WO2015037933A1 - 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극 - Google Patents
태양전지 전극 형성용 조성물 및 이로부터 제조된 전극 Download PDFInfo
- Publication number
- WO2015037933A1 WO2015037933A1 PCT/KR2014/008510 KR2014008510W WO2015037933A1 WO 2015037933 A1 WO2015037933 A1 WO 2015037933A1 KR 2014008510 W KR2014008510 W KR 2014008510W WO 2015037933 A1 WO2015037933 A1 WO 2015037933A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- glass frit
- solar cell
- composition
- cell electrode
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000011521 glass Substances 0.000 claims abstract description 72
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- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 9
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 229910020185 Pb—Bi—Te—O Inorganic materials 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 5
- -1 defoamers Substances 0.000 claims description 5
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- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 3
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- 238000002844 melting Methods 0.000 description 6
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- 229910052709 silver Inorganic materials 0.000 description 5
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- 238000002156 mixing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
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- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/80—Constructional details
- H10K10/82—Electrodes
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- 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
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/14—Compositions for glass with special properties for electro-conductive glass
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- 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
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- 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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- 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
- C03C2204/00—Glasses, glazes or enamels with special properties
-
- 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
- C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
-
- 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
Definitions
- the present invention relates to a solar cell electrode cell forming composition and an electrode prepared therefrom.
- the short-circuit current density Jsc is a current density in the reverse direction (negative value) which appears when light is received in a short-circuit state, that is, in the absence of external resistance. This value primarily depends on the intensity and spectral distribution of the incident light. However, in the state where such a condition is determined, it depends on how effectively the electrons and holes excited by the light absorption are recombined and lost, and are effectively sent from the inside of the cell to the external circuit. In this case, the loss due to recombination may occur inside the material or at the interface.
- An object of the present invention is to provide a solar cell electrode cell formation composition having a high open voltage and short circuit current density.
- Another object of the present invention is to provide a solar cell electrode cell formation composition having excellent conversion efficiency and fill factor value.
- One aspect of the invention is a silver powder; Glass frit; And an organic vehicle, wherein the glass frit has a glass transition temperature of about 100 ° C. to about 300 ° C., and an onset temperature at which an exothermic peak appears on a DTA curve upon thermogravimetric / differential heat (TG-DTA) analysis is about 200 ° C. It relates to a composition for forming a solar cell electrode that is from about 400 °C.
- the glass frit may be a leaded glass frit.
- the glass frit may include one or more of Pb-Bi-Te-O-based glass frit and Ag-V-Pb-O-based glass frit.
- the Pb-Bi-Te-O-based glass frit includes about 10 wt% to about 70 wt% of lead oxide (PbO), about 1 wt% to about 20 wt% of bismuth oxide (Bi 2 O 3 ), and tellurium oxide (TeO). 2 ) about 10% to about 70% by weight, wherein the Ag-V-Pb-O-based glass frit comprises about 10% to about 60% by weight silver oxide (Ag 2 O), vanadium oxide (V 2 O 5 ) About 10% to about 40% by weight and about 10% to about 60% by weight lead oxide (PbO).
- the glass frit is silicon oxide (SiO 2 ), barium oxide (BaO), vanadium oxide (V 2 O 5 ), phosphorus oxide (P 2 O 5 ), magnesium oxide (MgO), cerium oxide (CeO 2 ), boron oxide (B 2 O 3 ), strontium oxide (SrO), molybdenum oxide (MoO 3 ), titanium oxide (TiO 2 ), tin oxide (SnO), indium oxide (In 2 O 3 ), nickel oxide (NiO), copper oxide (Cu 2 O or CuO), antimony oxide (Sb 2 O 3 , Sb 2 O 4 or Sb 2 O 5 ), germanium oxide (GeO 2 ), gallium oxide (Ga 2 O 3 ), calcium oxide (CaO), oxide Arsenic (As 2 O 3 ), cobalt oxide (CoO or Co 2 O 3 ), zirconium oxide (ZrO 2 ), manganese oxide (MnO, Mn 2 O 3 or Mn 3 O 4 ), n
- the composition for forming a solar cell electrode may be about 60 wt% to about 95 wt% silver powder; From about 0.5% to about 20% by weight of the glass frit; And about 1% to about 30% by weight of the organic vehicle.
- the glass frit may have an average particle diameter (D50) of about 0.1 ⁇ m to about 10 ⁇ m.
- composition may further include one or more additives selected from the group consisting of dispersants, thixotropic agents, plasticizers, viscosity stabilizers, antifoams, pigments, ultraviolet stabilizers, antioxidants and coupling agents.
- additives selected from the group consisting of dispersants, thixotropic agents, plasticizers, viscosity stabilizers, antifoams, pigments, ultraviolet stabilizers, antioxidants and coupling agents.
- the solar cell electrode which is another aspect of the present invention may be formed from the solar cell electrode forming composition.
- the solar cell electrode manufactured from the solar cell electrode forming film composition of the present invention has high open-circuit voltage and short-circuit current density, and thus has excellent conversion efficiency and fill factor value.
- FIG. 1 is a schematic diagram schematically showing the structure of a solar cell according to an embodiment of the present invention.
- Figure 2 shows a graph of the DTA curve obtained by analyzing the thermogravimetric and differential thermal (TG-DTA) of the glass frit.
- the present invention is a silver powder; Glass frit; And it relates to a composition for forming a solar cell electrode comprising an organic vehicle.
- the glass frit has a glass transition temperature of about 100 ° C. to about 300 ° C., and an onset temperature at which exothermic peaks appear on a DTA curve upon thermogravimetric / differential heat (TG-DTA) analysis.
- the solar cell electrode manufactured from the solar cell electrode cell forming composition according to the embodiments of the present invention has high open voltage and high short-circuit current density, and thus has excellent conversion efficiency and fill factor value.
- the present invention will be described in detail.
- the photovoltaic composition for forming a solar cell electrode of the present invention uses silver (Ag) powder as the conductive powder.
- the silver powder may be a powder having a particle size of nano size or micro size.
- it may be a silver powder of several tens to hundreds of nanometers, a silver powder of several tens of micrometers, and may be used by mixing two or more kinds of silver powders having different sizes.
- the silver powder may have a spherical shape, a plate shape, or an amorphous shape.
- the average particle diameter (D50) of the silver powder is specifically about 0.1 ⁇ m to about 10 ⁇ m, and more specifically about 0.5 ⁇ m to about 5 ⁇ m.
- the average particle diameter was measured using a 1064LD model manufactured by CILAS after dispersing the conductive powder in isopropyl alcohol (IPA) at 25 ° C. for 3 minutes with ultrasonic waves. Within this range, the contact resistance and the wire resistance can be lowered.
- IPA isopropyl alcohol
- Silver powder may comprise from about 60% to about 95% by weight relative to the total weight of the composition. Within this range, it is possible to prevent the conversion efficiency from lowering due to an increase in the resistance. Specifically, the silver powder may be included in about 70% by weight to about 90% by weight.
- the glass frit may etch the anti-reflection film during the firing process of the electrode paste, and may generate silver crystal grains in the emitter region to melt the silver particles to lower the resistance.
- the adhesion between the conductive powder and the wafer is improved and softened during sintering, thereby inducing the effect of lowering the firing temperature.
- the glass frit of the present invention may be a low melting glass frit.
- the low melting point crystalline glass frit may have a glass transition temperature of about 100 ° C to about 300 ° C.
- the glass frit may have an onset temperature at which exothermic peaks appear on a DTA curve during thermogravimetric and differential thermal (TG-DTA) analysis, about 200 ° C. to about 400 ° C.
- the onset temperature means a temperature at which the first exothermic peak is expressed.
- the exothermic peak may be one or more, and when a plurality of exothermic peaks are expressed on the DTA curve, the first exothermic peak may appear in the range of about 200 ° C to about 400 ° C.
- Figure 2 shows a graph of the DTA curve of the glass frit according to an embodiment of the present invention showing an example in which the onset temperature of the exothermic peak on the DTA curve is 283.5 °C.
- thermogravimetric / differential thermal analysis (TG-DTA) analysis can measure the endotherm and the exothermic temperature, respectively, through the exothermic or endothermic peaks on the DTA curve that appear when the glass frit is heated up to 600 ° C. at a heating rate of 20 ° C./min.
- TG-DTA thermogravimetric / differential thermal analysis
- the glass frit may be, for example, leaded glass frit. In this case, excellent conversion efficiency can be ensured.
- the glass frit may be, for example, a low melting crystalline glass frit. In this case, the adhesive force with the ribbon can be secured.
- the glass frit may be a Pb-Bi-Te-O-based glass frit.
- the Pb-Bi-Te-O-based glass frit includes about 10 wt% to about 70 wt% of lead oxide (PbO), about 1 wt% to about 20 wt% of bismuth oxide (Bi 2 O 3 ), and tellurium oxide (TeO). 2 ) about 10% to about 70% by weight.
- the glass frit may be an Ag-V-Pb-O-based glass frit.
- the Ag-V-Pb-O-based glass frit includes about 10 wt% to about 60 wt% of silver oxide (Ag 2 O), about 10 wt% to about 40 wt% of vanadium oxide (V 2 O 5 ) and lead oxide (PbO). ) From about 10% to about 60% by weight.
- the Ag-V-Pb-O-based glass frit comprises about 20 wt% to about 45 wt% silver oxide (Ag 2 O), about 10 wt% to about 30 wt% vanadium oxide (V 2 O 5 ) And about 40 wt% to about 60 wt% lead oxide (PbO).
- the weight ratio of silver oxide (Ag 2 O) to vanadium oxide (V 2 O 5 ) may be about 1.5: 1 to about 3: 1. It is possible to secure excellent conversion efficiency and adhesion with the ribbon in the above range.
- the glass frit is silicon oxide (SiO 2 ), barium oxide (BaO), vanadium oxide (V 2 O 5 ), phosphorus oxide (P 2 O 5 ), magnesium oxide (MgO), cerium oxide (CeO 2 ), boron oxide (B 2 O 3 ), strontium oxide (SrO), molybdenum oxide (MoO 3 ), titanium oxide (TiO 2 ), tin oxide (SnO), indium oxide (In 2 O 3 ), nickel oxide (NiO), copper oxide (Cu 2 O or CuO), antimony oxide (Sb 2 O 3 , Sb 2 O 4 or Sb 2 O 5 ), germanium oxide (GeO 2 ), gallium oxide (Ga 2 O 3 ), calcium oxide (CaO), oxide Arsenic (As 2 O 3 ), cobalt oxide (CoO or Co 2 O 3 ), zirconium oxide (ZrO 2 ), manganese oxide (MnO, Mn 2 O 3 or Mn 3 O 4 ), n
- the glass frit is not particularly limited and may be prepared using conventional methods.
- the frit mixes the composition described above to produce a composition for glass frit.
- Mixing can be performed using a ball mill or planetary mill.
- the mixed composition is melted at conditions of about 900 ° C. to about 1300 ° C. and quenched at about 25 ° C.
- the obtained result can be pulverized by a disk mill, planetary mill or the like to obtain a glass frit.
- the glass frit may be included in an amount of about 0.5 wt% to about 20 wt% based on the total weight of the composition, and specifically, about 0.5 wt% to about 5 wt%. Within this range, the adhesion between the conductive powder and the wafer can be improved and softened during sintering to further lower the firing temperature.
- the shape of the glass frit may be, for example, spherical or indefinite.
- the organic vehicle imparts suitable viscosity and rheological properties to the paste composition by mechanical mixing with the inorganic component of the composition for forming a solar cell electrode.
- an organic vehicle used in a composition for forming a solar cell electrode may be used.
- the organic vehicle may include, for example, a conventional binder resin, a solvent, and the like.
- binder resin for example, acrylate or cellulose resin can be used.
- ethyl cellulose, ethyl hydroxyethyl cellulose, nitro cellulose, a mixture of ethyl cellulose and phenol resin, alkyd resin, phenolic resin, acrylic acid ester resin, xylene resin, polybutene resin, polyester type Resin, urea-based resin, melamine-based resin, vinyl acetate-based resin, wood rosin or polymethacrylate of alcohol may be used, but is not limited thereto.
- Solvents of glycol ethers such as propylene glycol monomethyl ether, butyl carbitol acetate (diethylene glycol monobutyl ether acetate), hexylene glycol, terpineol, methyl ethyl ketone, benzyl alcohol, gamma butyro Lactone, ethyl lactate, 3-pentanediol, 2,2,4-trimethyl- monoisobutyrate (Texanol, Texanol), etc. can be used individually or in mixture of 2 or more types.
- the blending amount of the organic vehicle may be about 1% to about 30% by weight based on the total weight of the composition. It is possible to secure sufficient adhesive strength and excellent printability in the above range.
- composition for forming a solar cell electrode of the present invention may further include a conventional additive as necessary to improve the flow characteristics, process characteristics and stability in addition to the above components.
- the additive may be used alone or in combination of two or more of a dispersant, thixotropic agent, plasticizer, viscosity stabilizer, antifoaming agent, pigment, ultraviolet stabilizer, antioxidant, coupling agent and the like.
- the content of the additive may be appropriately changed as necessary.
- the additive may be added at about 0.1% to about 5% by weight based on the total weight of the composition, but is not limited thereto. Within this range, the physical properties of the glass frit can be further improved.
- Another aspect of the present invention relates to an electrode formed from the composition for forming a solar cell electrode and a solar cell including the same.
- 1 illustrates a structure of a solar cell according to an embodiment of the present invention.
- the back electrode 210 may be printed and baked on a wafer 100 or a substrate including a p layer 101 and an n layer 102 as an emitter and then baked.
- the front electrode 230 may be formed.
- the composition for forming a solar cell electrode may be printed on the back side of the wafer and then dried at a temperature of about 200 ° C. to about 400 ° C. for about 10 seconds to about 60 seconds to perform a preliminary preparation step for the back electrode. have.
- the composition for forming a solar cell electrode on the front surface of the wafer may be printed and dried to perform a preliminary preparation step for the front electrode. Thereafter, a firing process may be performed at about 400 ° C. to about 950 ° C., specifically about 850 ° C. to about 950 ° C., for about 30 seconds to about 50 seconds to form a front electrode and a rear electrode.
- the glass frit I has a mean particle size (D50) of 1.0 ⁇ m through melting and sintering at 900 ° C. to 1300 ° C.
- the glass frit I has a glass transition temperature of 280 ° C. and has a first exothermic peak at 302 ° C. on a DTA curve when measuring thermogravimetric / differential heat (TG-DTA).
- ethyl cellulose (Dow chemical company, STD4) as an organic binder was dissolved in 5 wt% of butyl carbitol as a solvent at 60 ° C., and then spherical silver powder having an average particle diameter of 1.2 ⁇ m (Dowa Hightech CO.
- P-type polycrystalline wafer is textured with acid or base, phosphorus (P) is diffused to form N-type emitter, and then PECVD process is performed. After printing by printing a predetermined pattern with a composition for forming a solar cell electrode on the front surface of the solar cell wafer formed with a silicon nitride-based anti-reflection film through, and dried in an infrared drying furnace. After printing the aluminum paste on the back of the wafer and dried in the same manner. The cell formed by the above process was calcined for 30 seconds to 50 seconds between 400 ° C. and 900 ° C.
- Thermogravimetric and differential thermal (TG-DTA) measurement of glass frit Using EXSTAR's aluminum panel (P / N SSC515D001) and EXSTAR 6200, the glass frit is heated to 600 ° C at a heating rate of 20 ° C / min The temperature of the resulting exothermic peak was measured and the results are shown in Table 1 below.
- Example 2 It was prepared in the same manner as in Example 1, except that the composition for forming a solar cell electrode was prepared in the compositions of Tables 2 and 3.
- the composition of the glass frits I to V used in Examples 2 to 8 and Comparative Examples 1 to 5 and the initiation temperature at which the first exothermic peak appears in the glass transition temperature and thermogravimetric and differential thermal (TG-DTA) analysis are shown in Table 1 below. It was.
- the glass transition temperature has a low melting point in the range of 100 °C to 300 °C, while the starting temperature at which the exothermic peak appears, the glass frit (I and II) of 200 °C to 400 °C
- the glass transition temperature is comparative example 1 using the glass frit (III) does not express the exothermic peak at 200 °C to 400 °C even if included in the present invention and glass frit having a high melting point of more than 300 °C glass frit (IV)
- the conversion efficiency and the Fill Factor value is superior to Comparative Examples 2 to 3 using V).
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Abstract
Description
유리 프릿 | 유리프릿의 조성 (단위:중량%) | 유리전이온도(℃) | DTA곡선상개시온도(℃) | |||||||||
PbO | TeO2 | Bi2O3 | Ag2O | V2O5 | Li2O | SiO2 | Al2O3 | ZnO | Na2O | |||
Ⅰ | 31 | 56 | 13 | - | - | - | - | - | - | - | 280 | 302 |
Ⅱ | 55 | - | - | 32 | 13 | - | - | - | - | - | 280 | 294 |
Ⅲ | 89 | - | 2 | - | - | - | 7 | 2 | - | - | 290 | 없음 |
Ⅳ | 68 | - | - | - | - | 2 | 16 | 5 | 8 | 1 | 435 | 486 |
Ⅴ | 55 | - | - | - | - | - | 31 | 7 | 7 | - | 435 | 501 |
비교예1 | 비교예2 | 비교예3 | ||
은(Ag)분말 | 89 | 89 | 89 | |
유리프릿 | Ⅰ | - | - | - |
Ⅱ | - | - | - | |
Ⅲ | 2 | - | - | |
Ⅳ | - | 2 | - | |
Ⅴ | - | - | 2 | |
유기비히클 | 바인더 | 0.2 | 0.2 | 0.2 |
용매 | 5 | 5 | 5 | |
첨가제 | 가소제 | 2.5 | 2.5 | 2.5 |
분산제 | 0.7 | 0.7 | 0.7 | |
요변제 | 0.6 | 0.6 | 0.6 | |
Fill Factor(%) | 0.282 | 0.274 | 0.690 | |
Jsc(mA/cm2) | 0.031 | 0.032 | 0.034 | |
Voc(mV) | 598 | 608 | 612 | |
Efficiency(%) | 10.20 | 13.40 | 14.43 |
Claims (9)
- 은 분말; 유리 프릿; 및 유기 비히클을 포함하고,상기 유리 프릿은 유리전이온도가 약 100℃ 내지 300℃이고,열중량·시차열(TG-DTA) 분석시, DTA 곡선상 발열피크가 나타나는 개시온도가 약 200℃ 내지 약 400℃인 것을 특징으로 하는 태양전지 전극 형성용 조성물.
- 제1항에 있어서,상기 유리 프릿은 유연 유리 프릿인 것을 특징으로 하는 태양전지 전극 형성용 조성물.
- 제1항에 있어서,상기 유리 프릿은 Pb-Bi-Te-O계 유리 프릿 및 Ag-V-Pb-O계 유리 프릿 중 하나 이상을 포함하는 태양전지 전극 형성용 조성물.
- 제3항에 있어서,상기 Pb-Bi-Te-O계 유리 프릿은 산화납(PbO) 약 10 중량% 내지 약 70 중량%, 산화비스무스(Bi2O3) 약 1 중량% 내지 약 20 중량% 및 산화텔루륨(TeO2) 약 10 중량% 내지 약 70 중량%를 포함하고,상기 Ag-V-Pb-O계 유리 프릿은 산화은(Ag2O) 약 10 중량% 내지 약 60 중량%, 산화바나듐(V2O5) 약 10 중량% 내지 약 40 중량% 및 산화납(PbO) 약 10 중량% 내지 약 60 중량%를 포함하는 것을 특징으로 하는 태양전지 전극 형성용 조성물.
- 제4항에 있어서,상기 유리 프릿은 산화규소(SiO2), 산화바륨(BaO), 산화바나듐(V2O5), 산화인(P2O5), 산화마그네슘(MgO), 산화세륨(CeO2), 산화붕소(B2O3), 산화스트론튬(SrO), 산화몰리브덴(MoO3), 산화티탄(TiO2), 산화주석(SnO), 산화인듐(In2O3), 산화니켈(NiO), 산화구리(Cu2O or CuO), 산화안티몬(Sb2O3, Sb2O4 또는 Sb2O5), 산화게르마늄(GeO2), 산화갈륨(Ga2O3), 산화칼슘(CaO), 산화비소(As2O3), 산화코발트(CoO or Co2O3), 산화지르코늄(ZrO2), 산화망간(MnO, Mn2O3 or Mn3O4), 산화네오듐(Nd2O3), 산화텅스텐(WO3), 산화크롬(Cr2O3) 및 산화알루미늄(Al2O3)으로 이루어진 군에서 선택된 1종 이상의 금속산화물을 더 포함하는 것을 특징으로 하는 태양전지 전극 형성용 조성물.
- 제1항에 있어서,상기 은 분말 약 60 중량% 내지 약 95 중량%; 상기 유리 프릿 약 0.5 중량% 내지 약 20 중량%; 및 상기 유기 비히클 약 1 중량% 내지 약 30 중량%; 를 포함하는 태양전지 전극 형성용 조성물.
- 제1항에 있어서,상기 유리 프릿은 평균입경(D50)이 약 0.1㎛ 내지 약 10㎛인 것을 특징으로 하는 태양전지 전극 형성용 조성물.
- 제1항에 있어서,상기 조성물은 분산제, 요변제, 가소제, 점도 안정화제, 소포제, 안료, 자외선 안정제, 산화방지제 및 커플링제로 이루어진 군으로부터 선택되는 첨가제를 1종 이상 더 포함하는 것을 특징으로 하는 태양전지 전극 형성용 조성물.
- 제1항 내지 제8항 중 어느 한 항의 태양전지 전극 형성용 조성물로 제조된 태양전지 전극.
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US14/761,215 US10388803B2 (en) | 2013-09-13 | 2014-09-12 | Composition for forming solar cell electrode and electrode manufactured therefrom |
EP14844862.4A EP2998969A4 (en) | 2013-09-13 | 2014-09-12 | Composition for forming solar cell electrode and electrode manufactured therefrom |
CN201480004073.6A CN104903974A (zh) | 2013-09-13 | 2014-09-12 | 太阳能电池电极用组成物及使用此组成物制造的电极 |
JP2016542642A JP6392354B2 (ja) | 2013-09-13 | 2014-09-12 | 太陽電池電極形成用組成物及びこれによって製造された電極 |
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PCT/KR2014/008510 WO2015037933A1 (ko) | 2013-09-13 | 2014-09-12 | 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극 |
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US (1) | US10388803B2 (ko) |
EP (1) | EP2998969A4 (ko) |
JP (1) | JP6392354B2 (ko) |
KR (1) | KR101608123B1 (ko) |
CN (1) | CN104903974A (ko) |
TW (1) | TWI562168B (ko) |
WO (1) | WO2015037933A1 (ko) |
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US10134925B2 (en) | 2016-04-13 | 2018-11-20 | E I Du Pont De Nemours And Company | Conductive paste composition and semiconductor devices made therewith |
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JP7360085B2 (ja) * | 2019-06-05 | 2023-10-12 | 日本電気硝子株式会社 | 粉末材料及び粉末材料ペースト |
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KR102342518B1 (ko) * | 2019-12-31 | 2021-12-23 | 엘에스니꼬동제련 주식회사 | 태양전지 전극용 도전성 페이스트 조성물 및 이를 사용하여 제조된 전극을 포함하는 태양전지 |
CN112592068B (zh) * | 2020-12-15 | 2022-11-15 | 广州市儒兴科技股份有限公司 | 一种玻璃粉及其制备方法与在TOPCon电池中的应用 |
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CN110663119A (zh) * | 2017-05-31 | 2020-01-07 | 东洋铝株式会社 | 太阳能电池用膏状组合物 |
CN110663119B (zh) * | 2017-05-31 | 2023-08-29 | 东洋铝株式会社 | 太阳能电池用膏状组合物 |
Also Published As
Publication number | Publication date |
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JP6392354B2 (ja) | 2018-09-19 |
EP2998969A1 (en) | 2016-03-23 |
CN104903974A (zh) | 2015-09-09 |
JP2016532278A (ja) | 2016-10-13 |
EP2998969A4 (en) | 2017-01-25 |
US20160284891A1 (en) | 2016-09-29 |
TWI562168B (en) | 2016-12-11 |
KR101608123B1 (ko) | 2016-03-31 |
KR20150031142A (ko) | 2015-03-23 |
US10388803B2 (en) | 2019-08-20 |
TW201523638A (zh) | 2015-06-16 |
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