TW202026262A - Glass frit, method for manufacturing glass frit, and aluminium paste - Google Patents
Glass frit, method for manufacturing glass frit, and aluminium paste Download PDFInfo
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- TW202026262A TW202026262A TW109105857A TW109105857A TW202026262A TW 202026262 A TW202026262 A TW 202026262A TW 109105857 A TW109105857 A TW 109105857A TW 109105857 A TW109105857 A TW 109105857A TW 202026262 A TW202026262 A TW 202026262A
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- 239000011521 glass Substances 0.000 title claims abstract description 153
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000004411 aluminium Substances 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000006060 molten glass Substances 0.000 claims abstract description 29
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 28
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052788 barium Inorganic materials 0.000 claims abstract description 26
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012634 fragment Substances 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 29
- 239000011575 calcium Substances 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- 229910052791 calcium Inorganic materials 0.000 claims description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 14
- PSGCRHLFZJRYEA-UHFFFAOYSA-N phosphorus p2o5 Chemical compound P.O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 PSGCRHLFZJRYEA-UHFFFAOYSA-N 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000001506 calcium phosphate Substances 0.000 claims description 7
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 5
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 5
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 21
- 239000000523 sample Substances 0.000 description 19
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 229960005069 calcium Drugs 0.000 description 13
- 238000010586 diagram Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000002411 adverse Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010902 jet-milling Methods 0.000 description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012768 molten material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000004017 vitrification Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229960001714 calcium phosphate Drugs 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-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
- 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 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
- H01B3/084—Glass or glass wool in binder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
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Abstract
Description
本發明係有關於一種在形成太陽能電池的背面等的鋁電極之鋁膏所使用的玻璃料、玻璃料製造方法及鋁膏。 The present invention relates to a glass frit used in an aluminum paste forming an aluminum electrode such as the back surface of a solar cell, a glass frit manufacturing method, and an aluminum paste.
以往,屬於能夠再生利用的能源之一之太陽能電池之開發係基於20世紀的主角之半導體技術而進行。其係支配人類生存之全球性水準的重要開發。其開發課題不僅是將太陽光轉換成為電能之效率,而且亦在面對減低製造成本及無公害之課題之下進行。致力於實現該等開發課題中,一般認為特別是減低或削除在電極所使用的銀(Ag)和鉛(Pb)之使用量為重要的。 In the past, the development of solar cells, one of the renewable energy sources, was based on the semiconductor technology of the protagonist of the 20th century. It is an important development that governs the global level of human existence. The subject of its development is not only the efficiency of converting sunlight into electrical energy, but also the subject of reducing manufacturing costs and being pollution-free. In efforts to achieve these development issues, it is generally believed that reducing or eliminating the use of silver (Ag) and lead (Pb) used in electrodes is particularly important.
例如將鋁膏塗佈、燒結在構成太陽能電池之矽基板(p型)的背面全面而形成鋁電極(p+),並將引線焊接在此。 For example, aluminum paste is applied and sintered on the entire back surface of the silicon substrate (p-type) constituting the solar cell to form an aluminum electrode (p+), and the lead wire is welded there.
但是將引線直接焊接鋁電極時,其拉伸強度較弱,故以往是在鋁電極挖掘複數個孔穴且將銀膏塗佈、燒結在此處,並將引線焊接在此。 However, when the lead wire is directly welded to the aluminum electrode, the tensile strength is weak. Therefore, in the past, multiple holes were excavated in the aluminum electrode, silver paste was applied and sintered there, and the lead wire was welded there.
將鋁膏塗佈、燒結在太陽能電池背面而形成之鋁電極,因為長期間被暴露在嚴酷的條件,在構成鋁膏等之玻璃料中存在鐵、銅、鎳、鉻等金屬時,該等金屬有產生低劣作用致使太陽能電池的性能劣化之可能性。 The aluminum electrode formed by coating and sintering aluminum paste on the back of the solar cell is exposed to severe conditions for a long period of time. When iron, copper, nickel, chromium and other metals are present in the glass frit constituting the aluminum paste, the Metal has the possibility of degrading the performance of solar cells.
因此,期望出現一種在構成鋁膏等之玻璃料中不含有該等鐵等造成不良影響之材料且在低溫會熔融之新穎玻璃料。 Therefore, it is desired to produce a novel glass frit that does not contain such iron and other materials that cause adverse effects in the glass frit constituting the aluminum paste and the like, and will melt at low temperatures.
本發明者等係使製造一種不含有鐵、銅、鎳、鉻等金屬,且在製造太陽能電池等所必要的低溫會熔融,且主成分只有釩及鋇之玻璃料成為可能。 The inventors of the present invention made it possible to produce a glass frit that does not contain metals such as iron, copper, nickel, chromium, and which melts at a low temperature necessary for the production of solar cells, and has only vanadium and barium as its main components.
因此,本發明係製造一種玻璃料,其係要混入至在基板塗佈、燒結而形成導電性電極之導電性膏者,該玻璃料為:以55至80莫耳%的釩V2O5及15至30莫耳%的鋇BaO作為主材料進行加熱而生成熔融玻璃,且將該熔融玻璃急速冷卻而形成的碎片進行粉碎而製造者,該玻璃料係在650℃以下會熔融。 Therefore, the present invention is to produce a glass frit which is mixed into a conductive paste that is coated and sintered on a substrate to form a conductive electrode. The glass frit is: 55 to 80 mole% of vanadium V 2 O 5 And 15 to 30 mol% of barium BaO is heated as the main material to produce molten glass, and the fragments formed by the rapid cooling of the molten glass are crushed and the glass frit is melted at 650°C or lower.
此時,係使其不含有鐵、銅、鎳、鉻。 At this time, it should not contain iron, copper, nickel, and chromium.
又,係將0至15莫耳%的鋁Al2O3、0至10莫耳%的硼B2O3及0至7莫耳%的矽SiO2之一種以上混入主材料作為添加物且加熱而生成熔融玻璃。 In addition, one or more of 0 to 15 mol% aluminum Al 2 O 3 , 0 to 10 mol% boron B 2 O 3 and 0 to 7 mol% silicon SiO 2 are mixed into the main material as additives and Heating produces molten glass.
而且,係使用鋁膏作為導電性膏。 Furthermore, aluminum paste is used as the conductive paste.
又,前述之在基板塗佈、燒結而形成導電性電極一事,係在太陽能電池的基板塗佈、燒結而形成導電性鋁電極。 In addition, the aforementioned coating and sintering on the substrate to form a conductive electrode is coating and sintering on the solar cell substrate to form a conductive aluminum electrode.
而且,本發明係製造一種玻璃料,其係要混入至在基板塗佈、燒結而形成導電性電極之導電性膏者,該玻璃料為:以10至55莫耳%的釩V2O5及10至40莫耳%的鋇BaO作為主材料進行加熱而生成熔融玻璃,且將該熔融玻璃急速冷卻而形成的碎片進行粉碎而製造者,該玻璃料係在650℃以下熔融。 Furthermore, the present invention is to produce a glass frit that is mixed into a conductive paste that is coated and sintered on a substrate to form a conductive electrode. The glass frit is: 10 to 55 mol% of vanadium V 2 O 5 And 10-40 mol% of barium BaO is heated as a main material to produce molten glass, and the fragments formed by rapid cooling of the molten glass are crushed to produce the glass frit at 650°C or lower.
又,係將1至10莫耳%的鋁Al2O3及1至20莫耳%的硼B2O3混入主材料作為添加物且加熱而生成前述熔融玻璃。 In addition, 1 to 10 mol% of aluminum Al 2 O 3 and 1 to 20 mol% of boron B 2 O 3 are mixed into the main material as additives and heated to produce the molten glass.
而且,係將5至20莫耳%的磷P2O5及5至20莫耳%的鈣CaO混入主材料作為添加物且加熱而生成前述熔融玻璃。 In addition, 5 to 20 mol% of phosphorus P 2 O 5 and 5 to 20 mol% of calcium CaO are mixed into the main material as additives and heated to produce the aforementioned molten glass.
又,與屬於添加物之磷P2O5一起添加之鈣CaO,係設成為與磷及鹼土金屬之1種或1種以上的化合物。 In addition, calcium CaO added together with phosphorus P 2 O 5 which is an additive is set as a compound with one or more of phosphorus and alkaline earth metals.
而且,與屬於添加物之磷P2O5一起添加之前述鈣CaO,係設成為屬於與磷及鹼土金屬之1種或1種以上的化合物之磷酸三鈣Ca3(PO4)2或偏磷酸鈣Ca(PO3)2。 Furthermore, the aforementioned calcium CaO added together with phosphorus P 2 O 5 , which is an additive, is set to be tricalcium phosphate Ca 3 (PO 4 ) 2 or a partial compound with one or more of phosphorus and alkaline earth metals. Calcium phosphate Ca(PO 3 ) 2 .
本發明係如上所述,能夠製造一種不含有鐵、銅、鎳、鉻等金屬,且在製造太陽能電池等所必要的 低溫亦即650℃以下會熔融,且主成分只有釩及鋇之玻璃料。藉由該等玻璃料而具有下述的特徵。 The present invention is as described above, can produce a kind of metal that does not contain iron, copper, nickel, chromium, etc., and is necessary for the production of solar cells. Low temperature, that is, below 650℃, it will melt, and the main components are only vanadium and barium glass frit. These glass frits have the following characteristics.
(1)在玻璃料中能夠不含有鐵、銅、鎳、鉻等在太陽能電池的嚴酷的條件下會造成不良影響的物質。藉此,能夠消除在太陽能電池因含有鐵等而引起壽命低落一事。 (1) The glass frit may not contain iron, copper, nickel, chromium and other substances that can cause adverse effects under the harsh conditions of solar cells. Thereby, it is possible to eliminate the deterioration of the life of the solar cell due to the inclusion of iron or the like.
(2)能夠實現為了使用鋁膏所必要的較低熔點650℃以下。藉此,能夠在低熔點燒結,且能夠實現能夠使用在形成太陽能電池背面的鋁電極的鋁膏之玻璃料。 (2) It is possible to achieve the lower melting point of 650°C or lower, which is necessary for the use of aluminum paste. Thereby, it is possible to sinter at a low melting point, and it is possible to realize the glass frit of the aluminum paste that can be used to form the aluminum electrode on the back of the solar cell.
(3)藉由釩與鋇的構成,能夠消除鋁膏燒結時之太陽能電池基板的翹曲。 (3) The composition of vanadium and barium can eliminate the warpage of the solar cell substrate during aluminum paste sintering.
(4)添加磷P2O5及鹼土金屬(例如鈣CaO)而能夠改善I/V特性及密著性。 (4) Adding phosphorus P 2 O 5 and alkaline earth metals (for example, calcium CaO) can improve I/V characteristics and adhesion.
(5)以預定調配而添加鋁Al2O3及硼B2O3而能夠容易地玻璃化。 (5) Aluminum Al 2 O 3 and boron B 2 O 3 are added in a predetermined blending, so that it can be easily vitrified.
第1圖係本發明的ABS玻璃之製造流程圖。 Figure 1 is a manufacturing flow chart of the ABS glass of the present invention.
第2圖係本發明的ABS玻璃之製造試樣例。 Figure 2 is an example of manufacturing samples of the ABS glass of the present invention.
第3圖係本發明的太陽能電池用鋁膏用玻璃料例。 Fig. 3 shows an example of the glass frit for aluminum paste for solar cells of the present invention.
第4圖係本發明的ABS玻璃之各成分範圍的上限下限例說明圖。 Figure 4 is an explanatory diagram of an example of the upper and lower limits of the ranges of the respective components of the ABS glass of the present invention.
第5圖係本發明的太陽能電池用鋁電極煅燒用玻璃料說明圖。 Fig. 5 is an explanatory diagram of the glass frit for firing aluminum electrodes for solar cells of the present invention.
第6圖係本發明的ABS玻璃之概觀照相例。 Fig. 6 is an overview photographing example of the ABS glass of the present invention.
第7圖係本發明的ABS玻璃之製造流程圖(其2)。 Figure 7 is the manufacturing flow chart of the ABS glass of the present invention (Part 2).
第8圖係本發明的ABS玻璃之製造試樣例(其2)。 Fig. 8 is an example of manufacturing samples of the ABS glass of the present invention (Part 2).
第9圖係本發明的太陽能電池用鋁膏用玻璃料例(其2)。 Fig. 9 is an example of the glass frit for aluminum paste for solar cells of the present invention (Part 2).
第10圖係本發明的ABS玻璃之各成分範圍的上限下限例說明圖(其2)。 Fig. 10 is an explanatory diagram of an example of the upper and lower limit of each component range of the ABS glass of the present invention (No. 2).
第11圖係本發明的太陽能電池用鋁電極煅燒用玻璃料說明圖(其2)。 Fig. 11 is an explanatory diagram (Part 2) of the glass frit for firing aluminum electrodes for solar cells of the present invention.
第12圖係本發明的鋁膏之說明圖。 Figure 12 is an explanatory view of the aluminum paste of the present invention.
第13圖係本發明的鋁膏之製造流程圖。 Fig. 13 is a production flow chart of the aluminum paste of the present invention.
第14圖係本發明的鋁膏之煅燒流程圖。 Figure 14 is a flow chart of the calcination of the aluminum paste of the present invention.
第1圖係揭示本發明的ABS玻璃(Art Beam太陽能電池用玻璃)之製造流程圖。 Figure 1 shows a manufacturing flow chart of the ABS glass (Art Beam solar cell glass) of the present invention.
在第1圖,S1係調配玻璃原料而進行熔融(900℃至1200℃)(電爐溫度上升後,添加且放置1小時)。這是當電爐溫度令上升至以900℃至1200℃範圍之實驗而決定的最佳溫度時,將所調配的玻璃原料放入坩堝、插入、溶解並放置1小時。又,亦可藉由電爐上升至規定溫度而將已放入至坩堝之原料熔融且放置1小時。在實驗中,玻璃原料係例如後述之第2圖顯示之下述等。 In Fig. 1, the S1 system prepares and melts glass raw materials (900°C to 1200°C) (after the electric furnace temperature rises, it is added and left for 1 hour). This is when the temperature of the electric furnace rises to the optimal temperature determined by the experiment in the range of 900°C to 1200°C, put the prepared glass material into the crucible, insert, dissolve and leave it for 1 hour. In addition, the raw material put in the crucible may be melted by raising the temperature to a predetermined temperature by an electric furnace and left for 1 hour. In the experiment, the glass raw material is, for example, the following shown in Fig. 2 described later.
S2係製造玻璃碎片(3至5mm)。這是如在下側所記載,將S1所製造熔融玻璃一邊流動於經冷卻的金屬滾輪上一邊製造。亦即,將熔融玻璃流入至經水冷卻之旋轉金屬滾輪之間且急速冷卻而製造3至5mm左右的玻璃碎片。 S2 is the manufacturing of glass fragments (3 to 5mm). As described on the lower side, this is manufactured while flowing the molten glass manufactured by S1 on a cooled metal roller. That is, molten glass is poured between water-cooled rotating metal rollers and rapidly cooled to produce glass fragments of about 3 to 5 mm.
S3係進行粗粉碎(粉末2至3mm)及粉碎(~50μm)。這是將S2急速冷卻後之3至5mm的玻璃碎片進行粗粉碎而成為2至3mm的粉末,進一步將其粉碎至成為50μm左右粉末。
S3 system is coarsely crushed (
S4係進行微粉碎(2至3μm)(噴射研磨裝置)。這是使用噴射研磨裝置,將S3之~50μm的粉末進一步微粉碎而成為2至3μm左右的粉末(玻璃粉末、玻璃料)。 S4 system is finely pulverized (2 to 3 μm) (jet milling device). This is to use a jet milling device to further pulverize the S3 ~50μm powder into a powder (glass powder, glass frit) about 2 to 3μm.
S5係完成太陽能電池鋁電極用燒結助劑的 玻璃料。 S5 series completed the sintering aid for solar cell aluminum electrodes Frit glass.
如以上般,將原料上升至規定溫度(900℃至1200℃)且溶解而製造熔融玻璃,並將該熔融玻璃急速冷卻而製造玻璃碎片(3至5mm),將其粗粉碎、粉碎、微粉碎而製造2至3μm左右的玻璃料(玻璃粉末)(參照第6圖)。 As above, the raw materials are raised to a predetermined temperature (900°C to 1200°C) and dissolved to produce molten glass, and the molten glass is rapidly cooled to produce glass fragments (3 to 5 mm), which are coarsely crushed, crushed, and finely crushed And produce glass frit (glass powder) of about 2 to 3 μm (refer to Fig. 6).
第2圖係顯示本發明的ABS玻璃之製造試樣例。 Fig. 2 shows an example of manufacturing samples of the ABS glass of the present invention.
第2圖的(a)係顯示試樣No.1、試樣No.2、試樣No.3。該等係表示對試樣所賦予之名稱。 (A) of Figure 2 shows sample No. 1, sample No. 2, and sample No. 3. These are the names given to the samples.
第2圖的(b)係顯示各試樣的原料之莫耳%。例如試樣No.1係由 Figure 2(b) shows the molar% of the raw material of each sample. For example, sample No.1 is
又,右端的「範圍」係顯示能夠製造良好的玻璃料之原料範圍,圖示的下述範圍內時能夠製造良好的玻璃料。 In addition, the "range" at the right end shows the range of raw materials that can produce a good glass frit, and a good glass frit can be produced in the following range shown in the figure.
第2圖(c)係顯示調配比(g)。這是表示將各原料以第2圖(b)的莫耳%比率調配時之g的1例。 Figure 2 (c) shows the blending ratio (g). This is an example of g when each raw material is blended at the molar% ratio shown in Figure 2(b).
第2圖(d)係顯示本發明的玻璃料之特性例。 Figure 2 (d) shows an example of the characteristics of the glass frit of the present invention.
‧可觀察到即便將熔融玻璃流出至金屬板上,亦不結晶化。 ‧It can be observed that even if the molten glass flows out onto the metal plate, it does not crystallize.
‧可觀察到試樣No.2、No.3係任一者均不結晶化。 ‧It can be observed that none of the samples No.2 and No.3 are crystallized.
‧軟化性觀察:將第1圖所製造的玻璃料添加至坩堝且使溫度上升時, ‧Observation of softening: When the glass frit manufactured in Figure 1 is added to the crucible and the temperature rises,
‧試樣No.1係在570℃表面開始熔解,在595℃完全熔解。 ‧Sample No.1 starts to melt on the surface at 570℃ and completely melts at 595℃.
‧試樣No.2、No.3係任一者均是在572℃開始熔解,在587℃完全熔解。 ‧Either sample No.2 and No.3 series starts to melt at 572°C and completely melts at 587°C.
第2圖(e)係顯示玻璃的轉變溫度之例子。針對如圖示的各轉變溫度,各自可得到圖示之值。 Figure 2 (e) shows an example of the glass transition temperature. For each transition temperature as shown in the figure, the value shown in the figure can be obtained for each.
在此,清楚明白結晶熔融溫度係試樣No.1、2、3為515℃、525℃、524℃,任一者均為600℃以下,可實現作為目標之650℃以下。 Here, it is clear that the crystal melting temperature of Sample Nos. 1, 2, and 3 is 515°C, 525°C, and 524°C, and any of them is 600°C or less, and the target 650°C or less can be achieved.
第3圖係顯示本發明的太陽能電池用鋁膏用玻璃料例(成分莫耳比)。這是為了容易理解,而將前述實驗例的第2圖(a)、(b)的試樣No.1、2、3的莫耳%部分取出且整理而成。 Fig. 3 shows an example of the glass frit (component molar ratio) for aluminum paste for solar cells of the present invention. This is for easy understanding, and the molar% part of the sample Nos. 1, 2, and 3 in the second figures (a) and (b) of the aforementioned experimental example is taken out and arranged.
‧試樣No.1之釩V2O5為77.58莫耳%且在範圍55至80莫耳%的範圍內。鋇BaO為22.22莫耳%且在範圍15至30莫耳%的範圍內。 ‧The vanadium V 2 O 5 of sample No.1 is 77.58 mol% and is in the range of 55 to 80 mol%. Barium BaO is 22.22 mol% and is in the range of 15 to 30 mol%.
‧試樣No.2、No.3亦如圖示且在範圍內。 ‧Sample No.2 and No.3 are also within the range as shown in the figure.
針對以上的試樣No.1、2、3,可觀察、實測前述第2圖(d)、(e)記載之各種特性,特別是可達成熔融溫度為650℃以下,清楚明白可使用作為混合在太陽能電池的鋁膏之玻璃料。而且,本玻璃料不含有鐵、銅、鎳、鉻,即便長期間使用亦不會使太陽能電池的特性劣化。 For the above sample Nos. 1, 2, and 3, the various characteristics described in Figure 2 (d) and (e) can be observed and measured. In particular, the melting temperature can be reached below 650°C. It is clear that it can be used for mixing Glass frit in aluminum paste for solar cells. Moreover, this glass frit does not contain iron, copper, nickel, or chromium, and will not deteriorate the characteristics of the solar cell even if it is used for a long period of time.
第4圖係顯示本發明的ABS玻璃之各成分的範圍之上限下限例說明圖。 Fig. 4 is an explanatory diagram showing examples of the upper and lower limits of the ranges of the components of the ABS glass of the present invention.
第4圖(a)係顯示釩V2O5(55至80莫耳%)的上限下限例說明。 Figure 4(a) shows an example of the upper and lower limits of vanadium V 2 O 5 (55 to 80 mol%).
‧釩V2O5為下限(55莫耳%)以下時,不形成玻璃骨架。 ‧When vanadium V 2 O 5 is below the lower limit (55 mol%), no glass skeleton is formed.
‧釩V2O5為上限(80莫耳%)以上時,調整機械強度為困難的。耐水性劣化。 ‧When vanadium V 2 O 5 is above the upper limit (80 mol%), it is difficult to adjust the mechanical strength. Water resistance deteriorates.
第4圖(b)係顯示鋇BaO(實際上係添加BaCO3作為原料,加熱溶解時CO2被放出而成為BaO)的上限下限例說明。 Figure 4(b) shows an example of the upper and lower limits of barium BaO (actually, BaCO 3 is added as a raw material, and CO 2 is released when heated to dissolve to become BaO).
‧鋇BaO(BaCO3)為下限(15莫耳%)以下時,均質的玻璃化變為困難。 ‧When barium BaO (BaCO 3 ) is below the lower limit (15 mol%), homogeneous vitrification becomes difficult.
‧鋇BaO(BaCO3)為上限(30莫耳%)以上時,機械強度劣化。 ‧When barium BaO (BaCO 3 ) is above the upper limit (30 mol%), the mechanical strength deteriorates.
第4圖(c)係顯示其它添加物(例如第4圖(d)的3種類添加物)說明。 Figure 4(c) shows the description of other additives (for example, the three types of additives in Figure 4(d)).
‧下述添加物,係不會妨礙鋁材料(3價)對矽(4價)形成P型功能、或承擔增加的任務。依照情況亦可無添加物。 ‧The following additives will not prevent aluminum materials (trivalent) from forming P-type functions on silicon (quaternary) or assume additional tasks. Depending on the situation, there may be no additives.
第4圖(d)係顯示添加物的例子。 Figure 4(d) shows an example of additives.
‧鋁Al2O3(0至10莫耳%): ‧Aluminum Al 2 O 3 (0-10 mol%):
‧硼B2O3(0至7莫耳%): ‧Boron B 2 O 3 (0 to 7 mole%):
‧矽SiO2(0至7莫耳%): ‧Silicon SiO 2 (0-7 mol%):
‧該3成分的調配比率具有良好的平衡為重要的。否則無法保持均勻性而結晶析出。亦可為任意2成分或1成分或無。但是為了保持耐水性,以添加矽SiO2為佳。 ‧It is important that the blending ratio of the 3 ingredients has a good balance. Otherwise, the uniformity cannot be maintained and crystals will precipitate. It may be any two components or one component or none. However, in order to maintain water resistance, it is better to add silicon SiO 2 .
第5圖係顯示本發明的太陽能電池用鋁電極煅燒用玻璃料說明圖。將鋁膏塗佈、燒結在太陽能電池背面而形成鋁電極時,這是對應混入該鋁膏之玻璃料被認為必要的課題(要求)(1)、(2)、(3)、及本發明解決之手段而製成之表格。 Fig. 5 is an explanatory diagram showing the glass frit for firing aluminum electrodes for solar cells of the present invention. When aluminum paste is coated and sintered on the back of a solar cell to form an aluminum electrode, this is a problem (requirement) (1), (2), (3), and the present invention that are considered necessary for the glass frit mixed with the aluminum paste Forms made by means of solutions.
第5圖(a)係顯示課題「(1)較低的熔點」及本發明的解決手段。在本發明係如前述,係實現以釩及鋇作為主體,且600℃以下。這是因為燒結溫度係以鋁的熔點(660℃)與玻璃料的熔點之中間點來決定,所以在本發明係將玻璃料的熔點規定為650℃以下且在實驗中可實現600℃以下(第2圖(e)的結晶溶解溫度為515℃、525℃、524 ℃而可實現600℃以下)。 Figure 5(a) shows the problem "(1) Lower melting point" and the solution of the present invention. In the present invention, as described above, it is realized that vanadium and barium are the main components and the temperature is below 600°C. This is because the sintering temperature is determined by the midpoint between the melting point of aluminum (660°C) and the melting point of the glass frit. Therefore, in the present invention, the melting point of the glass frit is specified to be 650°C or less, and in the experiment, it can achieve 600°C or less ( The crystal dissolution temperature in Figure 2(e) is 515℃, 525℃, 524 ℃ and can achieve below 600 ℃).
第5圖(b)係顯示課題「(2)對矽太陽能電池的壽命造成影響之成分構成」及本發明的解決手段。在本發明係如前述,不含有鐵、銅、鎳、鉻等。基本為釩、鋇、矽、鋁、硼的組合。在此,矽、鋁、硼係背面鋁的接觸材料。 Fig. 5(b) shows the problem "(2) Composition affecting the life of silicon solar cells" and the solution of the present invention. In the present invention, as mentioned above, no iron, copper, nickel, chromium, etc. are contained. It is basically a combination of vanadium, barium, silicon, aluminum, and boron. Here, silicon, aluminum, and boron are contact materials for back aluminum.
如以上般,太陽能電池在長期嚴酷的使用條件之下,因為使用不含有會造成不良影響之鐵、銅、鎳、鉻等材料製造玻璃料,所以能夠避免該等不良影響。 As mentioned above, under long-term harsh conditions of use, solar cells are made of glass frit that does not contain iron, copper, nickel, chromium and other materials that will cause adverse effects, so such adverse effects can be avoided.
第5圖(c)係顯示課題「(3)矽基板係在燒結時不翹曲」及本發明的解決手段。在本發明係如前述,藉由釩、鋇的構成成分,使得鋁燒結時基板不翹曲。 Figure 5(c) shows the problem "(3) The silicon substrate does not warp during sintering" and the solution of the present invention. In the present invention, as described above, the constituent components of vanadium and barium prevent the substrate from warping during aluminum sintering.
第6圖係顯示本發明的ABS玻璃之概觀照相例。這是顯示前述第1圖的步驟所製造的ABS玻璃之概觀照相例。 Figure 6 shows an overview photograph of the ABS glass of the present invention. This is an overview photograph showing the ABS glass manufactured by the steps in Figure 1 above.
第6圖(a)係顯示ABS玻璃的照相例。這是顯示將前述第1圖的S2之玻璃碎片(稱為ABS玻璃)進行試作實驗時之概觀照相例。 Figure 6(a) shows a photographic example of ABS glass. This is an example of an overview photograph when the glass shards (called ABS glass) of S2 in the above-mentioned Figure 1 were subjected to a trial production experiment.
第6圖(b)係顯示粗碎(2至3mm)的ABS玻璃之概觀照相例。ABS玻璃係被粉碎成為2至3mm左右的玻璃片。 Figure 6(b) shows an overview photograph of coarsely broken (2 to 3mm) ABS glass. The ABS glass system is crushed into glass pieces of about 2 to 3 mm.
第6圖(c)係顯示粉碎(~50μm)的ABS玻璃之概觀照相例。ABS玻璃係被粉碎成為~50μm左右。而且,在噴射研磨裝置微粉碎成為2至3μm左右且完成玻璃料。 Figure 6(c) shows an overview photograph of crushed (~50μm) ABS glass. The ABS glass system is crushed to ~50μm. In addition, it is finely pulverized by a jet milling device to approximately 2 to 3 μm to complete glass frit.
又,在製造混入有玻璃料之鋁膏,係例如藉由依照順序將(1)鋁微粉末、(2)本發明的玻璃料(微粉末)、(3)有機材、(4)有機溶劑、(5)樹脂(或者亦可改變順序),添加至容器且充分地攪拌來製造。 In addition, in the production of aluminum paste mixed with glass frit, for example, by sequentially mixing (1) aluminum fine powder, (2) glass frit (fine powder) of the present invention, (3) organic material, and (4) organic solvent , (5) Resin (or the order can also be changed), add it to the container and fully stir to manufacture.
然後,為了將所製造的鋁膏在太陽能電池基板的背面形成需要的鋁圖案,係進行網版印刷、使溶劑消散及燒結而形成鋁電極。 Then, in order to form a required aluminum pattern on the back surface of the solar cell substrate with the manufactured aluminum paste, screen printing, solvent dissipation, and sintering are performed to form aluminum electrodes.
第7圖係顯示本發明的ABS玻璃(Art Beam太陽能電池用玻璃)之製造流程圖(其2)。 Fig. 7 shows the manufacturing flow chart (Part 2) of the ABS glass (glass for Art Beam solar cells) of the present invention.
在第7圖,S11係調配玻璃原料且進行熔融(900℃至1200℃)(電爐溫度上升後,添加且放置1小時)。此係會電爐溫度上升至以900℃至1200℃範圍之實驗決定的最佳溫度時,將所調配的玻璃原料放入坩堝插入、溶解,並放置1小時。又,亦可藉由電爐上升至規定溫度而將已放入至坩堝之原料熔融且放置1小時。在實驗中,玻璃原料係例如後述之第8圖及第9圖顯示之下述等。 In Fig. 7, the S11 system prepares and melts glass raw materials (900°C to 1200°C) (after the electric furnace temperature rises, it is added and left for 1 hour). When the temperature of the electric furnace rises to the optimal temperature determined by the experiment in the range of 900°C to 1200°C, the prepared glass material is inserted into the crucible, dissolved, and left for 1 hour. In addition, the raw material put in the crucible may be melted by raising the temperature to a predetermined temperature by an electric furnace and left for 1 hour. In the experiment, the glass raw material is, for example, the following shown in Fig. 8 and Fig. 9 described later.
S12係製造玻璃碎片(3至5mm)。這是如在下側所記載,將S11所製造熔融玻璃一邊流通於經冷卻的金屬滾輪上一邊製造。亦即,將熔融玻璃流入至經水冷卻之旋轉金屬滾輪之間且急速冷卻而製造3至5mm左右的玻璃碎片。 S12 is the manufacturing of glass fragments (3 to 5mm). This is manufactured while circulating the molten glass manufactured by S11 on a cooled metal roller as described on the lower side. That is, molten glass is poured between water-cooled rotating metal rollers and rapidly cooled to produce glass fragments of about 3 to 5 mm.
S13係進行粗粉碎(粉末2至3mm)及粉碎(~50μm)。這是將S12急速冷卻後之3至5mm的玻璃碎片進行粗粉碎而成為2至3mm的粉末,進一步將其粉碎至成為50μm左右粉末。
S13 system is used for coarse crushing (
S14係進行微粉碎(2至3μm)(噴射研磨裝置)。這是使用噴射研磨裝置,將S13之~50μm的粉末進一步微粉碎而成為2至3μm左右的粉末(玻璃粉末、玻璃料)。 S14 system performs fine pulverization (2 to 3 μm) (jet milling device). This is to use a jet milling device to further pulverize the S13 ~50μm powder into a powder (glass powder, glass frit) about 2 to 3μm.
S15係完成太陽能電池鋁電極用燒結助劑的玻璃料。 S15 is a glass frit used to complete the sintering aid for aluminum electrodes of solar cells.
如以上般,將原料上升至規定溫度(900℃至1200℃)且溶解而製造熔融玻璃,並將該熔融玻璃急速冷卻而製造玻璃碎片(3至5mm),將其粗粉碎、粉碎、微粉碎而製造2至3μm左右的玻璃料(玻璃粉末)。 As above, the raw materials are raised to a predetermined temperature (900°C to 1200°C) and dissolved to produce molten glass, and the molten glass is rapidly cooled to produce glass fragments (3 to 5 mm), which are coarsely crushed, crushed, and finely crushed And produce glass frit (glass powder) of about 2 to 3 μm.
第8圖係顯示本發明的ABS玻璃之製造試樣例(其2)。 Fig. 8 shows an example of manufacturing samples of the ABS glass of the present invention (Part 2).
在第8圖,(a)的「試樣11」係表示試樣11。
該等係表示對試樣11所賦予的名稱,其下段係顯示原料(材料)名稱。
In Fig. 8, "
在第8圖,(b)的「莫耳比%(範圍)」中之「莫耳比%」,係表示試樣原料的莫耳%。例如試樣11係由
In Figure 8, the "molar ratio%" in the "molar ratio% (range)" in (b) represents the molar percentage of the sample material. For example,
又,第8圖(b)的「莫耳比%(範圍」中之「範圍」係顯示能夠製造良好的玻璃料之各原料範圍,圖示之下述範圍內時係能夠製造良好的玻璃料。 In addition, the "range" in the "mole ratio% (range" in Figure 8(b)) shows the range of raw materials that can produce good glass frit. The following range in the figure shows that good glass frit can be produced .
在第8圖,(c)係表示質量(g)。這是表示將各原料以第8圖(b)的莫耳%比率調配時之g的1例。 In Figure 8, (c) indicates mass (g). This is an example of g when each raw material is blended at the molar% ratio shown in Figure 8(b).
在第8圖,(d)係顯示本發明的玻璃料之特性例。 In Fig. 8, (d) shows an example of the characteristics of the glass frit of the present invention.
‧坩堝內狀態為良好。這是將上述原料放入坩堝且熔解時的狀態為良好。 ‧The state of the crucible is good. This means that the state when the above-mentioned raw materials are put in a crucible and melted is good.
‧所謂流出狀態表面為「相當混濁」,係表示在將熔解後的熔解物從坩堝內急速地流出至冷卻裝置後的狀態下,熔解物表面為「相當混濁」之狀態。 ‧The surface of the outflow state is "substantially turbid", which means that the surface of the melt is "substantially turbid" in the state after the melted material is rapidly flowing out of the crucible to the cooling device.
‧所謂軟化性觀察為「500℃:顆粒為帶圓形。600℃:顆粒之間黏住」,係表示在將第7圖所製造的璃料放入坩堝且使溫度上升時,顆粒500℃時附近為帶圓形,在600℃時顆粒之間黏住且已熔解。 ‧The so-called softening observation is "500℃: the pellets are round. 600℃: the pellets are stuck together", which means that when the glass material manufactured in Figure 7 is put into the crucible and the temperature is increased, the pellets are 500℃ At 600℃, the particles are sticky and melted.
‧所謂冷卻後的狀態係表面為「棕色。上升至650℃為止而從坩堝剝落」,係表示在熔解物冷卻後的狀態下,表面為「棕色」,且將放入坩堝的熔解物上升至650℃為止時熔解物容易地從坩堝剝落。 ‧The so-called state after cooling means that the surface is "brown. It peels off from the crucible until it rises to 650℃", which means that the surface of the molten material is "brown" after cooling, and the molten material placed in the crucible rises to The melt easily peeled off from the crucible at 650°C.
在第8圖,在(e)的DTA,係在DTA測定(轉移點、軟化點、結晶化、結晶熔解等的各溫度測定)難以顯現尖峰。 In Fig. 8, the DTA in (e) is difficult to show sharp peaks in DTA measurement (measurement of transition point, softening point, crystallization, crystal melting, etc.).
第9圖係顯示本發明的太陽能電池用鋁膏用玻璃料例(成分莫耳比)(其2)。這是為了容易理解,而將前述實驗例的第8圖的試樣11及圖示外的其它試樣12、13的莫耳%部分取出且整理且附加其結果(密著性、I/V特性)而成。
Fig. 9 shows an example of the glass frit for aluminum paste for solar cells of the present invention (component molar ratio) (Part 2). This is for easy understanding, and the molar% part of
在此,添加鋁Al2O3時係容易玻璃化。 Here, when aluminum Al 2 O 3 is added, it is easy to vitrify.
又,磷P2O5係即便在該狀態下添加亦難以玻璃化。因此,係將磷以鹼土金屬(例如鈣)的化合物之方式添加後,才熔解在主材料(由鋇V2O5、釩BaO所構成之主骨架)的熔解物中而能夠玻璃化。例如以磷酸二氫鈣(或磷酸鈣)的水合物(Ca(H2PO4)2‧H2O)之方式添加。 In addition, the phosphorus P 2 O 5 system is difficult to vitrify even if it is added in this state. Therefore, phosphorus is added as a compound of an alkaline earth metal (for example, calcium) before it is melted in the molten material of the main material (the main skeleton composed of barium V 2 O 5 and vanadium BaO) and can be vitrified. For example, calcium dihydrogen phosphate (or calcium phosphate) hydrate (Ca(H 2 PO 4 ) 2 ‧H 2 O) is added.
針對以上的試樣11、12、13,可觀察、實測前述第8圖(d)、(e)記載之各種特性,特別是可達成熔融溫度為650℃以下,而且在試樣11進行評價在結果欄所記載的密著性(太陽能電池基板的例子係將使用玻璃料之太陽能電池的鋁膏塗附、乾燥、燒結在背面後之密著性)、以及太陽能電池的I/V特性,亦可得到比先前更良好(例如良好且為2倍左右以上)的結果。而且,本玻璃料不含有鐵、銅、鎳、鉻,即便長期間使用亦不會使太陽能電池的特性劣化。
For the
第10圖係顯示本發明的ABS玻璃之各成分的範圍之上限下限例說明圖(其2)。 Fig. 10 is an explanatory diagram showing an example of the upper and lower limit of the range of each component of the ABS glass of the present invention (No. 2).
第10圖(a)係顯示釩V2O5(10至55莫耳%)的上限下限例說明。 Figure 10(a) shows an example of the upper and lower limits of vanadium V 2 O 5 (10 to 55 mol%).
‧釩V2O5為下限(10莫耳%)以下時,係不 形成玻璃骨架。 ‧When vanadium V 2 O 5 is below the lower limit (10 mol%), no glass skeleton is formed.
‧釩V2O5為上限(55莫耳%)以上時,調整機械強度為困難的。耐水性劣化。 ‧When vanadium V 2 O 5 is above the upper limit (55 mol%), it is difficult to adjust the mechanical strength. Water resistance deteriorates.
在此,釩V2O5的範圍(10至55莫耳%)係從第4圖(55至80莫耳%)大幅度地減少,係因為添加磷P2O5(5至20莫耳%)及CaO(5至20莫耳%)等,所以最多的主材料之釩V2O5的添加比率減少。 Here, the range of vanadium V 2 O 5 (10 to 55 mol%) is greatly reduced from Figure 4 (55 to 80 mol%) because of the addition of phosphorus P 2 O 5 (5 to 20 mol%) %) and CaO (5 to 20 mol%), etc., so the addition ratio of vanadium V 2 O 5 , which is the most main material, decreases.
第10圖(b)係顯示鋇BaO(實際上係添加BaCO3作為原料,加熱溶解時CO2被放出而成為BaO)的上限下限例說明。 Figure 10(b) shows an example of the upper and lower limits of barium BaO (in fact, BaCO 3 is added as a raw material, and CO 2 is released when heated to dissolve to become BaO).
‧鋇BaO(BaCO3)為下限(10莫耳%)以下時,均質的玻璃化變為困難。 ‧When barium BaO (BaCO 3 ) is below the lower limit (10 mol%), homogeneous vitrification becomes difficult.
‧鋇BaO(BaCO3)為上限(40莫耳%)以上時,機械強度劣化。 ‧When barium BaO (BaCO 3 ) is above the upper limit (40 mol%), the mechanical strength will deteriorate.
第10圖(c)係顯示其它添加物(例如第10圖(d)之2種類的添加物)之說明。 Figure 10(c) shows an explanation of other additives (for example, the two types of additives in Figure 10(d)).
‧不會妨礙鋁材料(3價)對矽(4價)形成P型功能、或承擔增加的任務。依照情況亦可無添加物。 ‧It will not prevent aluminum materials (trivalent) from forming P-type functions on silicon (quaternary) or undertake additional tasks. Depending on the situation, there may be no additives.
第10圖(d)係顯示添加物的例子。 Figure 10(d) shows an example of additives.
‧鋁Al2O3(1至10莫耳%): ‧Aluminum Al 2 O 3 (1-10 mol%):
‧硼B2O3(5至20莫耳%): ‧Boron B 2 O 3 (5-20 mol%):
‧該2成分的調配比率具有良好的平衡為重要的。否則無法保持均勻性而結晶析出且不玻璃化。 ‧It is important that the blending ratio of the 2 components has a good balance. Otherwise, the uniformity cannot be maintained and the crystals will precipitate without vitrification.
第10圖(e)係顯示磷P2O5(5至20莫耳%)、鈣CaO(5至20莫耳%)的添加例。添加磷P2O5(5至20莫耳%)及鈣CaO(5至20莫耳%),係添加磷酸三鈣Ca3(PO4)2。 Figure 10(e) shows an example of addition of phosphorus P 2 O 5 (5 to 20 mol%) and calcium CaO (5 to 20 mol%). Phosphorus P 2 O 5 (5 to 20 mol%) and calcium CaO (5 to 20 mol%) are added, and tricalcium phosphate Ca 3 (PO 4 ) 2 is added .
‧因為磷係與水反應,以磷酸的方式添加為佳。 ‧Because the phosphorus system reacts with water, it is better to add phosphoric acid.
‧因為含有鹼金屬之化合物係使太陽能電池特性劣化,所以添加與鹼土金屬(例如鈣)的磷化合物。 ‧Because compounds containing alkali metals deteriorate the characteristics of solar cells, phosphorus compounds with alkaline earth metals (such as calcium) are added.
‧添加硼(3價)及磷(5價)及銻(5價)的化合物時,相較於添加硼、磷之2種而成之物,同時添加3種而成之物,係在I/V特性、密著性為較差。 ‧When boron (trivalent), phosphorus (5-valent) and antimony (5-valent) compounds are added, compared with the addition of two kinds of boron and phosphorus, the addition of three kinds at the same time is in I /V characteristics and adhesion are poor.
又,作為上述與鹼土金屬(例如鈣)的磷化合物,係添加磷酸三鈣Ca3(PO4)2或偏磷酸鈣Ca(PO3)2而進實驗,任一者均能夠得到良好的結果。特別是使用前者的磷酸三鈣Ca3(PO4)2作為食品添加材,就可廉價地取得而言,而且就相較於後者,氧O的數目為若干較多之8(後者之數目為6)而言,能夠得到良好的結果。又,在製造本發明的玻璃料時,碳C(亦包化合物)係有微量地附著或混入至原料之可能性,因為藉由該氧O將該微量的碳C氧化而以氣體(碳酸氣體CO2等)的方式放出,亦能夠淨化,所以必須含有若干的氧O。 In addition, as the above-mentioned phosphorus compound with alkaline earth metals (for example, calcium), tricalcium phosphate Ca 3 (PO 4 ) 2 or calcium metaphosphate Ca(PO 3 ) 2 was added and the experiment was carried out, and good results were obtained with either . In particular, the use of the former tricalcium phosphate Ca 3 (PO 4 ) 2 as a food additive can be obtained inexpensively, and compared with the latter, the number of oxygen O is 8 (the number of the latter is 6) In terms of, good results can be obtained. In addition, when manufacturing the glass frit of the present invention, carbon C (including compound) may be attached or mixed into the raw material in a small amount, because the oxygen O oxidizes the small amount of carbon C to produce gas (carbon dioxide gas). CO 2 etc.) can also be released, so it must contain some oxygen O.
而且,將磷酸P2O5與鈣CaO直接添加時,係無法製造良好的玻璃料。同樣地,添加成為鈣CaO的鹼土金屬以外之物,例如鈉、鉀等,在如太陽能電池長期間(例如10年以上)被暴露強烈的太陽光之情況,係劣化而無 法使用。 Moreover, when phosphoric acid P 2 O 5 and calcium CaO are directly added, it is impossible to produce a good glass frit. Similarly, substances other than alkaline earth metals added as calcium CaO, such as sodium, potassium, etc., are degraded and cannot be used when solar cells are exposed to strong sunlight for a long period of time (for example, 10 years or more).
第11圖係顯示本發明的太陽能電池用鋁電極煅燒用玻璃料說明圖(其2)。將鋁膏塗佈、燒結在太陽能電池背面而形成鋁電極時,這是對應混入該鋁膏之玻璃料被認為必要的課題(要求)(1)、(2)、(3)、(4)及本發明解決之手段而製成之表格。 Fig. 11 is an explanatory diagram showing the glass frit for firing aluminum electrodes for solar cells of the present invention (Part 2). When the aluminum paste is coated and sintered on the back of the solar cell to form the aluminum electrode, this is a problem considered necessary for the glass frit mixed with the aluminum paste (requirement) (1), (2), (3), (4) And the table created by the solution of the present invention.
第11圖(a)係顯示課題「(1)較低的熔點」及本發明的解決手段。在本發明係如前述,係實現以釩及鋇作為主體,且600℃以下。這是因為燒結溫度係以鋁的熔點(660℃)與玻璃料的熔點之中間點來決定,所以在本發明係將玻璃料的熔點規定為650℃以下,且在實驗中能夠實現600℃以下 Figure 11(a) shows the problem "(1) Lower melting point" and the solution of the present invention. In the present invention, as described above, it is realized that vanadium and barium are the main components and the temperature is below 600°C. This is because the sintering temperature is determined by the midpoint between the melting point of aluminum (660°C) and the melting point of the glass frit. Therefore, in the present invention, the melting point of the glass frit is specified to be 650°C or less, and in the experiment, it can achieve 600°C or less
第11圖(b)係顯示課題「對(2)矽太陽能電池的壽命造成影響之成分構成」及本發明的解決手段。在本發明係如前述,不含有鐵、銅、鎳、鉻等。基本為釩、鋇、矽、鋁、硼、磷、鈣、鋅的組合。在此,鋁、硼係背面鋁的接觸材料。 Fig. 11(b) shows the problem "(2) Composition affecting the life of silicon solar cell" and the solution of the present invention. In the present invention, as mentioned above, no iron, copper, nickel, chromium, etc. are contained. It is basically a combination of vanadium, barium, silicon, aluminum, boron, phosphorus, calcium, and zinc. Here, aluminum and boron are contact materials for back aluminum.
如以上般,太陽能電池在長期嚴酷的使用條件之下,因為使用不含有會造成不良影響之鐵、銅、鎳、鉻等材料製造玻璃料,所以可避免該等不良影響。 As mentioned above, under long-term harsh use conditions for solar cells, the glass frit is made of materials that do not contain iron, copper, nickel, chromium, etc. that will cause adverse effects, so such adverse effects can be avoided.
第11圖(c)係顯示課題「(3)矽基板係在燒結時不翹曲」及本發明的解決手段。在本發明係如前述,藉由釩、鋇的構成成分,使得鋁燒結時基板不翹曲。 Figure 11(c) shows the problem "(3) The silicon substrate does not warp during sintering" and the solution of the present invention. In the present invention, as described above, the constituent components of vanadium and barium prevent the substrate from warping during aluminum sintering.
第11圖(d)係顯示課題「(4)密著性、I/V改 善」及本發明的解決手段。在本發明係如前述,藉由添加有磷及鈣等之構成成分,鋁燒結時與基板的密著性變為良好且亦能夠改善I/V特性。 Figure 11(d) shows the topic "(4) Adhesion, I/V reform Good” and the solution of the present invention. In the present invention, as described above, by adding constituent components such as phosphorus and calcium, the adhesion of aluminum to the substrate during sintering becomes good and the I/V characteristics can also be improved.
其次,使用從第12圖至第14圖,詳細地依次說明下列步驟:在從第1圖至第11圖將前述本發明的玻璃料作為助劑而添加來製造鋁膏之步驟;及將該製成的鋁膏塗佈在太陽能電池背面且進行燒結,來形成鋁電極步驟。 Next, using FIGS. 12 to 14 to describe in detail the following steps: from FIGS. 1 to 11, adding the glass frit of the present invention as an auxiliary agent to produce aluminum paste; and The prepared aluminum paste is coated on the back of the solar cell and sintered to form an aluminum electrode step.
第12圖係顯示本發明的鋁膏之說明圖。這是鋁膏的構成成分之1例,例如下述之圖示。將該等構成成分混合而製造鋁膏(參照第13圖)。 Figure 12 is an explanatory diagram showing the aluminum paste of the present invention. This is an example of the constituent components of the aluminum paste, for example, as shown below. These components are mixed to produce an aluminum paste (see Fig. 13).
(1)鋁粉末: (1) Aluminum powder:
‧純度:99.7%以上 ‧Purity: 99.7% or more
‧平均粒度:1至20μm ‧Average particle size: 1-20μm
‧形狀:球狀、橢圓球狀 ‧Shape: spherical, elliptical
(2)本發明的釩酸鹽玻璃(玻璃料): (2) The vanadate glass (glass frit) of the present invention:
‧粒徑:1至3μm ‧Particle size: 1 to 3μm
‧鋁膏全體的重量比0.1至1% ‧The weight ratio of the whole aluminum paste is 0.1 to 1%
(3)其它玻璃粉末: (3) Other glass powder:
‧粒徑:1至3μm ‧Particle size: 1 to 3μm
鋁膏全體的重量比0至1% The weight ratio of the whole aluminum paste is 0 to 1%
(4)樹脂: (4) Resin:
‧鋁膏全體的重量比0.1至3% ‧The weight ratio of the whole aluminum paste is 0.1 to 3%
‧乙基纖維素類、硝基纖維素類等 ‧Ethyl cellulose, nitrocellulose, etc.
(5)溶劑: (5) Solvent:
‧鋁膏全體的重量比大約25%(適合於網版印刷等之黏土) ‧The weight ratio of the aluminum paste is about 25% (suitable for clay for screen printing, etc.)
‧二乙二醇、一丁醚等 ‧Diethylene glycol, monobutyl ether, etc.
第13圖係顯示本發明的鋁膏之製造流程圖。 Fig. 13 shows the manufacturing flow chart of the aluminum paste of the present invention.
在第13圖,S21係使用混合機將溶劑與樹脂摻混(有機媒液)。這是將前述第12圖(5)溶劑與(4)樹脂放入混合機且充分地混合而製造有機媒液。 In Figure 13, S21 uses a mixer to blend solvent and resin (organic vehicle). This is to put the solvent (5) and the resin (4) in the aforementioned Figure 12 into a mixer and mix them thoroughly to produce an organic medium.
S22係將玻璃摻混至有機媒液。這是將S21所製造的有機媒液、前述第12圖(2)本發明的釩酸鹽玻璃粉末(玻璃料)、及按照必要之(3)其它玻璃粉末放入混合機且充分地混合。 S22 is to blend glass into organic medium. This is to put the organic medium produced in S21, the vanadate glass powder (glass frit) of the present invention in Figure 12 (2), and other glass powders as necessary (3) into the mixer and mix them thoroughly.
S23係摻混鋁粉末。這是進一步摻混前述第12圖(1)的鋁粉末之步驟,相對於第12圖(1)的鋁粉末100重量份,係以有機媒液成為1.5至100重量份(較佳是30至50重量份)的方式混合該(1)的鋁粉末。 S23 is blended with aluminum powder. This is the step of further blending the aluminum powder of Figure 12 (1). With respect to 100 parts by weight of the aluminum powder in Figure 12 (1), the organic medium is used to make 1.5 to 100 parts by weight (preferably 30 to The aluminum powder of (1) was mixed by 50 parts by weight).
S24係完成鋁膏。 S24 series finished aluminum paste.
依照以上S21至S24的程序,將前述第12圖(5)溶劑、(4)樹脂、(2)本發明的釩酸鹽玻璃粉末(玻璃料)及按照必要之(3)其它玻璃粉末、進而(1)鋁粉末依照順序使用混合機且充分地混合,而能夠製造鋁膏。 In accordance with the procedures from S21 to S24 above, combine the solvent, (4) resin, (2) the vanadate glass powder (glass frit) of the present invention and (3) other glass powders as necessary, and then (1) The aluminum powder is mixed thoroughly using a mixer in order to produce aluminum paste.
第14圖係顯示本發明的鋁膏之煅燒流程圖。這是顯示將前述第13圖所製成的鋁膏,塗佈、乾燥、 煅燒在太陽能電池背面,來形成鋁電極時之煅燒流程圖的1例。 Figure 14 is a flow chart showing the calcination of the aluminum paste of the present invention. This is to show that the aluminum paste made in Figure 13 is applied, dried, An example of the calcining flow chart when calcining on the back of the solar cell to form an aluminum electrode.
在第14圖,S31係塗佈在太陽能電池單元的背面、矽面。例如以5至13mg/cm2的厚度塗佈。這是塗佈在形成鋁電極之對象例如太陽能電池單元背面,或直接塗佈在矽基板背面的矽面。 In Figure 14, S31 is coated on the back and silicon surface of the solar cell. For example, it is coated with a thickness of 5 to 13 mg/cm 2 . This is coated on the object that forms the aluminum electrode, such as the back of a solar cell, or directly coated on the silicon surface on the back of a silicon substrate.
S32係進行乾燥。這是將在S31所塗佈的鋁膏例如放入100至300℃的乾燥爐1分鐘至10分鐘使溶劑消散而乾燥。又,亦可輸送熱風而乾燥。 S32 system is dried. This is to put the aluminum paste applied in S31, for example, in a drying oven at 100 to 300°C for 1 minute to 10 minutes to dissipate the solvent and dry. Also, it can be dried by sending hot air.
S33係進行鋁燒結。這是例如放入500至900℃左右(必要時為1200℃)的燒結爐1至300秒進行燒結,而將鋁電極形成在太陽能電池單元的背面或矽面。又,亦可使用紅外線燈直接照射紅外線而進行燒結。該燒結時,特別是助劑之本發明的釩酸鹽玻璃熔融係堅固地固著在太陽能電池單元背面或矽面,同時亦堅強地固著在鋁粉末,能夠確認可發揮先前的玻璃粉末無法實現之較強的固著力。亦即,將引線焊接在藉由燒結而形成的鋁電極時,即便將該引線拉伸亦不會如先前地容易地剝離,而且經實驗確認固著強度為先前的數倍。 The S33 series performs aluminum sintering. For example, it is placed in a sintering furnace at about 500 to 900°C (1200°C if necessary) for sintering for 1 to 300 seconds, and the aluminum electrode is formed on the back surface or silicon surface of the solar cell. In addition, an infrared lamp may be used to directly irradiate infrared rays for sintering. During the sintering, the vanadate glass of the present invention, especially the additive, is firmly fixed on the back of the solar cell or on the silicon surface, and at the same time, is also firmly fixed on the aluminum powder. Achieve strong fixation. That is, when the lead wire is welded to the aluminum electrode formed by sintering, even if the lead wire is stretched, it is not easily peeled off as before, and it has been experimentally confirmed that the fixing strength is several times higher than before.
S34係進行室溫冷卻而完成。這是在S33進行鋁燒結之後,進行室溫冷卻而完成在太陽能電池背面、矽面形成鋁電極。 S34 is completed by cooling at room temperature. This is after aluminum sintering in S33 and cooling at room temperature to complete the formation of aluminum electrodes on the back and silicon surfaces of the solar cell.
如以上般,藉由將添加有本發明的釩酸鹽玻璃粉末作為助劑之鋁膏,塗佈在太陽能電池單元背面或 矽面(S31)、進行乾燥(S32)、其次進行煅燒(S33),而能夠在太陽能電池單元背面或矽面形成固著強度為先前數倍之堅強地固著的鋁電極。 As above, by applying the aluminum paste added with the vanadate glass powder of the present invention as an auxiliary agent on the back of the solar cell or The silicon surface (S31), drying (S32), and then calcining (S33) can form an aluminum electrode that is firmly fixed on the back surface or silicon surface of the solar cell with a fixing strength several times higher than before.
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