TWI614223B - BiO-TeO-SiO-WO glass - Google Patents
BiO-TeO-SiO-WO glass Download PDFInfo
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- TWI614223B TWI614223B TW105104999A TW105104999A TWI614223B TW I614223 B TWI614223 B TW I614223B TW 105104999 A TW105104999 A TW 105104999A TW 105104999 A TW105104999 A TW 105104999A TW I614223 B TWI614223 B TW I614223B
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- 239000011521 glass Substances 0.000 title claims description 109
- 239000000843 powder Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 34
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910052732 germanium Inorganic materials 0.000 claims description 15
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 15
- 239000004020 conductor Substances 0.000 claims description 14
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 13
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- -1 TeO 2 Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 230000003628 erosive effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 229910052715 tantalum Inorganic materials 0.000 description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 230000035515 penetration Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910020203 CeO Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910018245 LaO Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Inorganic materials [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Glass Compositions (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Description
本發明係關於一種Bi2O3-TeO2-SiO2-WO3系玻璃，特別是關於一種使用有該玻璃之結晶Si太陽電池。 The present invention relates to a Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass, and more particularly to a crystalline Si solar cell using the same.
通常之結晶Si太陽電池係於p型矽基板之一面設置有n型矽層之構造的半導體，且將該n型矽層側設為受光面，於該受光面側表面介隔氮化矽膜等抗反射膜而設置有與n型矽層連接之表面電極。進而，於上述p型矽基板之另一面設置背面電極，而提取藉由半導體之pn接合而產生之電力。上述抗反射膜係為了提高受光效率而設置，但另一方面，上述抗反射膜具有相對較高之電阻值，因此通常進行如下操作，即針對表面電極與n型矽層之接觸部分，藉由蝕刻或熔融而將該抗反射膜去除，而使n型矽層與表面電極之連接變良好。 A normal crystalline Si solar cell is a semiconductor having a structure in which an n-type germanium layer is provided on one surface of a p-type germanium substrate, and the n-type germanium layer side is a light receiving surface, and a tantalum nitride film is interposed on the light receiving surface side surface. A surface electrode connected to the n-type germanium layer is provided as an anti-reflection film. Further, a back electrode is provided on the other surface of the p-type germanium substrate, and electric power generated by pn junction of the semiconductor is extracted. The anti-reflection film is provided to improve the light-receiving efficiency. On the other hand, since the anti-reflection film has a relatively high resistance value, the operation is generally performed by the contact portion between the surface electrode and the n-type germanium layer. The antireflection film is removed by etching or melting, and the connection between the n-type germanium layer and the surface electrode is improved.
可使用稱為煅燒貫通(fire through)法之方法作為上述將抗反射膜去除之方法。所謂煅燒貫通法，係將表面電極之電極材料直接印刷至抗反射膜上後進行煅燒，藉此利用煅燒時之熱而將該抗反射膜熔融、去除之方法，且較佳為應用包含銀粉末、有機媒劑、及玻璃粉末材料(玻璃料等)之導電膏作為該電極材料(專利文獻1、2)。關於上述煅燒貫通法，已知其性能受上述電極材料之組成或煅燒溫度影響，但特別是受玻璃粉末材料之組成之影響。其原因在於：於煅燒導電膏時，玻璃粉末材料熔融而去除抗反射膜。因煅燒貫通法利用熱，故而要求為了抑制半導體之損傷、或提高作業效率，而降低所使用之玻璃粉末材 料之軟化點，例如於專利文獻3中，揭示有大量含有Li2O，且含有使玻璃為低軟化點之鉛之玻璃粉末材料。然而，於大量含有Li2O成分之情形時，Li擴散至n型矽層，結果存在使太陽電池之性能下降之可能性。 As a method of removing the antireflection film described above, a method called a fire through method can be used. The calcination penetration method is a method in which an electrode material of a surface electrode is directly printed on an antireflection film and then calcined, whereby the antireflection film is melted and removed by heat during firing, and preferably a silver powder is used. A conductive paste of an organic vehicle and a glass powder material (glass frit) is used as the electrode material (Patent Documents 1 and 2). Regarding the above-described calcination penetration method, it is known that the properties are affected by the composition of the above electrode material or the calcination temperature, but are particularly affected by the composition of the glass powder material. The reason for this is that when the conductive paste is fired, the glass powder material is melted to remove the antireflection film. Since the heat is used in the calcination penetration method, it is required to reduce the softening point of the glass powder material to be used in order to suppress the damage of the semiconductor or to improve the work efficiency. For example, Patent Document 3 discloses that Li 2 O is contained in a large amount and contains Glass is a glass powder material of lead with a low softening point. However, in the case where a large amount of the Li 2 O component is contained, Li diffuses to the n-type tantalum layer, and as a result, there is a possibility that the performance of the solar cell is lowered.
此處，作為玻璃粉末材料，使用有先前作為於低溫下可進行密封或被覆之玻璃而周知之粉末材料。作為此種玻璃粉末材料，眾所周知有於成分中含有鉛之PbO-B2O3系玻璃、PbO-B2O3-ZnO系玻璃、PbO-B2O3-Bi2O3系玻璃等。 Here, as the glass powder material, a powder material which has been conventionally known as a glass which can be sealed or coated at a low temperature is used. As such a glass powder material, PbO-B 2 O 3 -based glass, PbO-B 2 O 3 -ZnO-based glass, PbO-B 2 O 3 -Bi 2 O 3 -based glass containing lead in the composition is known.
例如，於專利文獻4中，揭示有於400~600℃下可密封之PbO-B2O3-ZnO-TeO2系玻璃粉末材料。又，於專利文獻5中，揭示有於500℃以下可密封之以PbO、B2O3、及TeO2為主成分之玻璃粉末材料，該玻璃粉末材料藉由於成分中含有TeO2而使玻璃穩定化。又，於專利文獻6中，揭示有於400℃以下可密封之PbO-B2O3-Bi2O3系玻璃粉末材料，該玻璃粉末材料藉由於成分中含有TeO2而提高玻璃之耐水性。 For example, Patent Document 4 discloses a PbO-B 2 O 3 -ZnO-TeO 2 -based glass powder material which is sealable at 400 to 600 ° C. Further, Patent Document 5 discloses a glass powder material containing PbO, B 2 O 3 , and TeO 2 as a main component which can be sealed at 500 ° C or lower, and the glass powder material is made of glass containing TeO 2 as a component. Stabilized. Further, Patent Document 6 discloses a PbO-B 2 O 3 -Bi 2 O 3 -based glass powder material which is sealable at 400 ° C or lower, and the glass powder material improves the water resistance of the glass by containing TeO 2 in the composition. .
[專利文獻1]日本專利特開昭62-49676號公報 [Patent Document 1] Japanese Patent Laid-Open No. 62-49676
[專利文獻2]日本專利特開2001-313400號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-313400
[專利文獻3]日本專利特開2012-015409號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-015409
[專利文獻4]日本專利特開昭62-36040號公報 [Patent Document 4] Japanese Patent Laid-Open No. 62-36040
[專利文獻5]日本專利特開平7-53237號公報 [Patent Document 5] Japanese Patent Laid-Open No. Hei 7-53237
[專利文獻6]日本專利特開平8-253344號公報 [Patent Document 6] Japanese Patent Laid-Open No. Hei 8-253344
如上所述，作為適於煅燒貫通法之玻璃粉末材料，要求有軟化點較低者。然而，另一方面，已知於使用有Bi2O3-TeO2系或PbO-TeO2 系等軟化點過低之玻璃粉末材料之情形時，有流動之玻璃不僅去除抗反射膜，亦侵蝕至n型矽層之虞。最近，有以提高轉換效率為目的而n型矽層變薄之傾向，因此存在由流動之玻璃導致之侵蝕變得更明顯之問題。 As described above, as the glass powder material suitable for the calcination penetration method, it is required to have a lower softening point. On the other hand, however, it is known that when a glass powder material having a softening point such as a Bi 2 O 3 -TeO 2 system or a PbO-TeO 2 system is used, the flowing glass not only removes the antireflection film but also erodes. To the n-type layer. Recently, there has been a tendency for the n-type tantalum layer to be thinned for the purpose of improving the conversion efficiency, and thus there is a problem that the erosion caused by the flowing glass becomes more conspicuous.
因此，本發明之目的在於獲得一種具有可作為結晶Si太陽電池之電極形成用導電膏而應用於煅燒貫通法之流動性，可抑制由流動之玻璃導致之n型矽層之侵蝕之玻璃。 In view of the above, it is an object of the present invention to obtain a glass which can be used as a conductive paste for electrode formation of a crystalline Si solar cell and which is applied to a calcination penetration method, and which can suppress erosion of an n-type tantalum layer caused by flowing glass.
通常，於藉由上述之煅燒貫通法而去除抗反射膜時，將電極材料加熱至800℃以上而煅燒電極材料中之玻璃粉末材料。關於粉末材料所使用之玻璃，要求其於煅燒時之流動性較高，但另一方面，流動性優異之玻璃係於去除抗反射膜後進而繼續流動，從而侵蝕n型矽層。本發明者等人基於上述見解而進行銳意研究，結果得知：若使用於成分中含有WO3與SiO2之玻璃，則可兼顧如下乍看相反之2種性質，即煅燒時之流動性與n型矽層之侵蝕之抑制。 Usually, when the antireflection film is removed by the above-described calcination penetration method, the electrode material is heated to 800 ° C or higher to calcine the glass powder material in the electrode material. The glass used for the powder material is required to have high fluidity at the time of firing, but on the other hand, the glass having excellent fluidity is continuously removed after the anti-reflection film is removed, thereby eroding the n-type layer. The present inventors conducted intensive studies based on the above findings, and as a result, it has been found that when the glass containing WO 3 and SiO 2 in the composition is used, it is possible to achieve the following two properties, that is, the fluidity at the time of calcination and The inhibition of the erosion of the n-type layer.
因此，本發明係一種Bi2O3-TeO2-SiO2-WO3系玻璃，其特徵在於：其係以Bi2O3、TeO2、SiO2、及WO3為必要成分者，且於該玻璃之成分中含有以質量%計30~60之Bi2O3、1~40之TeO2、1~20之SiO2、及1~20之WO3。 Therefore, the present invention is a Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass characterized in that Bi 2 O 3 , TeO 2 , SiO 2 , and WO 3 are essential components, and The glass component contains 30 to 60% by mass of Bi 2 O 3 , 1 to 40 of TeO 2 , 1 to 20 of SiO 2 , and 1 to 20 of WO 3 .
本發明之Bi2O3-TeO2-SiO2-WO3系玻璃係以Bi2O3、TeO2、SiO2、及WO3為必要成分之玻璃。又，除上述4種成分之必要成分以外，亦可以成為合計0~25質量%之範圍內之方式含有任意成分。 The Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass of the present invention is a glass containing Bi 2 O 3 , TeO 2 , SiO 2 , and WO 3 as essential components. In addition to the above-mentioned four components, the components may be contained in an amount of from 0 to 25% by mass in total.
作為上述任意成分，可列舉：ZnO、PbO、B2O3、Al2O3、R2O成分(K2O、Na2O、及Li2O)、及RO成分(MgO、CaO、SrO、及BaO)等調整玻璃軟化點或玻璃之穩定性之成分、或者V2O5、Sb2O5、ZrO2、Fe2O3、CuO、TiO2、In2O3、Bi2O3、LaO、CeO、NbO、及SnO2等以 提高玻璃之流動性或穩定性、表面電極之歐姆接觸為目的之成分。 Examples of the optional component include ZnO, PbO, B 2 O 3 , Al 2 O 3 , R 2 O components (K 2 O, Na 2 O, and Li 2 O), and RO components (MgO, CaO, and SrO). And BaO), etc., which adjust the softening point of the glass or the stability of the glass, or V 2 O 5 , Sb 2 O 5 , ZrO 2 , Fe 2 O 3 , CuO, TiO 2 , In 2 O 3 , Bi 2 O 3 LaO, CeO, NbO, and SnO 2 are components for the purpose of improving the fluidity or stability of the glass and the ohmic contact of the surface electrode.
又，上述任意成分中，於用作結晶Si太陽電池之電極形成用電極材料之情形時，為了如上所述般不使太陽電池之轉換效率下降，較佳為設為儘可能不含R2O成分之玻璃組成，例如較佳為設為10質量%以下。又，若含有B2O3，則有如下傾向，即存在作為受體元素對n型矽層發揮作用之情形，結果使太陽電池之性能下降，因此同樣地較佳為儘可能不含R2O成分，例如較佳為設為10質量%以下。 Further, in the case of using the electrode material for electrode formation of a crystalline Si solar cell, in order to prevent the conversion efficiency of the solar cell from being lowered as described above, it is preferable to contain R 2 O as much as possible. The glass composition of the component is preferably, for example, 10% by mass or less. Further, when B 2 O 3 is contained, there is a tendency that the acceptor element acts on the n-type germanium layer, and as a result, the performance of the solar cell is lowered. Therefore, it is preferable to contain R 2 as much as possible. The O component is preferably, for example, 10% by mass or less.
本發明可獲得一種具有可作為結晶Si太陽電池之電極形成用導電膏而進行應用之流動性，可抑制n型矽層之侵蝕之玻璃。 According to the present invention, it is possible to obtain a glass which has fluidity which can be used as a conductive paste for electrode formation of a crystalline Si solar cell and which can suppress erosion of the n-type tantalum layer.
1‧‧‧p型矽基板 1‧‧‧p type copper substrate
2‧‧‧n型矽層 2‧‧‧n type layer
3‧‧‧抗反射膜 3‧‧‧Anti-reflective film
4‧‧‧表面電極 4‧‧‧ surface electrode
5‧‧‧p+層 5‧‧‧p + layer
6‧‧‧鋁電極 6‧‧‧Aluminum electrode
圖1係表示結晶Si太陽電池之剖面之模式圖。 Fig. 1 is a schematic view showing a cross section of a crystalline Si solar cell.
本發明係一種Bi2O3-TeO2-SiO2-WO3系玻璃，其特徵在於：其係以Bi2O3、TeO2、SiO2、及WO3為必要成分者，且於該玻璃之成分中含有以質量%計30~60之Bi2O3、1~40之TeO2、1~20之SiO2、及1~20之WO3。 The present invention is a Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass characterized in that Bi 2 O 3 , TeO 2 , SiO 2 , and WO 3 are essential components, and the glass is The component contains 30 to 60% by mass of Bi 2 O 3 , 1 to 40 of TeO 2 , 1 to 20 of SiO 2 , and 1 to 20 of WO 3 .
本說明書中之所謂「流動性」，係將於下述之實施例中，將玻璃粉末材料之加壓成形體(2mm×10mm
又，對可抑制n型矽層之侵蝕之Bi2O3-TeO2-SiO2-WO3系玻璃進行評估，結果可知任一種玻璃於上述之流動性之評估後均發生結晶化。預測該結晶化係於煅燒過程中慢慢地發生。因此，將於流動性之評估試驗後發生結晶化者設為可抑制n型矽層之侵蝕。再者，抑制n型矽層之侵蝕之機制並不確定，但根據上述內容中顯現出之結果，推測其原因在於：由於加熱一定時間後發生結晶化而玻璃之流動停止。 Further, the Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass which can suppress the erosion of the n-type tantalum layer was evaluated, and as a result, it was found that any of the glasses was crystallized after the evaluation of the fluidity described above. It is predicted that this crystallization will occur slowly during the calcination process. Therefore, it is assumed that crystallization occurs after the fluidity evaluation test can suppress the erosion of the n-type ruthenium layer. Further, the mechanism for suppressing the erosion of the n-type tantalum layer is not certain, but based on the results revealed in the above, it is presumed that the reason is that the flow of the glass stops due to crystallization after heating for a certain period of time.
於將上述Bi2O3-TeO2-SiO2-WO3系玻璃用作結晶Si太陽電池之電極材料之情形時，就電極圖案之形成容易度而言，較理想為以粉末狀之玻璃粉末材料之形式使用。 When the above Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass is used as an electrode material of a crystalline Si solar cell, it is preferable to use a powdery glass powder in terms of ease of formation of the electrode pattern. The form of the material is used.
上述玻璃粉末材料較佳為平均粒徑D50為5μm以下。近年來，以增大太陽光之入射面積為目的而使電極圖案高精細化。藉由將平均粒徑D50設為5μm以下，可形成更高精細之電極圖案，其結果為，太陽電池之光電轉換效率提高。又，上述平均粒徑D50之下限值並無特別限定，例如亦可設為0.1μm以上。為了使該玻璃粉末材料為上述範圍內，亦可使用乳缽或球磨機、及噴射研磨方式之粉碎機等。再者，於本說明書之實施例中，以平均粒徑D50成為上述0.1~5μm之範圍內之方式進行粉碎。平均粒徑係使用日機裝股份有限公司製造之Microtrac MT3000，藉由雷射繞射、散射法而進行測定。具體而言，將於使玻璃粉末材料分散至溶劑後照射雷射光而獲得之粒度分佈之累計值50%時之粒徑的值設為平均粒徑D50。 The glass powder material preferably has an average particle diameter D 50 of 5 μm or less. In recent years, the electrode pattern has been made highly refined for the purpose of increasing the incident area of sunlight. By setting the average particle diameter D 50 to 5 μm or less, a finer electrode pattern can be formed, and as a result, the photoelectric conversion efficiency of the solar cell is improved. Further, the lower limit of the average particle diameter D 50 is not particularly limited, and may be, for example, 0.1 μm or more. In order to make the glass powder material within the above range, a mortar or a ball mill, a jet mill type pulverizer or the like may be used. Further, in the examples of the present specification, the pulverization is carried out so that the average particle diameter D 50 is in the range of 0.1 to 5 μm. The average particle diameter was measured by a laser diffraction or scattering method using a Microtrac MT3000 manufactured by Nikkiso Co., Ltd. Specifically, the value of the particle diameter when the cumulative value of the particle size distribution obtained by irradiating the glass powder material to the solvent and irradiated with the laser light is 50% is defined as the average particle diameter D 50 .
以下，對本發明之Bi2O3-TeO2-SiO2-WO3系玻璃之各成分進行記載。 Hereinafter, each component of the Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass of the present invention will be described.
Bi2O3係構成玻璃骨架之成分之一，且係對玻璃賦予流動性而提高去除抗反射膜之效果(以下，亦存在記載為「燒透性」之情形)之成分，於玻璃中以30~60質量%含有。若未達30質量%，則無法發揮其作用，若超過60質量%，則偏離玻璃化範圍而於玻璃原料之熔融時變得易於結晶化。較佳為亦可將下限值設為35質量%以上，將上限值設為55質量%以下。 Bi 2 O 3 is one of the components of the glass skeleton, and is a component which imparts fluidity to the glass and improves the effect of removing the antireflection film (hereinafter, also referred to as "burning property"). 30 to 60% by mass. If it is less than 30% by mass, the effect is not exhibited. When it exceeds 60% by mass, the glassy range is deviated and the crystallization of the glass raw material is facilitated. The lower limit is preferably 35 mass% or more, and the upper limit is 55 mass% or less.
TeO2係與Bi2O3同樣地對玻璃賦予流動性而提高燒透性之成分，於玻璃中以1~40質量%含有。又，上述TeO2係於煅燒時使銀等導電性材料良好地熔解，進而於與n型矽層之界面附近促進導電性材料之再結晶化之成分。藉此，表面電極與n型矽層之接觸電阻下降，光電 轉換效率提高。若未達1質量%，則無法發揮其作用，若超過40質量%，則偏離玻璃化範圍而於玻璃原料之熔融時變得易於結晶化。較佳為亦可將下限值設為3質量%以上、更佳為5質量%以上，將上限值設為35質量%以下。 In the same manner as the Bi 2 O 3 , the TeO 2 is a component which imparts fluidity to the glass and improves the fire-through property, and is contained in the glass in an amount of 1 to 40% by mass. Further, the above-mentioned TeO 2 is a component which satisfactorily melts a conductive material such as silver during firing, and further promotes recrystallization of the conductive material in the vicinity of the interface with the n-type tantalum layer. Thereby, the contact resistance between the surface electrode and the n-type germanium layer is lowered, and the photoelectric conversion efficiency is improved. If it is less than 1% by mass, the effect is not exhibited. When it exceeds 40% by mass, the glassy range is deviated and the crystallization of the glass raw material is facilitated. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and the upper limit is made 35% by mass or less.
SiO2係構成玻璃骨架之成分之一，且係調整煅燒時之流動性之成分。藉此，可抑制n型矽層之侵蝕。於本發明中，以1~20質量%之範圍含有該SiO2。若未達1質量%，則玻璃易於變得不穩定，若超過20質量%，則玻璃之軟化點上升而不適於本發明之目的。較佳為亦可將下限值設為2質量%以上、更佳為5質量%以上，將上限值設為18質量%以下、更佳為16質量%以下之範圍。 SiO 2 is one of the components of the glass skeleton and is a component that adjusts the fluidity at the time of firing. Thereby, the erosion of the n-type ruthenium layer can be suppressed. In the present invention, the SiO 2 is contained in an amount of from 1 to 20% by mass. If it is less than 1% by mass, the glass tends to be unstable, and if it exceeds 20% by mass, the softening point of the glass rises and is not suitable for the purpose of the present invention. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, and the upper limit is 18% by mass or less, and more preferably 16% by mass or less.
WO3係於煅燒時促進結晶化之成分之一，且以1~20質量%之範圍含有。於煅燒時去除抗反射膜後，該WO3於與玻璃所含有之Bi2O3之間引起結晶化。若未達1質量%時，則無法發揮其作用，又，若超過20質量%，則玻璃變得不穩定。較佳為亦可將下限值設為2質量%以上、更佳為5質量%以上，將上限值設為18質量%以下、更佳為16質量%以下。 WO 3 is one of the components which promote crystallization at the time of calcination, and is contained in the range of 1 to 20% by mass. After the antireflection film is removed during calcination, the WO 3 causes crystallization between the Bi 2 O 3 contained in the glass. If it is less than 1% by mass, the effect is not exhibited, and if it exceeds 20% by mass, the glass becomes unstable. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, and the upper limit is 18% by mass or less, and more preferably 16% by mass or less.
如上所述，本發明之玻璃粉末材料係以Bi2O3、TeO2、SiO2、及WO3為必要成分之Bi2O3-TeO2-SiO2-WO3系玻璃，且係藉由以Bi2O3及TeO2為主成分而具有較高之燒透性，並藉由向其中添加SiO2及WO3而可抑制n型矽層之侵蝕者。除上述4種成分之必要成分以外，亦可以成為0~25質量%之範圍內之方式含有任意成分。 As described above, the glass powder material of the present invention is Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass containing Bi 2 O 3 , TeO 2 , SiO 2 , and WO 3 as essential components, and Bi 2 O 3 and TeO 2 are mainly contained, and have high fire-through property, and by adding SiO 2 and WO 3 thereto, it is possible to suppress the erosion of the n-type ruthenium layer. In addition to the essential components of the above four components, the component may be contained in an amount of from 0 to 25% by mass.
作為上述之任意成分，如上所述，可列舉ZnO、PbO、B2O3、Al2O3、R2O成分(K2O、Na2O、及Li2O)、RO成分(MgO、CaO、SrO、及BaO)、V2O5、Sb2O5、ZrO2、Fe2O3、CuO、TiO2、In2O3、Bi2O3、LaO、CeO、NbO、及SnO2等。 Examples of the optional components include ZnO, PbO, B 2 O 3 , Al 2 O 3 , R 2 O components (K 2 O, Na 2 O, and Li 2 O), and RO components (MgO, as described above). CaO, SrO, and BaO), V 2 O 5 , Sb 2 O 5 , ZrO 2 , Fe 2 O 3 , CuO, TiO 2 , In 2 O 3 , Bi 2 O 3 , LaO, CeO, NbO, and SnO 2 Wait.
又，作為本發明之較佳之實施形態之一，較佳為含有合計0.1~ 25質量%之任意成分，且該任意成分為選自由ZnO、PbO、B2O3、Al2O3、R2O成分(選自由K2O、Na2O、及Li2O所組成之群中之至少1種)、及RO成分(選自由MgO、CaO、SrO、及BaO所組成之群中之至少1種)所組成之群中之至少1種。 Further, as one of preferred embodiments of the present invention, it is preferable to contain an optional component of 0.1 to 25 mass% in total, and the optional component is selected from the group consisting of ZnO, PbO, B 2 O 3 , Al 2 O 3 , and R 2 . The O component (selected from at least one of the group consisting of K 2 O, Na 2 O, and Li 2 O) and the RO component (selected from at least 1 selected from the group consisting of MgO, CaO, SrO, and BaO) At least one of the group consisting of.
ZnO係使玻璃之軟化點下降之成分，且亦可於0~15質量%之範圍內含於玻璃組成中。若超過15質量%，則偏離玻璃化範圍而於玻璃原料之熔融時變得易於結晶化。 ZnO is a component which lowers the softening point of the glass, and may be contained in the glass composition in the range of 0 to 15% by mass. When it exceeds 15% by mass, it deviates from the vitrification range and becomes easy to crystallize when the glass raw material is melted.
PbO係對玻璃賦予流動性而提高燒透性之成分，且亦可於0~15質量%之範圍內含於玻璃組成中。若超過15質量%，則流動性變得過大而變得易於侵蝕n型矽層。 PbO is a component which imparts fluidity to glass and improves the fire-through property, and may be contained in the glass composition in the range of 0 to 15% by mass. When it exceeds 15% by mass, the fluidity becomes too large and it becomes easy to erode the n-type layer.
B2O3係構成玻璃骨架之成分之一，可藉由含於玻璃組成中而形成穩定之玻璃。於本發明中，亦可於0~10質量%之範圍內含有該B2O3。若超過10質量%，則如上所述般存在作為受體元素對n型矽層發揮作用之情形，結果光電轉換效率變得易於下降。 The B 2 O 3 system constitutes one of the components of the glass skeleton and can be formed into a stable glass by being contained in the glass composition. In the present invention, the B 2 O 3 may be contained in the range of 0 to 10% by mass. When it exceeds 10 mass%, as described above, the role as an acceptor element acts on the n-type germanium layer, and as a result, the photoelectric conversion efficiency is liable to lower.
Al2O3係抑制玻璃之結晶化之成分，且亦可於10質量%以下之範圍內含於玻璃組成中。若超過10質量%，則會損害玻璃之流動性，故而不適於本發明之目的。 The Al 2 O 3 system suppresses the crystallization of the glass, and may be contained in the glass composition in a range of 10% by mass or less. If it exceeds 10% by mass, the fluidity of the glass is impaired, and it is not suitable for the purpose of the present invention.
R2O成分係使玻璃之軟化點下降之成分，且亦可於Li2O、Na2O、及K2O之合計為0~10質量%之範圍內含於玻璃組成中。又，該R2O成分可使用1種成分，亦可使用複數種成分。另一方面，若如上所述般超過10質量%，則鹼金屬向n型矽層擴散，故而不適於本發明之目的。 The R 2 O component is a component which lowers the softening point of the glass, and may be contained in the glass composition in a range of 0 to 10% by mass in total of Li 2 O, Na 2 O, and K 2 O. Further, as the R 2 O component, one component may be used, or a plurality of components may be used. On the other hand, if it exceeds 10% by mass as described above, the alkali metal diffuses into the n-type ruthenium layer, which is not suitable for the purpose of the present invention.
RO成分係抑制玻璃之結晶化之成分，且亦可於MgO、CaO、SrO、及BaO之合計為10質量%以下之範圍內含於玻璃組成中。又，該RO成分可使用1種成分，亦可使用複數種成分。若超過10質量%，則玻璃之軟化點上升，故而不適於本發明之目的。 The RO component is a component that suppresses the crystallization of the glass, and may be contained in the glass composition in a range of 10% by mass or less based on the total of MgO, CaO, SrO, and BaO. Further, one component may be used as the RO component, and a plurality of components may be used. If it exceeds 10% by mass, the softening point of the glass rises, which is not suitable for the purpose of the present invention.
又，除上述成分以外，只要為不損害本發明之Bi2O3-TeO2-SiO2-WO3系玻璃之性質之範圍內，則亦可以提高玻璃之流動性或穩定性、歐姆接觸等為目的，於5質量%以下之範圍內添加ZrO2、Fe2O3、CuO、TiO2、In2O3、P2O5、V2O5、Sb2O3、La2O3、CeO2、Nb2O5、及SnO2等作為任意成分。 Further, in addition to the above components, the fluidity, stability, ohmic contact, etc. of the glass can be improved as long as the properties of the Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass of the present invention are not impaired. For the purpose of adding 5% by mass or less, ZrO 2 , Fe 2 O 3 , CuO, TiO 2 , In 2 O 3 , P 2 O 5 , V 2 O 5 , Sb 2 O 3 , La 2 O 3 , CeO 2 , Nb 2 O 5 , and SnO 2 are optional components.
又，本發明之較佳之實施形態之一係於玻璃內含有導電性材料的Bi2O3-TeO2-SiO2-WO3系玻璃。該實施形態可列舉於玻璃內部分散有導電性材料之形態、或者於玻璃內部或表面形成有導電性材料之層之形態等。具體而言，例如可藉由於混合玻璃粉末材料與導電性材料後進行煅燒而獲得，且可用作電極構件等。 Further, a preferred embodiment of the present invention is a Bi 2 O 3 -TeO 2 -SiO 2 -WO 3 -based glass containing a conductive material in the glass. This embodiment is exemplified by a form in which a conductive material is dispersed in the glass or a layer in which a conductive material is formed inside or on the surface of the glass. Specifically, it can be obtained, for example, by mixing a glass powder material and a conductive material, followed by calcination, and can be used as an electrode member or the like.
上述導電性材料只要為具有導電性者即可，並無特別限定，較佳為選自由導電性優異之Ag、Au、Pd、Ni、Cu、Al及Pt所組成之群中之至少1種。 The conductive material is not particularly limited as long as it has conductivity, and is preferably at least one selected from the group consisting of Ag, Au, Pd, Ni, Cu, Al, and Pt having excellent conductivity.
又，本發明之較佳之實施形態之一係一種導電膏，其特徵在於含有：上述玻璃粉末材料、有機媒劑、及導電性材料。 Further, a preferred embodiment of the present invention is a conductive paste comprising: the glass powder material, an organic vehicle, and a conductive material.
導電膏中所含之玻璃粉末材料較佳為相對於導電性材料100質量%設為1~20質量%之範圍內。若超過20質量%，則存在電極之電阻變得過高之情形。又，若未達1質量%，則存在玻璃成分不足，而無法形成緻密之電極之情形。 The glass powder material contained in the conductive paste is preferably in the range of 1 to 20% by mass based on 100% by mass of the conductive material. If it exceeds 20% by mass, the electric resistance of the electrode may become too high. When the amount is less than 1% by mass, the glass component may be insufficient to form a dense electrode.
導電膏中所使用之導電性材料係與上述導電性材料同樣地，較佳為選自由具有良好之導電性之Ag、Au、Pd、Ni、Cu、Al及Pt所組成之群中之至少1種。又，為了使導電膏之塗佈或煅燒變得容易，該導電性材料較理想為粉末狀之導電性粉末。 The conductive material used in the conductive paste is preferably at least one selected from the group consisting of Ag, Au, Pd, Ni, Cu, Al, and Pt having good conductivity, similarly to the conductive material. Kind. Moreover, in order to facilitate the application or baking of the conductive paste, the conductive material is preferably a powdery conductive powder.
有機媒劑係包含有機溶劑與有機黏合劑者，且係於對導電膏進行加熱、煅燒後因燃燒、分解、或揮發等而消失者。再者，所謂有機黏合劑，係使玻璃粉末材料分散、擔持至導電膏中者。有機溶劑及有 機黏合劑只要適當選擇即可，且只要可於加熱時自導電膏去除即可，無特別限定。 The organic vehicle includes an organic solvent and an organic binder, and is a method in which the conductive paste is heated, calcined, and then disappeared by combustion, decomposition, or volatilization. Further, the organic binder is one in which the glass powder material is dispersed and carried to the conductive paste. Organic solvent and The organic binder may be appropriately selected as long as it can be removed from the conductive paste upon heating, and is not particularly limited.
又，本發明之較佳之實施形態之一係一種結晶Si太陽電池之製造方法，其特徵在於含有如下步驟：於形成於n型矽層上之抗反射膜上塗佈上述導電膏作為表面電極形成用材料之步驟；將該導電膏加熱至800℃以上之步驟；及藉由煅燒貫通法而去除上述抗反射膜之步驟。 Moreover, a preferred embodiment of the present invention is a method for producing a crystalline Si solar cell, comprising the steps of: coating the conductive paste on the anti-reflection film formed on the n-type germanium layer as a surface electrode; a step of using a material; a step of heating the conductive paste to 800 ° C or higher; and a step of removing the anti-reflection film by a calcination through method.
於圖1中表示結晶Si太陽電池之剖面之模式圖。以下，記載結晶Si太陽電池之製造方法之一例。 A schematic view of a cross section of a crystalline Si solar cell is shown in FIG. Hereinafter, an example of a method for producing a crystalline Si solar cell will be described.
關於結晶Si太陽電池，係首先於p型矽基板1上塗佈硼擴散劑及磷擴散劑，進行加熱或離子注入等，藉此形成p+層5、n型矽層2。 In the crystalline Si solar cell, a boron diffusion agent and a phosphorus diffusion agent are first applied onto the p-type germanium substrate 1, and heating or ion implantation is performed to form a p + layer 5 and an n-type germanium layer 2.
其次，於所形成之n型矽層2上形成抗反射膜3。作為該抗反射膜3，可列舉通常使用之氮化矽等。 Next, an anti-reflection film 3 is formed on the formed n-type germanium layer 2. Examples of the antireflection film 3 include tantalum nitride or the like which is usually used.
其次，於p+層5上形成作為背面電極之鋁電極6。鋁電極可藉由塗佈含有鋁粉末之膏等並進行燒付而形成。 Next, an aluminum electrode 6 as a back electrode is formed on the p + layer 5. The aluminum electrode can be formed by applying a paste containing aluminum powder or the like and baking it.
其次，於抗反射膜3上塗佈導電膏。該導電膏係為了於煅燒後成為表面電極4而塗佈成所期望之形狀。塗佈方法只要使用既存者即可，例如若使用網版印刷，則亦可較佳地進行圖案形成，故而較為有用。於塗佈該導電膏後，加熱至800℃以上。此時，導電膏內所含之有機媒劑被去除，同時發生玻璃粉末材料之煅燒及表面電極4之部分之抗反射膜3的去除，從而獲得與n型矽層連接之表面電極4。 Next, a conductive paste is applied onto the anti-reflection film 3. This conductive paste is applied to a desired shape in order to form the surface electrode 4 after firing. The coating method can be used as long as it is used. For example, if screen printing is used, pattern formation can be preferably performed, which is useful. After coating the conductive paste, it is heated to 800 ° C or higher. At this time, the organic vehicle contained in the conductive paste is removed, and at the same time, the glass powder material is calcined and the anti-reflection film 3 of the surface electrode 4 is removed, thereby obtaining the surface electrode 4 connected to the n-type layer.
[實施例] [Examples]
實施例1~6 Examples 1 to 6
首先，以成為表1所記載之特定組成之方式稱量各種無機原料，進行混合而製作原料批料。將該原料批料投入至白金坩堝中，於電加熱爐內以1000~1200℃加熱熔融1~2小時而獲得表1之實施例1~6所示之組成之玻璃。所獲得之玻璃係利用急冷雙輥成形機而製成鱗片 狀，於粉碎裝置中整粒成平均粒徑為1~5μm、最大粒徑未達20μm之粉末狀而獲得玻璃粉末材料。 First, various inorganic raw materials were weighed so as to have a specific composition shown in Table 1, and mixed to prepare a raw material batch. The raw material batch was placed in a platinum crucible, and heated and melted at 1000 to 1200 ° C for 1 to 2 hours in an electric heating furnace to obtain glasses of the compositions shown in Examples 1 to 6 of Table 1. The obtained glass is made into a scale by a quenching twin roll forming machine In the pulverization apparatus, a glass powder material is obtained by granulating into a powder having an average particle diameter of 1 to 5 μm and a maximum particle diameter of less than 20 μm.
又，針對玻璃粉末材料，使用手壓機加壓成形為2mm×10mm
比較例1~5 Comparative example 1~5
以成為表2所記載之特定組成之方式稱量各種無機原料，進行混合而製作原料批料，除此之外，利用與實施例相同之方法進行玻璃之 製作。然而，關於比較例1，因未玻璃化，故而未進行流動性之評估，關於比較例2、3、5，係流動不充分。又，關於比較例4，雖係流動性良好且適於煅燒貫通法者，但未發生結晶化，故而推測不適於抑制n型矽層之侵蝕。 The various inorganic raw materials were weighed so as to have a specific composition shown in Table 2, and mixed to prepare a raw material batch, and the glass was used in the same manner as in the examples. Production. However, in Comparative Example 1, since the fluidity was not evaluated because it was not vitrified, the flow of the comparative examples 2, 3, and 5 was insufficient. Further, in Comparative Example 4, although the fluidity was good and it was suitable for the calcination penetration method, since crystallization did not occur, it was estimated that it was not suitable for suppressing the erosion of the n-type tantalum layer.
如實施例1~6所示般，可知於本發明之組成範圍內，玻璃之流動性良好，且亦未發現高溫時之結晶化，因此可作為結晶Si太陽電池之表面電極形成用導電膏進行應用。另一方面，比較例1~5成為未玻璃化、流動性較低、或雖流動性較高但未結晶化等不適於本發明之目的者。 As shown in Examples 1 to 6, it is understood that the fluidity of the glass is good in the composition range of the present invention, and crystallization at a high temperature is not observed, so that it can be used as a conductive paste for forming a surface electrode of a crystalline Si solar cell. application. On the other hand, Comparative Examples 1 to 5 were not vitrified, have low fluidity, or were not crystallized, and were not suitable for the purpose of the present invention.
1‧‧‧p型矽基板 1‧‧‧p type copper substrate
2‧‧‧n型矽層 2‧‧‧n type layer
3‧‧‧抗反射膜 3‧‧‧Anti-reflective film
4‧‧‧表面電極 4‧‧‧ surface electrode
5‧‧‧p+層 5‧‧‧p + layer
6‧‧‧鋁電極 6‧‧‧Aluminum electrode
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| JP6714275B2 (en) * | 2016-08-23 | 2020-06-24 | ナミックス株式会社 | Conductive paste and solar cell |
| CN106448803A (en) * | 2016-08-31 | 2017-02-22 | 王立建 | Hole-poured electronic slurry for back contact solar cell |
| CN106128554B (en) * | 2016-09-23 | 2017-10-13 | 苏州柏特瑞新材料有限公司 | A kind of anti-aging crystal silicon solar batteries back electrode silver paste |
| TWI745562B (en) * | 2017-04-18 | 2021-11-11 | 美商太陽帕斯特有限責任公司 | Conductive paste composition and semiconductor devices made therewith |
| CN107195354B (en) * | 2017-04-20 | 2019-02-26 | 广东爱康太阳能科技有限公司 | A kind of back passivation silicon solar cell positive electrode silver paste and preparation method thereof |
| CN106972081B (en) * | 2017-05-18 | 2018-06-26 | 阳光中科（福建）能源股份有限公司 | A kind of preparation method of white solar cell |
| CN107162426A (en) * | 2017-06-21 | 2017-09-15 | 苏州卡睿知光电科技有限公司 | A kind of glass capsulation material, sealing material paste and preparation method thereof |
| CN107265872B (en) * | 2017-07-10 | 2020-08-04 | 上海银浆科技有限公司 | Double-component lead-free glass powder suitable for front silver paste of crystalline silicon battery |
| US10040717B1 (en) * | 2017-09-18 | 2018-08-07 | Jiangxi Jiayin Science and Technology, Ltd. | Thick-film paste with multiple discrete frits and methods for contacting crystalline silicon solar cell emitter surfaces |
| CN111268915B (en) * | 2018-12-04 | 2023-02-03 | 上海银浆科技有限公司 | Bi-component high-contact glass powder for solar front silver paste |
| CN109659066B (en) * | 2019-01-10 | 2020-04-17 | 四川东树新材料有限公司 | Front silver paste for preparing PERC silicon solar cell |
| CN109694202A (en) * | 2019-01-20 | 2019-04-30 | 江苏正能电子科技有限公司 | A kind of back passivated battery silver paste glass powder |
| CN111875254A (en) * | 2020-07-27 | 2020-11-03 | 上海银浆科技有限公司 | Lead-free glass powder suitable for front silver paste of black silicon + perc battery and preparation method thereof |
| CN116062999A (en) * | 2022-12-12 | 2023-05-05 | 广州市儒兴科技股份有限公司 | Glass powder combination and preparation method thereof, electronic paste and battery |
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