lead-free glass powder: have lead glass powder to include Pb-Si-O, Pb-B-O and Pb-Te-O system；Lead-free glass powder include Bi-Si-O, Bi-B-O, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O and V-P-Ba-O system.This glass dust size is not particularly limited, and in a case study on implementation, it is smaller in size than 10 μm, and in another case study on implementation, it is smaller in size than 5 μm.
Pb-Si-O glass dust of the present invention is made up of one or more in the addition element oxides such as the oxide of plumbous, silicon and Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, B, Al, Sn, P, Bi, above oxide is mixed in proportion, heat to molten condition, then, the mixture of molten condition is quenched, grinds and obtain its glass dust.Described glass dust is noncrystal.In an exemplary embodiment, described Pb-Si-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry.
Pb-Te-O glass dust of the present invention is made up of one or more in plumbous, the oxide of tellurium and the oxide of addition element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, P, Bi etc., it is by the one in plumbous, the oxide of tellurium and the oxide of above addition element or two or more is mixed in proportion, heat to molten condition, then, the mixture of molten condition is quenched, grinds and obtain this glass dust.This glass dust is noncrystal.In an exemplary embodiment, described Pb-Te-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
Pb-B-O glass dust of the present invention is made up of one or more in plumbous, the oxide of boron and the oxide of addition element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, Al, Sn, P, Te, Bi etc., by the one in plumbous, the oxide of boron and the oxide of above addition element or two or more be mixed in proportion, heat to molten condition, then, the mixture of molten condition is quenched, grinds and obtain its glass dust.This glass dust is noncrystal.
In an exemplary embodiment, described Pb-B-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
Bi-Si-O glass dust of the present invention is made up of one or more in bismuth, the oxide of silicon and the oxide of Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, B, Al, Sn, P, Te etc., it is by the one in bismuth, the oxide of silicon and the oxide of above addition element or two or more is mixed in proportion, heat to molten condition, then, the mixture of molten condition is quenched, grinds and obtain its glass dust.This glass dust is noncrystal.
In an exemplary embodiment, this Bi-Si-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust can be 5/95～95/5.
Bi-B-O glass dust of the present invention is made up of one or more in bismuth, the oxide of boron and the oxide of addition element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, Al, Sn, P, Te etc., it is by the one in bismuth, the oxide of boron and the oxide of above addition element or two or more is mixed in proportion, heat to molten condition, then, the mixture of molten condition is quenched, grinds and obtain this glass dust.This glass dust is noncrystal.
In an exemplary embodiment, described Bi-B-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry.
Bi-Te-O glass dust of the present invention is made up of one or more in the oxide of bismuth and tellurium and the oxide of addition element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, P etc., it is by the one in bismuth, the oxide of tellurium and the oxide of above addition element or two or more is mixed in proportion, heat to molten condition, then, the mixture of molten condition being quenched, grinds and obtain its glass dust. described glass dust is noncrystal..In an exemplary embodiment, described Bi-Te-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
P-Zn-Na-O glass dust of the present invention is made up of one or more in phosphorus, zinc, the oxide of sodium and the oxide of addition element Li, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Si, Ag, B, Al, Sn, Te, Bi etc., it is by the one in phosphorus, zinc, the oxide of sodium and the oxide of above addition element or two or more is mixed in proportion, heat to molten condition, then, the mixture of molten condition being quenched, grinds and obtain its glass dust. described glass dust is noncrystal..In an exemplary embodiment, described P-Zn-Na-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
Na-Al-B-O glass dust of the present invention is made up of one or more in sodium sodium, aluminum, the oxide of boron and the oxide of addition element Li, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, Sn, P, Bi, Te etc., it is by the one in sodium, aluminum, the oxide of boron and the oxide of above addition element or two or more is mixed in proportion, heat to molten condition, then, the mixture of molten condition is quenched, grinds and obtain its glass dust.Described glass dust is noncrystal.In an exemplary embodiment, described P-Zn-Na-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
B-Zn-Ba-O glass dust of the present invention is made up of one or more in boron, zinc, the oxide of barium and the oxide of addition element Li, Na, K, Mg, Ca, Sr, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Si, Ag, Al, Sn, P, Bi, Te etc., it is by the one in boron, zinc, the oxide of barium and the oxide of above addition element or two or more is mixed in proportion, heat to molten condition, then, the mixture of molten condition is quenched, grinds and obtain its glass dust.Described glass dust is noncrystal.In an exemplary embodiment, described B-Zn-Ba-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
V-P-Ba-O glass dust of the present invention is made up of one or more in vanadium, phosphorus, the oxide of barium and the oxide of addition element Li, Na, K, Mg, Ca, Sr, Sc, Ti, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, Bi, Te etc., it is by the one in vanadium, phosphorus, the oxide of barium and the oxide of above addition element or two or more is mixed in proportion, heat to molten condition, then, the mixture of molten condition is quenched, grinds and obtain its glass dust.Described glass dust is noncrystal.In an exemplary embodiment, described V-P-Ba-O glass dust is 0.5～10% with corrosion etching agent weight ratio in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
III. metal powder
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains metal powder.In a case study on implementation, described metal powder is the metal powder of non-silver cladding, including at least one in silver, gold, platinum, copper, ferrum, nickel, zinc, titanium, cobalt, chromium, manganese, palladium, rhodium.
In another one case study on implementation, described metal powder is at least one in the copper of silver cladding, ferrum, nickel, aluminum, zinc, titanium, cobalt, chromium, manganese, and wherein the thickness of silver coating is 10～2000nm, and the metal powder of this silver cladding is of a size of 0.1-5.0 μm.
In another one case study on implementation, described metal powder is the mixture of the metal powder that the metal powder that non-silver is coated with is coated with silver, and the part by weight of the metal powder of its non-silver cladding and the metal powder of silver-colored cladding is 95/5～5/95.Specifically, the effect in embodiments of the present invention of above-mentioned metal powder is the composition constituting electrode, plays electric action.In a preferred embodiment, this metal powder fusing point is preferably 350 DEG C～2000 DEG C, more preferably 450 DEG C～1800 DEG C, more preferably 600 DEG C～1450 DEG C.Inventor finds under study for action, if the fusing point of this metal powder is lower than 350 DEG C, in sintering; metallic particles meeting premature melt, can hinder the discharge to organic carrier, thus the discharge of organic carrier can be have impact on; and obvious flowing can be produced in sintering process, reduce the depth-width ratio of grid line；If fusing point is higher than 2000 DEG C, being difficult to effective sintering in sintering process process, electric metal block space is more, causes that path resistance is big, performance degradation.
It is preferred that in embodiment, this metal powder at least one in silver, gold, platinum, palladium, rhodium, or doped with copper, ferrum, nickel, zinc, titanium, cobalt, chromium, at least one metal of manganese or its alloy in silver, gold, platinum, palladium or rhodium, such as copper-manganese, constantan, nichrome.
In further preferred embodiment, this metal powder is the metal powder of the silver-colored clad structure of any one in the copper of silver cladding, ferrum, nickel, aluminum, zinc, titanium, cobalt, chromium, manganese, that is to say that the outer surface continuous print of any one metallic particles in copper, ferrum, nickel, aluminum, zinc, titanium, cobalt, chromium, manganese is coated with one layer of silver metal.In the embodiment of the metal powder of this silver clad structure, the thickness of this silver coating is preferably 1～2000nm, more preferably 2～1000nm.Inventor finds under study for action, if Ag layer thickness is less than 1nm, Ag content is very few, and the contact resistance of electrode or leakage current can significantly increase；If Ag layer thickness is more than 104Nm, the particle diameter that can make conductive metal powder is excessive, owing to Ag is precious metal, then also results in metal dust high cost, thus increasing the cost of crystal silicon solar batteries.Certainly, the silver layer of the metal powder of this silver clad structure can substitute with other precious metals, such as gold, platinum etc..The metallic particles being coated with by silver yet alloy to be the metals such as copper, ferrum, nickel, aluminum, zinc, titanium, cobalt, chromium, manganese, such as copper-manganese, constantan, nichrome.The metal powder of silver cladding realizes by plating one layer of silver on copper, ferrum, nickel, aluminum, zinc, titanium, cobalt, chromium, manganese metal powder.
In an exemplary case, by particle diameter 0.1～5.0 μm copper, ferrum, nickel, titanium, cobalt, chromium, zinc, manganese etc. or its alloy one or more metallic particles be placed in rare weak acid immersion 10～300s, remove out oxidation on metal surface layer, then, the method using chemical plating, plates the silver of about 10～2000nm on its metal powder.
In another exemplary case study on implementation, solution composition and the process conditions of chemical plating are as follows: AgNO3:2.4～14.2g/L, ammonia: 0.8g/L, formaldehyde: 1～3g/L, hydrazine hydrate: 1～4g/L, composite dispersing agent: 1.0g/L, pH value: 11, bath temperature: 60 DEG C, mixing speed: 1000r/min, dry: 50 DEG C, 30min.
In another exemplary case, by particle diameter 0.1～5.0 μm copper, ferrum, nickel, titanium, cobalt, chromium, zinc, manganese etc. or its alloy one or more metallic particles be placed in rare weak acid immersion 10～300s, remove out oxidation on metal surface layer.
Adopt deionized water repeatedly to wash, remove residual acid.Wet powder is dried in vacuum drying oven, then, the metallic particles of dry non-oxidation layer is placed in vacuum evaporation equipment, by being deposited with the metal powder obtaining silver cladding.
In the embodiment of above-mentioned each metal powder, first the size of this metal powder granule should can meet the requirement of printing, as blocked Printing screen etc..Therefore, preferably, this metal powder grain diameter is preferably distributed in 0.1～5.0 μm of μ m, if easily cause the blocking problem such as Printing screen and electrode broken string more than 5 μm μm, if less than 0.1 μm μm, the viscosity of slurry can be made to be greatly improved, to such an extent as to can not normally print.It addition, the metal powder granule of this preferable particle size can also effectively reduce area shared by electrode, thus improving the solaode conversion efficiency to light, can also effectively reduce the thick end of electrode simultaneously, saving materials, reduce production cost.
IV. organic carrier；
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains organic carrier, and described organic carrier includes organic solvent, polymer, wetting dispersing agent, thixotropic agent and other function additive etc..Described organic carrier weight ratio in electrode conductive paste is 5～25.Being divided into 100 listed as parts by weight with described organic carrier assembly, wherein organic solvent accounts for 50～95 weight portions；Polymer accounts for 1～40 weight portion；Wetting dispersing agent accounts for 0.1～10 weight portion；Thixotropic agent and other function additive account for 1～20 weight portion.
In an exemplary case study on implementation, this organic solvent is selected from alcohol (such as terpineol, fourth card), alcohol ester (such as lauryl alcohol ester), at least one in the solvent of high boiling range in terpenes etc., its polymer is selected from least one in ethyl cellulose, polymethacrylates, alkyd resin etc.；Wetting dispersing agent is adapted to assist in inorganic particle dispersion in organic carrier, without particular/special requirement；Thixotropic agent, for increasing slurry thixotropy in printing process, to ensure electrode pattern clarity and good depth-width ratio, can be selected for the organic thixotropic agents such as castor oil hydrogenated derivant or polyamide wax；Other function additives can select to add as required, as added microwax etc. to reduce surface tension, adds the pliability to improve slurry such as DBP, and addition PVB etc. improves adhesive force.
V. electrocondution slurry preparation method
The invention provides a kind of technique simple, condition is easily-controllable, the crystal silicon solar batteries front electrode electrocondution slurry preparation method that production cost is low, comprises the steps:
Prepare described corrosion etching agent；Weighing the plumbous and oxide of tellurium and the oxide of relevant addition element and prepare corrosion etching agent, the method for preparation corrosion etching agent is as described above.
Prepare described glass dust；Weigh relevant oxide and prepare glass dust, preparing the method for glass dust as described above.
Prepare described organic carrier；Weigh relevant organic material and prepare organic carrier, preparing the method for organic carrier as described above.The formula of crystal silicon solar batteries front electrode electrocondution slurry described in claim 1 weighs described corrosion etching agent, glass dust, metal powder and organic carrier；
Described corrosion etching agent, glass dust, metal powder and organic carrier are mixed, grinds, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
First, weigh metal powder, including metal powder and the silver-colored metal powder being coated with of non-silver cladding, secondly, weigh oxide and prepare glass dust, above-described corrosion etching agent, glass dust and metal powder are pre-mixed.Then, weigh Organic substance and prepare organic carrier.Finally, then the corrosion etching agent, glass dust and the metal powder that are pre-mixed being mixed with organic carrier, milled processed obtains electrode conductive paste.
Below, we are further discussed below case prepared by several electrode conductive paste.
In one embodiment, first the corrosion etching agent, glass dust and the metal powder that weigh being pre-mixed, then be mixed thing and mix with the organic carrier weighed, then, milled processed obtains described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, first the corrosion etching agent, glass dust and the organic carrier that weigh being pre-mixed, then add the metal powder weighed in the mixture, mix further, then, milled processed obtains described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, first the metal powder weighed and organic carrier being pre-mixed, then addition corrosion etching agent, glass dust mix further in the mixture, then, milled processed obtains described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, first the metal powder weighed and part organic carrier are pre-mixed, then corrosion etching agent, glass dust and part organic carrier are pre-mixed, then, be pre-mixed thing mixing again by two kinds, milled processed obtains described crystal silicon solar batteries front electrode electrocondution slurry.
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention, containing corrosion etching agent and glass dust.Its corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 0.5～10%, and the part by weight of its corrosion etching agent and glass dust can be 5/95～95/5.Corrosion etching agent of the present invention is at least one crystalline compounds formed with oxygen in plumbous, tellurium and/or addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium, and its melting temperature is 250 DEG C～760 DEG C.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Corrosion etching agent of the present invention includes following plumbous tellurium system crystalline compounds PbTe4O9、PbTeO3、PbTeO4、PbTe3O7、PbTe5O11、Pb2TeO4、Pb2Te3O7、Pb2Te3O8、Pb3TeO5、Pb3TeO6、Pb4Te1.5O7、Pb5TeO7、Pb5TeO7、PbTe2O5、Li2TeO3、Bi6B10O24、Na2B8O13、Bi4TeO8、Pb6Bi4O18、PbBi6Te10、Bi2TeO5、PbBi6TeO12、BiTe0.5Pb0.5SrNb2O9、Pb0.25SrBi1.5Te0.25Nb2O9、Pb3Te2Br2O6、Pb3TeBr2O4、Pb2CaTeO6、Pb2TeCoO6、PbTe2CuO6、PbTeCu3O7、Pb3Te2Fe2O12、Pb(Te0.33Fe0.67)O3、Pb2(Hf1.5Te0.5)O6.5、Pb2Te(Li0.5Al0.5)O6、Pb2Te(Li0.5Bi0.5)O6、Pb2TeLi0.5Fe0.5O6、PbTeLiFeO6、Pb2Te(Li0.5La0.5)O6、Pb2(Ti1.5Te0.5)O6.5、Pb2(Ti1.5Te0.5)O6.5、Pb2(Li0.5Sc0.5)TeO6、Pb2Li0.5Y0.5TeO6、Li0.5Pb2Yb0.5TeO6、Pb2MgTeO6、Pb11Si3O17、Ba(Fe0.5Mg0.5)PbTa0.5Te0.5O6、PbBaMgTeO6、Pb0.5BaNbTe2O9、BaTeO5、BaTe4O9、Pb2MgTeO6、Pb2Mg0.5Fe0.5(Ta0.5Te0.5)O6、Pb2MgSrTeO6、Pb2Mg(W0.9Te0.1)O6、Pb2Mg(W0.7Te0.3)O6、Pb2Mg(W0.5Te0.5)O6、Pb2Mg(W0.4Te0.6)O6、Pb2Mg(W0.4Te0.6)O6、PbMnTeO6、Pb(Mn0.5Te0.5)O3、Pb2MnTeO6、PbMn2Ni6Te3O18、Pb(Na0.4Te0.6)O3、Pb2(Na0.5Bi0.5)TeO6、Na0.5Pb2Fe0.5TeO6、Pb2(Na0.5La0.5)TeO6、Pb2Na0.5Sc0.5TeO6、Na0.5Pb2Yb0.5TeO6、Na0.5Pb2Y0.5TeO6、Pb4Te6Nb10O41、Pb3Ni4.5Te2.5O15、Pb2NiTeO6、PbSc0.5Ti0.25Te0.25O3、Pb2Sn1.5Te0.5O6.5、Pb2(Sn1.5Te0.5)O6.5、Pb2SrTeO6、Pb2ZnTeO6、Pb3Zn3TeAs2O14、Pb2(Zr1.5Te0.5)O6.5、PbTe5O11、Pb3(Te2O6)Cl2、Pb2ZnTeO6In at least one., its melting temperature is 250 DEG C～760 DEG C.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.
Glass dust of the present invention includes lead glass powder and lead-free glass powder.Lead glass powder is had to include Pb-Si-O, Pb-B-O and Pb-Te-O；Lead-free glass powder include Bi-Si-OBi-B-O, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O and V-P-Ba-O.
In a case study on implementation, metal powder of the present invention is the metal powder of non-silver cladding, including the alloy of at least one metal in silver, gold, platinum, copper, ferrum, nickel, zinc, titanium, cobalt, chromium, manganese, palladium, rhodium or described metal.
In another one case study on implementation, metal powder of the present invention is any one in the copper of silver cladding, ferrum, nickel, aluminum, zinc, titanium, cobalt, chromium, manganese or its two or more mixture, and wherein, the thickness of described silver coating is 2～2000nm.The metal powder of described silver cladding is of a size of 0.1～5.0 μm.
In another one case study on implementation, metal powder of the present invention is the mixture of the metal powder that the metal powder that non-silver is coated with is coated with silver, and the part by weight of the metal powder of its non-silver cladding and the metal powder of silver-colored cladding is 95/5～5/95.
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains glass dust and corrosion etching agent, in use, when temperature reaches the fusing point of corrosion etching agent, corrosion etching agent is converted into liquid by solid, antireflection layer surface can be deposited on rapidly, fully react with it in the short period of time, the blockage problem of glass dust softening state can be solved by the sharp transition of its physical aspect generation solid-state Yu liquid, glass dust is then in soft state, and the discharge for organic carrier provides space.This mushy stage coordinates, it is not only able to effectively corrode and penetrate the antireflective insulating barrier in crystal silicon solar energy battery front, and organic carrier can be made to be easily drained, it also is able to effective moistening conductive metal powder simultaneously, urge into the combination between metal powder, make conductive metal powder and crystal silicon solar energy battery form good Ohmic contact, form the crystal silicon solar batteries front electrode that electric conductivity is excellent, make it finer and close, improve weld strength and bulk conductivity.
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with exemplary case study on implementation, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, be not intended to limit the present invention.
In an exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Pb-Si-Al-B-O system glass dust and corrosion etching agent.Its described corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 2wt%, and the part by weight of its described corrosion etching agent and glass dust can be 3: 7.Corrosion etching agent of the present invention is one or more by a kind of of plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium etc. or the two or more crystalline compounds formed with oxygen, and its melting temperature is between 250 DEG C and 760 DEG C.Described corrosion etching agent is crystalline compounds, and its performance and preparation method are as described above.Described Pb-Si-Al-B-O system glass dust includes lower weight percent composition:
PbO65～85%
SiO210～20%
Al2O30.1～10%
B2O30.1～10%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metal such as Li, Na, K, Mg, Ca, Sr, Ba, Ti, Zr, Sc, Zn, Bi maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Bi-Si-B-Zn-O system glass dust and corrosion etching agent.Its described corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 5wt%, its described corrosion etching agent and the part by weight of glass dust can be 3:7. corrosion etching agent of the present invention is that one or more are by plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more crystalline compounds formed with oxygen of germanium etc., its melting temperature is between 250 DEG C and 760 DEG C.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Described Bi-Si-B-Zn-O system glass dust includes lower weight percent composition:
Bi2O365～85%
SiO210～20%
B2O30.1～10%
ZnO0.1～10%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of any one metal such as Li, Na, K, Mg, Ca, Sr, Ba, Ti, Al, Zr, Sc, W, Co, Cu, Fe, Ni, Sn, Mn, Ag maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Zn-B-P-Na-O system glass dust and corrosion etching agent.Its described corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 8wt%, its described corrosion etching agent and the part by weight of glass dust can be 3:7. corrosion etching agent of the present invention is that one or more are by plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more crystalline compounds formed with oxygen of germanium etc., its melting temperature is between 250 DEG C and 760 DEG C.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Described Zn-B-P-Na-O system glass dust includes lower weight percent composition:
B2O30.1～10%
ZnO30～50%
P2O530～50%
Na2O0.1～10%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metal such as Li, K, Mg, Ca, Sr, Ba, Ti, Al, Zr, Sc, Ni, Co, Cu, Fe, Sn, Mn, Ag, Bi, Ga maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Ba-B-Zn-O system glass dust and corrosion etching agent.Its corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 1.5wt%, its corrosion etching agent and the part by weight of glass dust can be 9:1. corrosion etching agent of the present invention is that one or more are by plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more crystalline compounds formed with oxygen of germanium etc., its melting temperature is between 250 DEG C and 760 DEG C.Described corrosion etching agent is crystalline compounds, and its performance and preparation method are as described above.Described Ba-B-Zn-O system glass dust includes lower weight percent composition:
BaO10～35%
B2O330～60%
ZnO25～35%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metal such as Li, Na, K, Mg, Ca, Sr, Ba, Ti, Zr, Sc, Zn, Co, Cu, Fe, Sn, Mn, Ag maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Pb-Te-Li-O system glass dust and corrosion etching agent.Its corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 3wt%, and the part by weight of its corrosion etching agent and glass dust can be 5:5.Corrosion etching agent of the present invention is one or more by a kind of of plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium etc. or the two or more crystalline compounds formed with oxygen, and its melting temperature is between 250 DEG C and 760 DEG C.Described corrosion etching agent is crystalline compounds, and its performance and preparation method are as described above.Described Pb-Te-Li-O system glass dust includes lower weight percent composition:
PbO20～50%
TeO240～70%
Li2O0.1～10%
Other oxides 3～15%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metal such as Na, K, Mg, Ca, Sr, Ba, Ti, Si, B, Al, Zr, Sc, Zn, Co, Cu, Fe, Sn, Mn, Ag maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Na-Al-B-O system glass dust and corrosion etching agent.Its corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 10wt%, its corrosion etching agent and the part by weight of glass dust can be 9:1. corrosion etching agent of the present invention is that one or more are by plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more crystalline compounds formed with oxygen of germanium etc., its melting temperature is between 250 DEG C and 760 DEG C.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Described Na-Al-B-O system glass dust includes lower weight percent composition:
Na2O5～20%
Al2O35～40%
B2O335～75%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metal such as Li, K, Mg, Ca, Zn, Sr, Ba, Ti, Zr, Sc, Si, Ni, Co, Cu, Fe, Sn, Mn, Ag maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Sb-V-Ba-P-O system glass dust and corrosion etching agent.Its corrosion etching agent and glass dust total amount weight ratio in electrode conductive paste are 5wt%, the part by weight of its corrosion etching agent and glass dust can be 8wt% for its described corrosion etching agent of 8:2. and glass dust total amount weight ratio in electrode conductive paste, its described corrosion etching agent can be 3 with the part by weight of glass dust: 7. corrosion etching agent of the present invention is that one or more are by plumbous and tellurium and addition element lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more crystalline compounds formed with oxygen of germanium etc., its melting temperature is between 250 DEG C and 760 DEG C.Described corrosion etching agent is crystalline compounds, and its performance and preparation method are as described above.Described Sb-V-Ba-P-O system glass dust includes lower weight percent composition:
V2O545～60%
Sb2O35～25%
BaO5～25%
P2O515～30%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metal such as Li, Na, K, Mg, Ca, Si, Zn, Sr, Ti, Zr, Sc, Cr, Co, Cu, Fe, Sn, Mn, Ag maybe can be decomposed into its oxide.
Embodiment 1
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to gross weight, and it includes 3 parts of corrosion etching agent, 85 parts of metal powders, 2 parts of glass dust, 10 parts of organic carriers.Wherein, corrosion etching agent is Li2TeO3And Bi6B10O24The mixture of crystalline compounds;Metal powder is argentum powder;Glass dust is Pb-Si-Al-B-O system glass dust.Organic carrier is 100 parts of calculating according to gross weight, it include terpineol organic solvent be 70 parts, ECN7NF 14 parts, wetting dispersing agent 10 parts, thixotropic agent 5.5 parts, microwax 0.5 part.
The preparation process of corrosion etching agent is: first by 12gTeO2And 8gPb3O4Oxide powder mixes, and then, is sequentially added into 0.625gB2O3、1.25gBi2O3And 1.25gLi2CO3Oxide powder, further Homogeneous phase mixing, be subsequently placed in crucible, put into heating furnace, be warming up to 900 DEG C, in the air atmosphere at 900 DEG C, it is made to react 60min in the molten state, then melted mixture is taken out from stove, be placed under atmospheric environment natural cooling, form block, the block obtained is carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, and the powder body of ball milling is in 0.1～7 μ m, obtains its crystalline compounds.
Metal powder is argentum powder, its particle size D50It it is 1～3 μm；Glass dust is Pb-Si-Al-B-O, and its percentage by weight consists of: PbO79wt%, SiO217wt%、Al2O33wt%、B2O31wt%, is mixed above-mentioned each component by mixer, heats after loading container in Muffle furnace, and peak temperature is 1000 DEG C, is incubated 60min at peak value so as to melt become uniform liquid completely.Molten mass is poured into water-cooled quench prepared glass, then through ball milling or after grinding diameter of particle less than 5 μm.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are weighed according to above-mentioned formula, corrosion etching agent, glass dust are mixed homogeneously with organic carrier, add metal powder mix homogeneously, it is ground to particle diameter less than 5 μm finally by three-roll grinder, obtains crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 2
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to gross weight, it corrosion etching agent including 4 parts, the metal powder of 83 parts, the glass dust of 1.6 parts, organic carrier of 11.4 parts.Wherein, corrosion etching agent is Bi4TeO8, Bi2TeO5, PbTeO3The mixture of crystalline compounds, metal powder is silver coated nickel powder；Glass dust is Bi-Si-B-Zn-O system glass dust.Organic carrier is 100 parts of calculating according to gross weight, it include lauryl alcohol ester organic solvent be 50 parts, polymethacrylate polymer 40 parts, wetting dispersing agent 5 parts, thixotropic agent 4 parts, DBP1 part.
The preparation process of corrosion etching agent is: by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.25gBi2O3Further Homogeneous phase mixing, is subsequently placed in crucible, puts into heating furnace, it is warming up to 900 DEG C, in air atmosphere at 900 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment natural cooling, form block, the block obtained is carried out pulverizing and obtains little granule, little granule is formed powder body again through ball milling, the powder body D of ball milling is in 0.1～7 μ m, obtains its crystalline compounds.
Metal powder is the method using chemical plating, plates the silver of about 200nm on nikel powder, and the particle size of nikel powder is 0.5～3 μm.The weight percent composition of glass dust is: Bi2O367wt%、SiO218wt%、B2O33wt%, ZnO7wt%, other oxides BaO3.5wt%, CuO1.5wt%, above-mentioned each component is mixed by knife-edge mixer, heating in Muffle furnace after loading container, peak temperature can set 1200 DEG C, is incubated 60min at peak value so as to melt become uniform liquid completely.Molten mass is poured into water-cooled quench prepared glass, then through ball milling or after grinding diameter of particle less than 5 μm.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are weighed according to above-mentioned formula, metal powder is mixed homogeneously with organic carrier, add corrosion etching agent and glass dust mix homogeneously, it is ground to particle diameter less than 5 μm finally by three-roll grinder, obtains crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 3
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to gross weight, it corrosion etching agent including 2 parts, the metal powder of 86 parts, the glass dust of 0.5 part, organic carrier of 11.5 parts.Wherein, corrosion etching agent is Bi24B2O39、Pb5B2O5, Pb5TeO7And Li6TeO6The mixture of crystalline compounds, metal powder is silver copper-clad；Glass dust is Zn-B-P-Li-O system glass dust.Organic carrier is 100 parts of calculating according to gross weight, it include terpineol organic solvent be 65 parts, alkyd polymer 20 parts, wetting dispersing agent 0.1 part, thixotropic agent 12.5 parts, PVB2.4 part.
The preparation process of corrosion etching agent is: by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, is sequentially added into 0.05gB2O3, 1.44gBi2O3, and 1.25gLi2CO3, further Homogeneous phase mixing, it is subsequently placed in crucible, put into heating furnace, be warming up to 900 DEG C, in the air atmosphere at 900 DEG C, it is made to react 60min in the molten state, then melted mixture is taken out from stove, be placed under atmospheric environment natural cooling, form block, the block obtained is carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, and the powder body of ball milling, in 0.1～7 μ m, obtains its crystalline compounds.
Metal powder is at silver-coated copper powder, the method using chemical plating, plates the silver of about 200nm on copper powder, and the particle size of copper powder is 0.5～3 μm μm.The percentage by weight of glass dust is: B2O336%、ZnO2%、P2O536%、Li2O1%、MgO4%、MnO21%, each component in described glass dust is mixed by gravity mixer, heats in Muffle furnace after loading container, peak temperature can set 1200 DEG C, is incubated 60min at peak value so as to melt become uniform liquid completely.Molten mass is poured into corrosion resistant plate and prepares glass, obtain diameter of particle less than 5 μm then through after ball milling or grinding.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are weighed according to above-mentioned formula, metal powder, glass dust are mixed homogeneously with corrosion etching agent, add organic carrier mix homogeneously, it is ground to particle diameter less than 5 μm finally by three-roll grinder, obtains crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 4
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to gross weight, it corrosion etching agent including 0.5 part, the metal powder of 88.5 parts, the glass dust of 1 part, organic carrier of 10 parts.Wherein, corrosion etching agent is PbTeO3, Li2TeO3, and Al2O3Crystalline compounds mixture, metal powder is titanium valve；Glass dust is B-Zn-Ba-O system glass dust.Organic carrier is 100 parts of calculating according to gross weight, it include fourth card organic solvent be 60 parts, ECN7NF 15 parts, wetting dispersing agent 5 parts, thixotropic agent 15 parts, PVB5 part.
The preparation process of corrosion etching agent is: by 14gTeO2And 8.75gPb3O4Oxide powder mixes, and then, is sequentially added into 0.75gAl2O3And 1.5gLi2CO3, further Homogeneous phase mixing, it is subsequently placed in crucible, put into heating furnace, be warming up to 900 DEG C, in the air atmosphere at 900 DEG C, it is made to react 60min in the molten state, then melted mixture is taken out from stove, be placed under atmospheric environment natural cooling, form block, the block obtained is carried out pulverizing and obtains little granule, again through ball milling, little granule is formed powder body, and the powder body of ball milling, in 0.1～7 μ m, obtains its crystalline compounds.
Metal powder is titanium valve, and its granules Particle Size is 0.5～10 μm；The percentage by weight of glass dust consists of: B2O355%、ZnO30%、BaO12%、Li2O3%, is mixed each component in described glass dust by gravity mixer, heats after loading container in Muffle furnace, and peak temperature can set 1200 DEG C, is incubated 60min at peak value so as to melt become uniform liquid completely.Molten mass is poured into corrosion resistant plate and prepares glass, obtain diameter of particle less than 5 μm then through after ball milling or grinding.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are weighed according to above-mentioned formula, metal powder, glass dust, corrosion etching agent are added mix homogeneously in organic carrier, it is ground to particle diameter less than 5 μm again through three-roll grinder, obtains crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 5
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to gross weight, it corrosion etching agent including 1.5 parts, the metal powder of 90 parts, the glass dust of 0.5 part, organic carrier of 8 parts.Wherein, corrosion etching agent is PbTeO3And Pb11Si3O17Compound, metal powder is argentum powder；Glass dust is Sb-V-Ba-P-O system glass dust.Organic carrier is 100 parts of calculating according to gross weight, it include lauryl alcohol ester organic solvent be 95 parts, ECN7NF 1 part, wetting dispersing agent 3 parts, thixotropic agent 1 part.
The preparation process of corrosion etching agent is: by 3.5gTeO2And 6.6gPb3O4Oxide powder mixes, and then, adds 0.45gSiO2Further Homogeneous phase mixing, is subsequently placed in crucible, puts into heating furnace, it is warming up to 900 DEG C, in air atmosphere at 900 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment natural cooling, form block, the block obtained is carried out pulverizing and obtains little granule, little granule is formed powder body again through ball milling, the powder body of ball milling, in 0.1～7 μ m, obtains its crystalline compounds.
The weight percent composition of glass dust is: Sb2O35%、V2O545%、BaO20%、P2O530%.Each component in described glass dust being mixed by gravity mixer, heat after loading container in Muffle furnace, peak temperature can set 1000 DEG C, is incubated 60min at peak value so as to melt become uniform liquid completely.Molten mass is poured into corrosion resistant plate and prepares glass, obtain diameter of particle less than 5 μm then through after ball milling or grinding.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are weighed according to above-mentioned formula, metal powder, glass dust, corrosion etching agent are added mix homogeneously in organic carrier, it is ground to particle diameter less than 5 μm again through three-roll grinder, obtains crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 6
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to gross weight, it corrosion etching agent including 2 parts, the metal powder of 87.5 parts, the glass dust of 0.5 part, organic carrier of 10 parts.Wherein, corrosion etching agent is Bi4TeO8And PbTeO3Compound, metal powder is argentum powder；Glass dust is Pb-Te-Li-O system glass dust.Organic carrier is 100 parts of calculating according to gross weight, it include lauryl alcohol ester organic solvent be 70 parts, ECN7NF 15 parts, wetting dispersing agent 2 parts, thixotropic agent 10 parts, PVB3 part.
The preparation process of corrosion etching agent is: by 4.9gTeO2And 7.56gPb3O4Oxide powder mixes, and then, adds 1.44gBi2O3Further Homogeneous phase mixing, is subsequently placed in crucible, puts into heating furnace, it is warming up to 900 DEG C, in air atmosphere at 900 DEG C, make it react 60min in the molten state, then melted mixture is taken out from stove, it is placed under atmospheric environment natural cooling, form block, the block obtained is carried out pulverizing and obtains little granule, little granule is formed powder body again through ball milling, the powder body of ball milling, in 0.1～7 μ m, obtains its crystalline compounds.
The weight percent composition of glass dust is: PbO38%, TeO258%、Li2CO31.5% and B2O3Each component in above-mentioned glass dust is mixed by 2.5% by gravity mixer, heats after loading container in Muffle furnace, and peak temperature can set 900 DEG C, is incubated 60min at peak value so as to melt become uniform liquid completely.Molten mass is poured into corrosion resistant plate and prepares glass, obtain diameter of particle less than 5 μm then through after ball milling or grinding.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are weighed according to above-mentioned formula, metal powder, glass dust, corrosion etching agent are added mix homogeneously in organic carrier, it is ground to particle diameter less than 5 μm again through three-roll grinder, obtains crystal silicon solar batteries front electrode electrocondution slurry.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (20)
1. a crystal silicon solar batteries front electrode electrocondution slurry, is 100 parts of calculating according to gross weight, is made up of the component of following formula proportion:
Corrosion etching agent and 0.5～10 part of glass dust,
Wherein, described corrosion etching agent is crystalline compounds；Described crystalline compounds is two kinds in addition element and lead or two or more oxides；Or two kinds or two or more oxides in addition element and tellurium；Or addition element and three kinds and above oxide in lead, tellurium；The melting temperature of described crystalline compounds is 250 DEG C～760 DEG C；Described glass dust is amorphization compound；
Metal powder 70～93 parts；
Organic carrier 5～25 parts.
2. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterised in that the weight ratio of described corrosion etching agent and glass dust is 5/95～95/5.
3. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterized in that, described addition element is at least one in lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, bromine, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium.
4. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterised in that described crystalline compounds is Li2TeO3、Bi4TeO8、Pb6Bi4O18、Bi2TeO5、PbBi6TeO12、BiTe0.5Pb0.5SrNb2O9、Pb0.25SrBi1.5Te0.25Nb2O9、Pb3Te2Br2O6、Pb3TeBr2O4、Pb2CaTeO6、Pb2TeCoO6、PbTe2CuO6、PbTeCu3O7、Pb3Te2Fe2O12、Pb(Te0.33Fe0.67)O3、Pb2(Hf1.5Te0.5)O6.5、Pb2Te(Li0.5Al0.5)O6、Pb2Te(Li0.5Bi0.5)O6、Pb2TeLi0.5Fe0.5O6、PbTeLiFeO6、Pb2Te(Li0.5La0.5)O6、Pb2(Ti1.5Te0.5)O6.5、Pb2(Li0.5Sc0.5)TeO6、Pb2Li0.5Y0.5TeO6、Li0.5Pb2Yb0.5TeO6、Pb2MgTeO6、Pb11Si3O17、Ba(Fe0.5Mg0.5)PbTa0.5Te0.5O6、PbBaMgTeO6、Pb0.5BaNbTe2O9、BaTeO5、BaTe4O9、Pb2Mg0.5Fe0.5(Ta0.5Te0.5)O6、Pb2MgSrTeO6、Pb2Mg(W0.9Te0.1)O6、Pb2Mg(W0.7Te0.3)O6、Pb2Mg(W0.5Te0.5)O6、Pb2Mg(W0.4Te0.6)O6、PbMnTeO6、Pb(Mn0.5Te0.5)O3、Pb2MnTeO6、PbMn2Ni6Te3O18、Pb(Na0.4Te0.6)O3、Pb2(Na0.5Bi0.5)TeO6、Na0.5Pb2Fe0.5TeO6、Pb2(Na0.5La0.5)TeO6、Pb2Na0.5Sc0.5TeO6、Na0.5Pb2Yb0.5TeO6、Na0.5Pb2Y0.5TeO6、Pb4Te6Nb10O41、Pb3Ni4.5Te2.5O15、Pb2NiTeO6、PbSc0.5Ti0.25Te0.25O3、Pb2Sn1.5Te0.5O6.5、Pb2(Sn1.5Te0.5)O6.5、Pb2SrTeO6、Pb2ZnTeO6、Pb3Zn3TeAs2O14、Pb2(Zr1.5Te0.5)O6.5、Pb3(Te2O6)Cl2、Pb2ZnTeO6In at least one.
5. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterized in that, described glass dust is at least one in Pb-Si-O, Bi-Si-O, Pb-B-O, Bi-B-O, Pb-Te-O, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O, V-P-Ba-O system glass dust, wherein, described glass dust contains at least one in the oxide of Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, P or Bi.
6. according to the arbitrary described crystal silicon solar batteries front electrode electrocondution slurry of Claims 1 to 5, it is characterised in that described corrosion etching agent be spherical, class is spherical, at least one in lamellar, graininess, colloid particle, is of a size of 0.1～10.0 μm.
7. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterised in that: described metal powder is at least one in silver, gold, platinum, copper, ferrum, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium, rhodium.
8. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterized in that: described metal powder is at least one in the copper of silver cladding, ferrum, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, wherein, the thickness of silver coating is 10～2000nm.
9. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterized in that: described metal powder is the metal powder mixture with the metal powder of silver cladding of non-silver cladding, wherein, the weight ratio of the metal powder that the metal powder of described non-silver cladding is coated with silver is 5/95～95/5, the metal powder of non-silver cladding is silver, gold, platinum, copper, ferrum, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium, at least one in rhodium, the metal powder of silver cladding is copper, ferrum, nickel, zinc, titanium, cobalt, chromium, aluminum, at least one in manganese, the thickness of described silver coating is 10～2000nm.
10. a preparation method for crystal silicon solar batteries front electrode electrocondution slurry, comprises the steps:
Prepare described corrosion etching agent；
Prepare described glass dust；
Prepare described organic carrier；
The formula of crystal silicon solar batteries front electrode electrocondution slurry described in claim 1 weighs described corrosion etching agent, glass dust, metal powder and organic carrier；
Described corrosion etching agent, glass dust, metal powder and organic carrier are mixed, grinds, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
11. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterized in that, the preparation method of described corrosion etching agent is: by the telluric acid solution that 0.1～6mol/l temperature is 60-90 DEG C, tellurous acid solution, tellurate solution, the lead acetate solution mixing of tellurite solution and 0.1～10mol/l, making the tellurium in mixed solution is 0.1/10～10/0.1 with plumbous mol ratio, it is subsequently adding lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the saline solution of at least one addition element in germanium, stir 2～5 hours at 50 DEG C～250 DEG C, mixing speed is 1000～1500r/min, solid-liquid separation, washing, until filtrate PH is 5～7, collect solid, dry, pulverize, grind, obtain described corrosion etching agent crystalline compounds.
12. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterized in that, the preparation method of described corrosion etching agent is: by the plumbous steam with tellurium and/or lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, bromine, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, in germanium, the steam of at least one addition element imports in the reative cell containing oxygen atmosphere, react 1～4 hour at 1000～3000 DEG C, cooling, pulverize, grind, obtain described corrosion etching agent crystalline compounds.
13. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterized in that, the preparation method of described corrosion etching agent is: by the oxide of tellurium with plumbous oxide and/or lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, bromine, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the oxide mixing of at least one addition element in germanium, non-reducing atmosphere is heated to 700～1200 DEG C, frit reaction 30～120 minutes, natural cooling, pulverize, grind, obtain described corrosion etching agent crystalline compounds.
14. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterized in that, the preparation method of described corrosion etching agent is: by the oxide of tellurium and with plumbous oxide/or lithium, bismuth, boron, titanium, zinc, aluminum, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, ferrum, silicon, barium, magnesium, manganese, tungsten, nickel, stannum, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the oxide mixing of at least one addition element in germanium, the atmosphere of vacuum is heated to 700～1200 DEG C, frit reaction 30～120 minutes, natural cooling, pulverize, grind, obtain described corrosion etching agent crystalline compounds.
15. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterized in that, described glass dust is Pb-Si-O, Bi-Si-O, Pb-B-O, Bi-B-O, Pb-Te-O, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O, at least one in V-P-Ba-O system glass dust, wherein, described glass dust contains Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, at least one in the oxide of P or Bi, it is of a size of 0.1～10.0 μm.
16. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterized in that, described glass dust includes Pb-Te-O glass dust, and described Pb-Te-O glass dust is made up of at least one in plumbous, the oxide of tellurium and the oxide of addition element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, P or Bi；Described Pb-Te-O glass dust is at least one in plumbous, the oxide of tellurium and the oxide of above-mentioned addition element to be mixed in proportion, and the mixture of molten condition, to molten condition, is then quenched by heating, grinds and obtains described glass dust.
17. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterised in that: described metal powder is at least one in silver, gold, platinum, copper, ferrum, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium, rhodium.
18. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterized in that: described metal powder is at least one in the copper of silver cladding, ferrum, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, wherein, the thickness of silver coating is 10～2000nm.
19. the preparation method of crystal silicon solar batteries front electrode electrocondution slurry according to claim 10, it is characterized in that: described metal powder is the mixture of the metal powder that the metal powder that non-silver is coated with is coated with silver, the weight ratio of the metal powder of described non-silver cladding and the metal powder of silver-colored cladding is 5/95-95/5；Wherein, the metal powder of non-silver cladding is at least one in silver, gold, platinum, copper, ferrum, nickel, zinc, titanium, cobalt, chromium, manganese, palladium, rhodium, the metal powder of silver cladding is at least one in copper, ferrum, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, and the thickness of silver coating is 10～2000nm.
20. a manufacture method for crystal silicon solar batteries front electrode, comprise the steps:
Thering is provided the crystal silicon semiconductor element that a kind of upper face has dielectric film, wherein, described dielectric film is superimposed layer at least one in silicon nitride, titanium oxide, aluminium oxide, silicon oxide；
The electrocondution slurry that the preparation method of arbitrary to arbitrary for claim 1～9 described crystal silicon solar batteries front electrode electrocondution slurry or claim 10～18 described crystal silicon solar batteries front electrode electrocondution slurry obtains is printed on described dielectric film；
Sintering, the step of described sintering is: is dried at 180 DEG C～260 DEG C by the described electrocondution slurry being printed on dielectric film, is heated to 700 DEG C～950 DEG C sintering；
Cooling, obtains described crystal silicon solar batteries front electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495909.4A CN103545016B (en) | 2013-10-21 | 2013-10-21 | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495909.4A CN103545016B (en) | 2013-10-21 | 2013-10-21 | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103545016A CN103545016A (en) | 2014-01-29 |
| CN103545016B true CN103545016B (en) | 2016-06-29 |
Family
ID=49968393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310495909.4A Active CN103545016B (en) | 2013-10-21 | 2013-10-21 | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103545016B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150206992A1 (en) * | 2014-01-17 | 2015-07-23 | Heraeus Precious Metals North America Conshohocken Llc | Lead-tellurium inorganic reaction systems |
| JP5998178B2 (en) * | 2014-06-05 | 2016-09-28 | 株式会社ノリタケカンパニーリミテド | Photovoltaic surface electrode paste for solar cell, method for producing the same, and method for producing solar cell |
| CN105097071B (en) * | 2015-07-22 | 2017-01-25 | 深圳市春仰科技有限公司 | Positive conductive silver paste of silicon solar cell and preparation method of positive conductive silver paste |
| US20170144920A1 (en) * | 2015-11-20 | 2017-05-25 | Giga Solar Materials Corp. | Crystalline oxides, preparation thereof and conductive pastes containing the same |
| JP6236557B1 (en) * | 2016-03-18 | 2017-11-22 | Ｄｏｗａエレクトロニクス株式会社 | Silver tellurium-coated glass powder and method for producing the same, and conductive paste and method for producing the same |
| CN105810287A (en) * | 2016-03-22 | 2016-07-27 | 广西吉宽太阳能设备有限公司 | Paste for crystalline silicon solar cell |
| CN105655010A (en) * | 2016-03-22 | 2016-06-08 | 广西吉宽太阳能设备有限公司 | Mixed electrode slurry for crystalline silicon solar cells |
| CN105702384B (en) * | 2016-03-24 | 2017-09-19 | 广州市尤特新材料有限公司 | A kind of high heat generating pastes of slug type and preparation method thereof |
| CN105858623A (en) * | 2016-03-30 | 2016-08-17 | 苏州开元民生科技股份有限公司 | Preparation method for silver tellurite, crystalline solar cell positive pole silver paste and preparation method therefor |
| CN107673624A (en) * | 2017-09-20 | 2018-02-09 | 无锡帝科电子材料科技有限公司 | For preparing glass powder including its paste composition, the electrode of solar battery and solar cell of electrode of solar battery |
| CN110557965B (en) * | 2018-03-30 | 2021-04-27 | 深圳市首骋新材料科技有限公司 | Crystalline silicon solar cell front conductive paste and preparation method thereof and solar cell |
| WO2019183932A1 (en) * | 2018-03-30 | 2019-10-03 | 深圳市首骋新材料科技有限公司 | Front side conductive paste of crystalline silicon solar cell, preparation method therefor, and solar cell |
| CN110603606B (en) * | 2018-03-30 | 2021-06-08 | 深圳市首骋新材料科技有限公司 | Crystalline silicon solar cell front conductive paste and preparation method thereof and solar cell |
| CN110603605A (en) * | 2018-03-30 | 2019-12-20 | 深圳市首骋新材料科技有限公司 | Crystalline silicon solar cell front conductive paste and preparation method thereof and solar cell |
| CN110663087A (en) * | 2018-04-28 | 2020-01-07 | 深圳市首骋新材料科技有限公司 | Crystalline silicon solar cell front conductive silver paste and preparation method thereof and solar cell |
| CN109994248B (en) * | 2019-03-28 | 2020-05-22 | 宁波职业技术学院 | Conductive phase compound, thick-film resistor paste based on aluminum substrate and preparation method of thick-film resistor paste |
| CN111200041B (en) * | 2020-03-09 | 2022-07-22 | 北京大学深圳研究生院 | Etching method and application of silicon nitride in crystalline silicon solar cell |
| CN111599506B (en) * | 2020-04-08 | 2021-10-08 | 常州聚和新材料股份有限公司 | Solar cell conductive paste, glass material and solar cell |
| CN111524639B (en) * | 2020-06-02 | 2021-09-28 | 佛山市瑞纳新材科技有限公司 | Electrode silver paste, preparation method and N-type crystalline silicon solar cell |
| CN115732120B (en) * | 2022-11-28 | 2023-11-07 | 苏州三环科技有限公司 | Resistance paste and preparation method and application thereof |
| CN116313216B (en) * | 2022-12-28 | 2024-02-02 | 广州市儒兴科技股份有限公司 | Aluminum paste and solar cell |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590333A (en) * | 2003-09-04 | 2005-03-09 | 株式会社村田制作所 | Conductive paste and ceramic electronic component |
| CN1883012A (en) * | 2003-11-18 | 2006-12-20 | 默克专利有限公司 | Functional paste |
| CN102476919A (en) * | 2010-11-24 | 2012-05-30 | 比亚迪股份有限公司 | Glass powder and its preparation method and conductive paste for solar cell |
| CN102610297A (en) * | 2012-04-01 | 2012-07-25 | 昆明理工大学 | Silver coated copper conductor slurry for front electrode of solar battery and preparation method of silver coated copper conductor slurry |
| CN102603196A (en) * | 2012-02-13 | 2012-07-25 | 江苏瑞德新能源科技有限公司 | Glass mixing powder, preparation method thereof and conductive silver paste containing glass mixing powder |
| CN102881350A (en) * | 2012-09-25 | 2013-01-16 | 深圳首创光伏有限公司 | Positive electrode slurry of solar battery and glass powder |
| CN102947235A (en) * | 2010-05-04 | 2013-02-27 | E·I·内穆尔杜邦公司 | Thick-film pastes containing lead-tellurium-boron-oxides, and their use in the manufacture of semiconductor devices |
| CN103021511A (en) * | 2011-09-22 | 2013-04-03 | 比亚迪股份有限公司 | Front electrode silver paste of crystalline silicon solar battery and preparation method for front electrode silver paste |
| CN103226989A (en) * | 2012-01-30 | 2013-07-31 | 比亚迪股份有限公司 | Corrosive carrier, preparation method thereof, crystalline silicon solar battery front/back side silver conductive paste and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8916069B2 (en) * | 2011-08-18 | 2014-12-23 | E I Du Pont De Nemours And Company | Conductive compositions containing rhodium and Pb-Te-O and their use in the manufacture of semiconductor devices |
-
2013
- 2013-10-21 CN CN201310495909.4A patent/CN103545016B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590333A (en) * | 2003-09-04 | 2005-03-09 | 株式会社村田制作所 | Conductive paste and ceramic electronic component |
| CN1883012A (en) * | 2003-11-18 | 2006-12-20 | 默克专利有限公司 | Functional paste |
| CN102947235A (en) * | 2010-05-04 | 2013-02-27 | E·I·内穆尔杜邦公司 | Thick-film pastes containing lead-tellurium-boron-oxides, and their use in the manufacture of semiconductor devices |
| CN102958861A (en) * | 2010-05-04 | 2013-03-06 | E·I·内穆尔杜邦公司 | Thick-film pastes containing lead-tellurium-lithium-titanium-oxides, and their use in the manufacture of semiconductor devices |
| CN102971268A (en) * | 2010-05-04 | 2013-03-13 | E·I·内穆尔杜邦公司 | Thick-film pastes containing lead-tellurium-lithium-oxides, and their use in the manufacture of semiconductor devices |
| CN103038186A (en) * | 2010-05-04 | 2013-04-10 | E·I·内穆尔杜邦公司 | Thick-film pastes containing lead- and tellurium-oxides, and their use in the manufacture of semiconductor devices |
| CN102476919A (en) * | 2010-11-24 | 2012-05-30 | 比亚迪股份有限公司 | Glass powder and its preparation method and conductive paste for solar cell |
| CN103021511A (en) * | 2011-09-22 | 2013-04-03 | 比亚迪股份有限公司 | Front electrode silver paste of crystalline silicon solar battery and preparation method for front electrode silver paste |
| CN103226989A (en) * | 2012-01-30 | 2013-07-31 | 比亚迪股份有限公司 | Corrosive carrier, preparation method thereof, crystalline silicon solar battery front/back side silver conductive paste and preparation method thereof |
| CN102603196A (en) * | 2012-02-13 | 2012-07-25 | 江苏瑞德新能源科技有限公司 | Glass mixing powder, preparation method thereof and conductive silver paste containing glass mixing powder |
| CN102610297A (en) * | 2012-04-01 | 2012-07-25 | 昆明理工大学 | Silver coated copper conductor slurry for front electrode of solar battery and preparation method of silver coated copper conductor slurry |
| CN102881350A (en) * | 2012-09-25 | 2013-01-16 | 深圳首创光伏有限公司 | Positive electrode slurry of solar battery and glass powder |
Non-Patent Citations (1)
| Title |
|---|
| 太阳能电池正极用银浆的研究及进展;李纪等;《金属功能材料》;20121031;第19卷(第5期);46-50 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103545016A (en) | 2014-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103545016B (en) | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof | |
| CN103545015B (en) | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof | |
| CN103596648B (en) | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof | |
| US9508877B2 (en) | Method for manufacturing a front electrode of a semiconductor device | |
| CN103377751B (en) | Free conductive thick film paste for solar cell contact | |
| CN103377752B (en) | For the tellurium inorganic reaction system of the free conductive thick film paste of solar cell contact | |
| US8486308B2 (en) | Conductive paste composition containing lithium, and articles made therefrom | |
| TW201140914A (en) | Paste composition for electrode and photovoltaic cell | |
| US9087937B2 (en) | Glass composition and its use in conductive silver paste | |
| CN102354544A (en) | Silver conductive paste for front electrode of crystalline silicon solar cell and preparation method thereof | |
| TWI778207B (en) | Glass, glass powder, conductive paste and solar cells | |
| EP2652750A1 (en) | Conductive paste composition containing lithium, and articles made therefrom | |
| CN110603648A (en) | Crystalline silicon solar cell front conductive paste and preparation method thereof and solar cell | |
| CN104039728A (en) | Glass frit, and conductive paste composition and solar cell comprising the same | |
| TW201251066A (en) | Paste composition for electrode and photovoltaic cell | |
| CN109524150A (en) | A kind of full Al-BSF back silver paste and the preparation method and application thereof | |
| WO2013085961A1 (en) | Conductive silver paste for a metal-wrap-through silicon solar cell | |
| CN112041994A (en) | Crystalline silicon solar cell front conductive paste and preparation method thereof and solar cell | |
| CN104157331A (en) | Silicon solar cell electrode silver coated copper sizing agent and preparing method thereof | |
| US11634355B2 (en) | Ceramic glass powder and solar cell metallization paste containing ceramic glass powder | |
| TW201546825A (en) | Paste for solar cell light receiving surface electrodes, manufacturing method thereof, and solar cell unit | |
| WO2019183934A1 (en) | Front-side conductive paste of crystalline silicon solar cell, preparation method thereof, and solar cell | |
| JP2011077222A (en) | Solar battery cell, electronic component, and conductive paste | |
| WO2019183930A1 (en) | Crystalline silicon solar battery front conductive slurry and preparation method therefor and solar battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENZHEN SHOUCHENG NEW MATERIAL TECHNOLOGY CO., LT Free format text: FORMER OWNER: SOLTRIUM TECHNOLOGY LTD. SHENZHEN Effective date: 20141203 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20141203 Address after: 518000 Guangdong, Longhua, New District, Longhua street, Xiang Xiang, No. 1, science and Technology Park on the ground floor, block C, building 9, building 5 Applicant after: Shou Cheng new material Science and Technology Ltd. of Shenzhen Address before: 518000 Guangdong city of Shenzhen province Futian District 105 Meihua road from industrial park 13 1 floor Applicant before: Shenzhen Soltrium Photovoltaic Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Positive electrode electrocondution slurry of crystalline silicon solar cell and preparation method therefor Effective date of registration: 20180710 Granted publication date: 20160629 Pledgee: Shenzhen SME financing Company limited by guarantee Pledgor: Shou Cheng new material Science and Technology Ltd. of Shenzhen Registration number: 2018990000546 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20200610 Granted publication date: 20160629 Pledgee: Shenzhen SME financing Company limited by guarantee Pledgor: Soltrium Technology, Ltd. Registration number: 2018990000546 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof Effective date of registration: 20200610 Granted publication date: 20160629 Pledgee: Shenzhen SME financing Company limited by guarantee Pledgor: Soltrium Technology, Ltd. Registration number: Y2020990000599 |