CN102263158A - Preparation method of composite film used for solar cell and composite film prepared by same - Google Patents
Preparation method of composite film used for solar cell and composite film prepared by same Download PDFInfo
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- CN102263158A CN102263158A CN2011101351035A CN201110135103A CN102263158A CN 102263158 A CN102263158 A CN 102263158A CN 2011101351035 A CN2011101351035 A CN 2011101351035A CN 201110135103 A CN201110135103 A CN 201110135103A CN 102263158 A CN102263158 A CN 102263158A
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- Prior art keywords
- solar cell
- coating
- film
- nesa coating
- constituent
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract 2
- 238000000576 coating method Methods 0.000 claims abstract description 192
- 239000011248 coating agent Substances 0.000 claims abstract description 137
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- 238000000034 method Methods 0.000 claims description 113
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- 239000000758 substrate Substances 0.000 abstract description 9
- 230000009466 transformation Effects 0.000 abstract 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
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- 150000002334 glycols Chemical class 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 101150107144 hemC gene Proteins 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- PLYIPBIZXSTXCW-UHFFFAOYSA-N octanoic acid;tin Chemical compound [Sn].CCCCCCCC(O)=O PLYIPBIZXSTXCW-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- FXIOPNIFFZQLSF-UHFFFAOYSA-N phenol phosphorous acid Chemical compound OP(O)O.OP(O)O.OC1=CC=CC=C1 FXIOPNIFFZQLSF-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- VILMUCRZVVVJCA-UHFFFAOYSA-M sodium glycolate Chemical compound [Na+].OCC([O-])=O VILMUCRZVVVJCA-UHFFFAOYSA-M 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- Y02E10/52—PV systems with concentrators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a preparation method of a composite film used for a solar cell and a composite film prepared by the same. A photoelectric transformation layer is laminated on a substrate via a surface electrode. Dispersion liquid containing conductive oxide particles, dispersion liquid containing binder component or a transparent conductive film containing the conductive oxide particles and the binder component are/is coated on the photoelectric transformation layer in a wet coating method to form a transparent conductive coating film, and conductive reflective film components are coated on the coating film in a wet coating method to form a conductive reflective coating film. The substrate is sintered to form a combined film composed of the transparent conductive film and the conductive reflective film. The conductive oxide particles comprise non-ball-shaped anisotropic-shaped particles or anisotropic-shaped aggregate formed by a plurality of particles.
Description
Technical field
The present invention relates to form the method for the composite membrane that the solar cell that is made of nesa coating and conductive reflecting film on the light-to-current inversion layer that is arranged on solar cell uses and the composite membrane that forms by this method.In more detail, relate to make between light-to-current inversion layer and the nesa coating, the contact resistance between nesa coating and the conductive reflecting film descends, series resistance in the solar cell in when generating is reduced, thereby can improve the formation method of the composite membrane that the solar cell of generating efficiency uses and the composite membrane that forms by this method.
Background technology
At present, from the angle of protection environment, the research and development of clean energy resource constantly develop.Wherein, solar cell causes that owing to its resource is that sunlight is unlimited and nuisanceless etc. people pay close attention to.In the past, in utilizing the solar power generation of solar cell, used piece (bulk) solar cell, that is, made the block crystallization of monocrystalline silicon or polysilicon, it was carried out wafer processes, as thick tabular semiconductor.But,, in the growth of crystallization, need many energy and time about the above-mentioned silicon crystallization of in the piece solar cell, using, and in back to back manufacturing process, also need complicated step, so, be difficult to improve to produce in batches efficient, thereby the solar cell that provides price low be provided.
On the other hand, for used thickness is semi-conductive thin film semiconductor solar cells (hereinafter referred to as thin film solar cell) such as amorphous silicon below several microns, and only need form the light-to-current inversion layer on the substrate of cheapnesss such as glass or stainless steel is that semiconductor layer gets final product.Therefore, this thin film solar cell is because slim, light weight, low cost of manufacture, large tracts of landization etc. easily, and becomes the main flow of solar cell from now on.
About thin film solar cell, studying the structure that forms by the order that for example obtains by transparency electrode, amorphous silicon, polysilicon, backplate and improving generating efficiency (for example, with reference to non-patent literature 1).In the structure shown in this non-patent literature 1, amorphous silicon or polysilicon constitute the light-to-current inversion layer.Particularly, utilize silicon class material to constitute under the situation of solar cell at the light-to-current inversion layer, owing to the absorptivity of the light-to-current inversion layer that is formed by above-mentioned material is smaller, so, at the light-to-current inversion layer is in the micron-sized thickness of number, the part of incident light sees through the light-to-current inversion layer, and the light that sees through is helpless to generating.Therefore, usually as get off to carry out, that is, backplate as reflectance coating or form reflectance coating on the electrode overleaf, is utilized the reflectance coating reflection not to absorb and through the light of light-to-current inversion layer, made it get back to the light-to-current inversion layer once more, thus, the raising generating efficiency.
In the past, when making such thin film solar cell, utilized the sputtering method equal vacuum to become embrane method to form each layer.But, usually, since large-scale vacuum film formation apparatus keep and turn round in need expensive, so developing following method, promptly, become embrane method by becoming embrane method to be replaced as wet type the sputtering method equal vacuum as far as possible, thereby make thin film solar cell more at an easy rate (for example, with reference to patent documentation 1).In the method shown in this patent documentation 1, the formation that discloses the nesa coating that will be positioned at the base material side and be surface electrode 12 shown in Figure 1 is replaced as the method that wet type becomes embrane method.
Patent documentation 1: Japanese kokai publication hei 10-12059 communique (paragraph ［ 0028 ］, paragraph ［ 0029 ］).
Non-patent literature 1: Shozo Yanagida etc. works, " film too the most preceding Line of Yang Electricity pond development～high efficiency mass production popularize short Jin To け て～", the エ ヌ テ ィ ー エ ス of Co., Ltd., in March, 2005, Fig. 1 (a) P.113.
But, in thin film solar cell,, seek to reduce layer that constitutes each electrode or the resistance that film self is had, realize between light-to-current inversion layer and the electrode or electrode excellent contact or conduction each other in order to improve generating efficiency.The inventor is replaced into wet type to the formation of the electrode that will be positioned at rear side and becomes the method for embrane method to study, following method etc. is so far proposed: in the formation of the nesa coating that has used the wet type coating process, on the light-to-current inversion layer, apply with the liquid that contains transparent conductive oxides particulate and binding agent composition, and to the method for its sintering; At first, the transparent conductive oxides particulate is coated on the light-to-current inversion layer, carries out the method for sintering after then it being fixed with the binding agent composition.
But, as the transparent conductive oxides particulate, use general spherical particulate, forming under the situation of nesa coating by the wet type coating process, because at light-to-current inversion layer and the intermembranous binding agent composition that exists of electrically conducting transparent, thereby the film problems such as conduction in the vertical that hinder produced, particularly, under the low situation of the carrier density of light-to-current inversion layer, be subjected to the influence that this conduction hinders effect easily, distinguish that this becomes the obstacle that improves generating efficiency.For example, when the conductivity of light-to-current inversion layer 13 and nesa coating 14a worsens, light-to-current inversion layer 13 during generating and the contact resistance between the nesa coating 14a rise, and this series resistance that becomes in the solar cell that makes when generating electricity rises, and the result hinders the reason that improves generating efficiency.
Summary of the invention
The object of the present invention is to provide make between light-to-current inversion layer and the nesa coating, the contact resistance between nesa coating and the conductive reflecting film descends, series resistance in the solar cell in when generating is descended, improve the formation method of the composite membrane that the solar cell of the generating efficiency of solar cell uses and the composite membrane that forms by this method thus.
First viewpoint of the present invention, as shown in Figure 1, on the light-to-current inversion layer 13 of the solar cell on being layered on the base material 11 via surface electrode 12, utilize wet type coating process coating to contain the atomic dispersion liquid of electroconductive oxide and contain the dispersion liquid of binding agent composition or contain the electroconductive oxide particulate and the two nesa coating of binding agent composition forms and uses constituent, form the electrically conducting transparent coated film, by wet type coating process coating electrically conductive sexual reflex film constituent on the electrically conducting transparent coated film, form conductivity reflection coated film, then, base material 11 with electrically conducting transparent coated film and conductivity reflection coated film is carried out sintering, thereby the composite membrane 14 that the solar cell that formation is made of nesa coating 14a and conductive reflecting film 14b is used, it is characterized in that the electroconductive oxide particulate comprises the particle with aspheric anisotropy shape, perhaps a plurality of particle coacervations and in the agglomerate that forms any with anisotropic structure.
Second viewpoint of the present invention is based on the invention of first viewpoint, it is characterized in that, and then the aspect ratio of anisotropy shaped particle or anisotropic structure agglomerate is more than 3.
The 3rd viewpoint of the present invention is based on the invention of first viewpoint, it is characterized in that, and then, at anisotropy shaped particle or anisotropic structure agglomerate when being tabular, the tabular particle or the thickness of agglomerate are 50～1500nm, and the width and thickness ratio is 2～100.
The 4th viewpoint of the present invention is based on the invention of first to the 3rd viewpoint, it is characterized in that, and then the wet type coating process is any in spraying process, distributor coating process, spin-coating method, scraper plate coating process, slit coating method, ink-jet coating method, silk screen print method, hectographic printing method or the mold coating process.
The 5th viewpoint of the present invention is a kind of nesa coating formation constituent, sintering forms the nesa coating of formation solar cell with composite membrane to be used for applying also by the wet type coating process, it is characterized in that, above-mentioned constituent is made of atomic dispersion liquid of the electroconductive oxide that does not comprise the binding agent composition and the dispersion liquid that do not comprise the atomic binding agent composition of electroconductive oxide, perhaps constitute by comprising the two dispersion liquid of electroconductive oxide particulate and binding agent composition, the electroconductive oxide particulate comprises the particle with aspheric anisotropy shape, perhaps a plurality of particle coacervations and in the agglomerate that forms any with anisotropic structure.
The 6th viewpoint of the present invention is based on the invention of the 5th viewpoint, it is characterized in that, and then the aspect ratio of anisotropy shaped particle or anisotropic structure agglomerate is more than 3.
The 7th viewpoint of the present invention is based on the invention of the 5th viewpoint, it is characterized in that, and then, at anisotropy shaped particle or anisotropic structure agglomerate when being tabular, the tabular particle or the thickness of agglomerate are 50～1500nm, and the width and thickness ratio is 2～100.
The 8th viewpoint of the present invention is the composite membrane of being used by the solar cell that nesa coating that forms by the method based on first to fourth viewpoint and conductive reflecting film constitute.
The 9th viewpoint of the present invention is the solar cell with composite membrane of using based on the solar cell of the 8th viewpoint.
Be formed in the method for the composite membrane that the solar cell that is made of nesa coating and conductive reflecting film that forms on the light-to-current inversion layer of solar cell uses in the formation method of first viewpoint of the present invention, form electroconductive oxide particulate as employed conductive particle dispersion liquid or nesa coating in the formation of above-mentioned nesa coating, use any the particle in the agglomerate that comprises particle with aspheric anisotropy shape or a plurality of particle coacervation and form with anisotropic structure with constituent.The spherical atomic situation of electroconductive oxide of this anisotropy shaped particle or anisotropic structure agglomerate and use is in the past compared, and can increase interparticle contact area, can improve conductivity.Thus, make between the light-to-current inversion layer and nesa coating in when generating, the contact resistance between nesa coating and the conductive reflecting film descends, the series resistance in the solar cell when making generating descends, thereby can improve the generating efficiency of solar cell.In addition, owing to pass through the formation of wet type coating process, do not need the vacuum technology as vacuum vapour deposition or sputtering method etc., more qurer manufacturing.
It is to be used for applying and sintering forms and constitutes the nesa coating formation constituent of solar cell with the nesa coating of composite membrane by the wet type coating process that the nesa coating of the 5th viewpoint of the present invention forms with constituent, above-mentioned constituent is made of atomic dispersion liquid of the electroconductive oxide that does not comprise the binding agent composition and the dispersion liquid that do not comprise the atomic binding agent composition of electroconductive oxide, perhaps constitute by comprising the two dispersion liquid of electroconductive oxide particulate and binding agent composition, as the electroconductive oxide particulate, use to comprise particle with aspheric anisotropy shape, or a plurality of particle coacervations and any particle in the agglomerate that forms with anisotropic structure.The spherical atomic situation of electroconductive oxide of this anisotropy shaped particle or anisotropic structure agglomerate and use is in the past compared, and can increase interparticle contact area, can improve conductivity.Thus, make between the light-to-current inversion layer and nesa coating in when generating, the contact resistance between nesa coating and the conductive reflecting film descends, the series resistance in the solar cell when making generating descends, thereby improves the generating efficiency of solar cell.
The solar cell of the 8th viewpoint of the present invention with composite membrane since the method by the invention described above form, so, in the formation of the nesa coating that constitutes composite membrane, electroconductive oxide particulate as the conductive particle dispersion liquid, use has the particle of aspheric anisotropy shape, or a plurality of particle coacervations and the agglomerate that forms with anisotropic structure, so, compare with the atomic situation of electroconductive oxide that use in the past is spherical, can increase interparticle contact area, consequently, can form nesa coating with high conductivity.Thus, make between the light-to-current inversion layer and nesa coating in when generating, the contact resistance between nesa coating and the conductive reflecting film descends, the series resistance in the solar cell when making generating descends, and further improves the generating efficiency of solar cell.
The solar cell of the 9th viewpoint of the present invention is owing to have the composite membrane that the solar cell of the invention described above is used, so the series resistance in the solar cell during generating is little, generating efficiency is very high.
Description of drawings
Fig. 1 is the cutaway view that schematically shows the stepped construction of general solar cell.
Wherein, description of reference numerals is as follows:
11 base materials
12 surface electrodes
13 light-to-current inversion layers
14 composite membranes
The 14a nesa coating
The 14b conductive reflecting film.
Embodiment
Then, describe being used to implement mode of the present invention based on accompanying drawing.
As shown in Figure 1, the manufacture method of the composite membrane that solar cell of the present invention is used is as follows, be layered in via surface electrode 12 on the light-to-current inversion layer 13 of the solar cell on the base material 11, utilize the wet type coating process, coating contains the atomic dispersion liquid of electroconductive oxide and contains the dispersion liquid of binding agent composition, perhaps containing the two nesa coating of electroconductive oxide particulate and binding agent composition forms and to use constituent, form the electrically conducting transparent coated film, on the electrically conducting transparent coated film, utilize wet type coating process coating electrically conductive sexual reflex film constituent, form conductivity reflection coated film, then, base material 11 with electrically conducting transparent coated film and conductivity reflection coated film is carried out sintering, thus, form the composite membrane 14 that the solar cell that is made of nesa coating 14a and conductive reflecting film 14b is used.
As base material 11, can use any or the stacked body of two or more light transmissions from the group that constitutes by glass, pottery, macromolecular material and silicon, selected in the light-transmitting substrate that constitutes by glass, pottery or macromolecular material.As polymeric substrate, can enumerate by polyimides or PET(PETG) etc. the substrate that forms of organic polymer.
Surface electrode 12 is following transparent and films with conductivity: makes from the light of base material 11 side incidents to see through to light-to-current inversion layer 13, and, as electrode performance function.As this surface electrode 12, for example can enumerate ITO(Indium Tin Oxide:Sn doped indium oxide), ATO(Antimony Tin Oxide:Sb doped stannum oxide), SnO
2(tin oxide), ZnO(zinc oxide), IZO(Indium Zinc Oxide:Zn doped indium oxide) etc. film.In addition, surface electrode 12 also can utilize from ZnO, In
2O
3, SnO
2, CdO, TiO
2, CdIn
2O
4, Cd
2SnO
4Or Zn
2SnO
4In any in mixed that selected one or more metal oxide constitutes in the group of any metal oxide that forms among Sn, Sb, F or the Al.For example, can enumerate AZO(Aluminum Zinc Oxide:Al doping zinc-oxide), TZO(Tin Zinc Oxide:Sn doping zinc-oxide).Above-mentioned surface electrode 12 can be not particularly limited by for example known method formation in the past such as hot CVD method, sputtering method, vacuum vapour deposition, wet type coating process.Utilizing the wet type coating process to form under the situation of surface electrode 12, can similarly carry out with the situation of utilizing the wet type coating process to form the nesa coating 14a that constitutes composite membrane 14 described later.In addition, above-mentioned ZnO is because to have high photopermeability, low resistive, plasticity and price low, so, preferably as the material of surface electrode 12.
On above-mentioned surface electrode 12, form the light-to-current inversion layer 13 that utilizes light to generate electricity.This light-to-current inversion layer 13 by in amorphous silicon or the microcrystal silicon any or the two constitute.In this embodiment, light-to-current inversion layer 13 has first light-to-current inversion layer that is formed by amorphous silicon semiconductor and the second light-to-current inversion layer that is formed by microcrystalline silicon semiconductor.Specifically, the first light-to-current inversion layer is to stack gradually p type a-Si(amorphous silicon from base material 11 sides), i type a-Si(amorphous silicon) and n type a-Si(amorphous silicon) amorphous silicon layer of the p-i-n type that forms.In addition, the second light-to-current inversion layer is to stack gradually p type μ c-Si(microcrystal silicon from the first light-to-current inversion layer side), i type μ c-Si(microcrystal silicon) and n type μ c-Si(microcrystal silicon) the p-i-n type microcrystal silicon layer that forms.
Like this, light-to-current inversion layer 13 has adopted the i type a-Si(first light-to-current inversion layer) with the i type μ c-Si(second light-to-current inversion layer) series connection (tandem) the type solar cell two kinds of different semiconductor structures of light absorption wavelength that have been stacked, can effectively utilize sunlight spectrum.At this, in this manual, " crystallite " is meant, not only comprises complete crystalline state, and comprise part noncrystalline (amorphous) state.
In addition, the light-to-current inversion layer can be obtained by any the single maqting type that constitutes in amorphous silicon layer or the microcrystal silicon layer or comprise any form in any one or two kinds of many maqting types in a plurality of amorphous silicon layers or the microcrystal silicon layer.In addition, also can obtain p type a-SiC:H(noncrystalline silicon carbide)/the such structure of i type a-Si/n type μ c-Si.These are not particularly limited, and still, can form by the known method in the past as plasma CVD method.And then, when so that for example above-mentioned tandem type example of structure is represented, also can between first light-to-current inversion layer (amorphous silicon photoelectric conversion units) and the second light-to-current inversion layer (microcrystal silicon photoelectric conversion units), form the intermediate layer.As this intermediate layer, the preferred material that uses as in the nesa coating 14a of surface electrode 12 or formation composite membrane 14 described later, use.
Form composite membrane 14 by the wet type coating process on light-to-current inversion layer 13, this composite membrane 14 is made of the conductive reflecting film 14b that is formed on the nesa coating 14a on the light-to-current inversion layer 13 and be formed on the nesa coating 14a.The nesa coating 14a that constitutes composite membrane 14 has diffusion each other that suppresses light-to-current inversion layer 13 and conductive reflecting film 14b and the effect that improves the reflection efficiency of conductive reflecting film 14b.
In order to form nesa coating 14a by the wet type coating process, studied following method, that is, on the light-to-current inversion layer, apply and it is carried out the method for sintering with the liquid that contains transparent conductive oxides particulate and binding agent composition; At first, the transparent conductive oxides particulate is coated on the light-to-current inversion layer, then, it is carried out the method for sintering etc. after fixing with the binding agent composition, but, adopt general spherical particulate as transparent conductive oxides under the atomic situation, owing between light-to-current inversion layer and nesa coating, there is the binding agent composition, thereby producing the problem that hinders film conduction in the vertical etc.Therefore, when the conductivity of light-to-current inversion layer 13 and nesa coating 14a worsens, between light-to-current inversion layer 13 and the nesa coating 14a or the contact resistance between light-to-current inversion layer 13 and the conductive reflecting film 14b rise, series resistance in solar cell during generating rises, consequently, hinder the raising of the generating efficiency of solar cell.
In the present invention, in order to improve the conductivity of nesa coating 14a, as the electroconductive oxide particulate that in the formation of nesa coating, uses, use any electroconductive oxide particulate of the agglomerate comprise particle with aspheric anisotropy shape or a plurality of particle coacervation and to form with anisotropic structure.The spherical atomic situation of electroconductive oxide of this anisotropy shaped particle or anisotropic structure agglomerate and employing is in the past compared, and can increase interparticle contact area, can improve the conductivity of formed nesa coating.
Anisotropy shaped particle or anisotropic structure agglomerate preferably aspect ratio are needle-like more than 3 or bar-shaped.At this, described aspect ratio is meant, the ratio of the limit of longest diameter during divided by the limit of minor axis.If aspect ratio is less than 3, then the conductivity of the nesa coating that forms with using spheroidal particle does not in the past have significant difference, can not fully obtain this effect.Wherein, particularly preferred aspect ratio is 3～30.In addition, the length on the limit of minor axis is preferably 5～100nm.
For example, in the manufacture method of bar-shaped indium tin oxide target, at first, with the indium trichloride aqueous solution (InCl
3The aqueous solution) and the butter of tin aqueous solution (SnCl
4The aqueous solution) mix, in this mixed liquor, add alkaline aqueous solutions such as sodium acid carbonate, pH is adjusted into 5.0～8.5, preferably pH is adjusted into 6.0～8.0, by in the liquid temperature be more than 5 ℃, preferred liquid temperature is 10～80 ℃ makes its reaction, thereby generate sediment.Sediment is the sediment by the coprecipitation phenomena generation of indium hydroxide and stannic hydroxide.Then, the sediment that is generated is carried out Separation of Solid and Liquid and recovery, carried out drying in 2～24 hours with 100～200 ℃ of heating, then, under atmosphere,, be that 5～50nm, major diameter are that 30～150nm, aspect ratio are the bar-shaped indium tin oxide target powder more than 3 thereby produce minor axis with more than 250 ℃, preferably carried out sintering in 1～6 hour with 400～800 ℃ of heating.In addition, the evaluation method of shape of particle is following carries out.At first, utilize SEM that powder is carried out photography more than 5 visual fields,, measure the longest limit and the shortest limit for the particle more than 100 in the image of being photographed, averaged, with these respectively as major diameter and minor axis.And, obtain the ratio of this average major diameter and minor axis, as the aspect ratio of the coccoid that becomes object.
In addition, when being tabular, the preferred tabular particle or the thickness of agglomerate are 50～1500nm at anisotropy shaped particle or anisotropic structure agglomerate, and the width and thickness ratio is 2～100.Said herein width and thickness is than being the width of the extreme length ratio during divided by thickness that becomes sheet.If width and thickness is than less than 2, then the conductivity of the nesa coating that forms with in the past use spheroidal particle does not have significant difference, can not fully obtain this effect.In addition, if width and thickness then has problems under the dispersion of nano-particles state than surpassing 100.Wherein, preferred thickness is that 70～200nm, width and thickness are than the scale shape that is 5～30.
For example, in the manufacture method of flakey tin oxide, at first, add hydrochloric acid in the gelinite that obtains the stannic chloride aqueous solution being neutralized with ammonia, the tin colloid freezing solution that the salt acidolysis is coagulated, then, to carry out freeze-dried and lepidiod oxidizing aqueous tin that obtain carries out sintering with 350～900 ℃, thereby produce thickness is that 1～100nm, width and thickness are than the flakey stannic oxide powder that is 2～100, wherein, while freeze-driedly be meant that remaining on temperature that scars do not thaw carries out common vacuumize and remove and desolvate.
In addition, in this manual, the value of the limit of particle or agglomerate, width, thickness etc. is by SEM image viewing (Ri Li System Zuo Suo System Electricity Microscopy Wei Mirror S800) value calculating or measure.Utilize SEM to photograph 5 more than the visual field,, measure the longest limit and the shortest limit for the particle more than 100 in the image of being photographed.The aspect ratio of likening to its mean value for the coccoid that becomes object.
As utilizing the wet type coating process to form the method for nesa coating 14a, mainly enumerate two kinds of formation methods.First method is following method: contain electroconductive oxide particulate and the two nesa coating constituent that is modulated into of binding agent composition by the coating of wet type coating process on light-to-current inversion layer 13, form the electrically conducting transparent coated film, carry out sintering then.Second method is following method: use the coating of wet type coating process not contain the atomic dispersion liquid of electroconductive oxide of binding agent composition on light-to-current inversion layer 13, form the atomic coated film of electroconductive oxide, then, use the wet type coating process on the atomic coated film of this electroconductive oxide, to flood and do not contain the atomic binding agent dispersion liquid of electroconductive oxide, carry out sintering then.
Nesa coating constituent in first method is to contain above-mentioned electroconductive oxide particulate and this electroconductive oxide particulate to be dispersed in constituent in the decentralized medium.As decentralized medium, except water, can enumerate hydrocarbon, N such as ketones such as alcohols such as methyl alcohol, ethanol, isopropyl alcohol, butanols, acetone, butanone, cyclohexanone, isophorone, toluene, dimethylbenzene, hexane, cyclohexane, dinethylformamide, N, gylcol ethers such as glycols, ethylene glycol ethyl ether such as sulfoxide class such as amines such as N-dimethylacetylamide, methyl-sulfoxide or ethylene glycol etc.
In addition, preferred electroconductive oxide particulate nesa coating in the solid constituent that constituent comprised shared contain proportional in the scope of 50～90 quality %.With electroconductive oxide atomic contain proportional be located in the above-mentioned scope be because, if less than lower limit, then since conductivity descend, so unsatisfactory, if surpass higher limit, then since close property descend, so unsatisfactory.Wherein, in the scope particularly preferably in 70～90 quality %.
The nesa coating constituent is the constituent that comprises the polymer-type binding agent that hardens by heating or any or both in the non-polymeric binding agent.As the polymer-type binding agent, can enumerate allyl resin, Merlon, polyester, alkyd resins, polyurethane, acroleic acid polyurethane, polystyrene, polyformaldehyde, polyamide, polyvinyl alcohol, polyvinyl acetate, cellulose and siloxane polymer etc.In addition, as the polymer-type binding agent, preferably include the hydrolysis body of metallic soap, metal fluor-complex or the metal alkoxide of aluminium, silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin.In the hydrolysis body of this metal alkoxide, contain collosol and gel.As the non-polymeric binding agent, can enumerate metallic soap, metal fluor-complex, metal alkoxide, halogenated silanes class, 2-alkoxyethanol, beta-diketon and alkylamide etc.In addition, the contained metal of metallic soap, metal fluor-complex or metal alkoxide is aluminium, silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony.These polymer-type binding agents, non-polymeric binding agent harden by heating, thereby can form the lower turbidity rate (haze rate) under the low temperature and the nesa coating 14a of specific insulation.Proportional for containing of these binding agents, as shared ratio in the solid constituent of using at nesa coating in the constituent, preferably in the scope of 5～50 quality %, more preferably in the scope of 10～30 quality %.
The preferably clear conducting film adds coupling agent with constituent according to employed other compositions.This is for the associativity that improves electroconductive oxide particulate and binding agent and utilizes nesa coating 14a that this nesa coating forms with constituent and the close property of light-to-current inversion layer 13 or conductive reflecting film 14b.As coupling agent, can enumerate silane coupler, aluminum coupling agent and titanium coupling agent etc.
As silane coupler, can enumerate ethene triethoxy trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-methacryloxypropyl trimethoxy silane etc.In addition, as aluminum coupling agent, can enumerate the aluminum coupling agent of the acetyl alkoxyl that contains following formula (1) expression.And then, as titanium coupling agent, can enumerate the dialkyl phenol phosphorous acid alkali that has shown in following formula (2)～(4) titanium coupling agent, have the titanium coupling agent of the dialkyl phosphite shown in the following formula (5).
(Chemical formula 1)
(Chemical formula 2)
(chemical formula 3)
(chemical formula 4)
(chemical formula 5)
Proportional about containing of coupling agent, as solid constituent at nesa coating with shared ratio in the constituent, be preferably in the scope of 0.2～5 quality %, wherein more preferably in the scope of 0.5～2 quality %.
In addition, according to employed composition, preferably add low resistance agent or water-soluble cellulose dielectric etc.As the low resistance agent, preferably from by a kind that selects the inorganic acid salt of cobalt, iron, indium, Nie , tin, titanium and zinc and the group that acylate constitutes or two or more.For example, can enumerate the mixture etc. of mixture, acetoacetic acid titanium and caprylic acid cobalt of mixture, indium nitrate and lead acetate of mixture, zinc naphthenate, caprylic acid tin and the antimony chloride of nickel acetate and iron chloride.Containing of these low resistance agent proportionally is preferably 0.2～15 quality % with respect to the electroconductive oxide powder.The water-soluble cellulose dielectric is the nonionic activating agent, but compares with other interfacial agent, even a small amount of the interpolation, the ability that conductivity acidulants powder is disperseed is also high, in addition, by adding the water-soluble cellulose dielectric, the transparency of formed nesa coating also improves.As the water-soluble cellulose dielectric, can enumerate hydroxypropyl cellulose, hydroxypropyl methylcellulose etc.The dielectric addition of preferred water cellulose of solubleness is in the scope of 0.2～5 quality %.
In order to use above-mentioned nesa coating to form nesa coating 14a with constituent, at first, is 0.01～0.5 μ m, the preferred mode in the scope of 0.05～0.1 μ m with nesa coating with the thickness of the nesa coating 14a of constituent after with sintering, is coated on the light-to-current inversion layer 13 by the wet type coating process.At this, the scope that the thickness of nesa coating 14a is limited to 0.01～0.5 μ m is because when less than 0.01 μ m or when surpassing 0.5 μ m, can not fully obtain increasing reflecting effect.After being coated on the light-to-current inversion layer 13 with constituent nesa coating,, obtain the electrically conducting transparent coated film with 20～100 ℃ temperature dryings 1～10 minute.
Above-mentioned wet type coating process is any in spraying process, distributor coating (dispensercoating) method, spin-coating method, scraper plate coating process, slit coating method, ink-jet coating method, silk screen print method, hectographic printing method or the mold coating process especially preferably, but be not limited to this, can utilize all methods.
Spraying process be utilize compressed air make dispersion become vaporific be coated on the base material or dispersion self pressurizeed make it become the vaporific method that is coated on the base material, the distributor coating process is for example dispersion to be put into syringe, makes dispersion spray the method that is coated on the base material from the minute nozzle of syringe front end by the piston that pushes this syringe.Spin-coating method is that dispersion is dropped on the rotating base material, utilize its centrifugal force to make the dispersion of this drippage be diffused into the method for base material periphery, the scraper plate coating process is that the base material that the front end with scraper plate separates predetermined gap is set to and can moves in the horizontal direction, to than this scraper plate more by supplying with dispersion on the base material of upstream side, and make the base material method that moves horizontally of side downstream.The slit coating method is to make dispersion flow out and it is coated in method on the base material from narrow slit, and the ink-jet coating method is to fill dispersion in the print cartridge of the ink-jet printer of selling on market, and carries out the method for ink jet printing on base material.Silk screen print method is to use yarn to indicate material as pattern, looks like to make dispersion to transfer to method on the base material by making thereon domain.The hectographic printing method is not make in the dispersion that has on the version to be attached directly on the base material, and is transferred to the rubber sheet last time from version, transfers to the hydrophobic printing process that utilizes printing ink on the base material again from the rubber sheet again.Mold coating (die coating) method is to divide the dispersion of supplying with in the orientation mold with runner, and it is expressed on the film from slit, the method that the surface of the base material that moves is applied.As the mold coating process, have slit application pattern or slip application pattern, curtain formula application pattern.
Like this, after forming the electrically conducting transparent coated film on the light-to-current inversion layer 13, on this electrically conducting transparent coated film, use conductive reflecting film described later to form conductivity reflection coated film, and under condition described later, the base material 11 with these coated film is carried out sintering with constituent.Thus, form nesa coating 14a with forming conductive reflecting film 14b.
The atomic dispersion liquid of the electroconductive oxide that does not contain the binding agent composition in second method is that above-mentioned electroconductive oxide particulate is dispersed in the dispersion liquid in the decentralized medium.In addition, employed decentralized medium in the modulation of the atomic dispersion liquid of electroconductive oxide can use and the decentralized medium decentralized medium of the same race that uses in constituent at the nesa coating of above-mentioned first method.In order to obtain good film forming, containing of the decentralized medium in the dispersion liquid is proportional preferred in the scope of 50～99.99 quality %.Electroconductive oxide in the dispersion liquid is atomic contain proportional preferred in the scope of 0.01～50 quality %.
The preferred atomic dispersion liquid of electroconductive oxide adds coupling agent according to employed other compositions.This is the nesa coating 14a that forms for the associativity that improves electroconductive oxide particulate and binding agent and by atomic dispersion liquid of this electroconductive oxide and binding agent dispersion liquid and the close property of light-to-current inversion layer 13 or conductive reflecting film 14b.In addition, the coupling agent that uses in the modulation of the atomic dispersion liquid of electroconductive oxide can use and the coupling agent coupling agent of the same race that uses in constituent at the nesa coating of above-mentioned first method.About the ratio of the coupling agent in the dispersion liquid, preferred coupling agent with respect to decentralized medium and the atomic total 100 quality % of electroconductive oxide and coupling agent in the scope of 0.01～10 quality %.
In addition, about containing the dispersion liquid of binding agent composition, as the binding agent composition, comprise in the polymer-type binding agent that hardens by heating or the non-polymeric binding agent any or the two.These polymer-type binding agents, non-polymeric binding agent harden by heating, thereby can form the lower turbidity rate under the low temperature and the nesa coating 14a of specific insulation.Containing of these binding agents in the binding agent dispersion liquid is proportional preferred in the scope of 0.01～50 quality %, in the scope particularly preferably in 0.5～20 quality %.In addition, employed polymer-type binding agent and non-polymeric binding agent can use and the polymer-type binding agent and the non-polymeric binding agent binding agent of the same race that use in constituent at the nesa coating of above-mentioned first method in the modulation of binding agent dispersion liquid.
In the modulation of binding agent dispersion liquid, the preferred use and the decentralized medium decentralized medium of the same race that in the modulation of the atomic dispersion liquid of above-mentioned electroconductive oxide, uses.In order to form uniform film, containing of preferred decentralized medium is proportional in the scope of 50～99.99 quality %.
In addition, preferably according to employed composition, add low resistance agent or water-soluble cellulose dielectric etc.As the low resistance agent, the low resistance agent low resistance agent of the same race that can enumerate Yu in the first above-mentioned method, use.These low resistance agent contain proportional 0.1～10 quality % that is preferably.In addition, owing to add the water-soluble cellulose dielectric, also improve the transparency of formed nesa coating.As the water-soluble cellulose dielectric, the dielectric dielectric of the same race of enumerating Yu in the first above-mentioned method, using.The dielectric addition of water-soluble cellulose is preferably in the scope of 0.1～10 quality %.
State in the use in the method that atomic dispersion liquid of electroconductive oxide and binding agent dispersion liquid form nesa coating 14a following method is arranged: will contain the two ground floor of electroconductive oxide particulate and binding agent composition as lower floor, and will mainly comprise the formation method of the second layer of binding agent composition as the upper strata; To contain the two ground floor of electroconductive oxide particulate and binding agent composition as lower floor, will not contain the method for the second layer of binding agent composition as the upper strata.
The nesa coating that forms with the former formation method forms under the state that the bonded dose of layer in the whole surface of electroconductive oxide particulate sublayer covers, so, have such advantage with low uncertainty in time.In this formation method, at first, on light-to-current inversion layer 13, apply the atomic dispersion liquid of above-mentioned electroconductive oxide by the wet type coating process,, thereby form the atomic coated film of electroconductive oxide with 20～120 ℃ of temperature, preferred 25～60 ℃ of dryings 1～30 minute, preferred 2～10 minutes.
Then, apply in the mode that covers the whole surface of the atomic coated film of electroconductive oxide with the binding agent dispersion liquid fully.In addition, in this preferably coating as follows of coating: the atomic gross mass that the quality of the binding agent composition in the binding agent dispersion liquid that applies contains in respect to the atomic coated film of coated electroconductive oxide is 0.5～10 mass ratio (the atomic quality of quality/electroconductive oxide of the binding agent composition in the coated binding agent dispersion liquid).If less than lower limit, then be difficult to obtain sufficient close property, if surpass higher limit, sheet resistance is increased.The coating of atomic dispersion liquid of above-mentioned electroconductive oxide and binding agent dispersion liquid is coating as follows preferably: the thickness of the nesa coating 14a behind the sintering is the thickness of 0.01～0.5 μ m, preferred 0.03～0.1 μ m.After making binding agent dispersion liquid dipping,, form the electrically conducting transparent coated film with 20～120 ℃ of temperature, preferred 25～60 ℃ of dryings 1～30 minute, preferred 2～10 minutes.
After forming the electrically conducting transparent coated film on the light-to-current inversion layer 13, with above-mentioned first method similarly, under condition described later, the base material 11 with electrically conducting transparent coated film and conductivity reflection coated film is carried out sintering.Thus, the formation with conductive reflecting film 14b forms nesa coating 14a.
On the other hand, the nesa coating 14a that forms with the latter's formation method is effective aspect the activity coefficient that increases one of factor as the decision generating efficiency.In this formation method, at first, on light-to-current inversion layer 13, apply the atomic dispersion liquid of above-mentioned electroconductive oxide by the wet type coating process, form the atomic coated film of electroconductive oxide.The thickness of nesa coating 14a after this coating is with sintering is that the mode of the thickness of 0.01～0.5 μ m, preferred 0.03～0.1 μ m applies, by with 20～120 ℃ of temperature, preferred 25～60 ℃ of dryings 1～30 minute, preferred 2～10 minutes, thereby form the atomic coated film of electroconductive oxide.
Then, on the atomic coated film of electroconductive oxide, flood above-mentioned binding agent dispersion liquid by the wet type coating process.At this moment, expose 1～30% mode of the volume of ground floor with the second layer that does not contain the binding agent composition among the nesa coating 14a that behind sintering, forms, make the predetermined degree of depth of binding agent dispersion liquid thorough impregnation to the atomic coated film of electroconductive oxide.In addition, in this preferably coating as follows of coating: the atomic gross mass that the quality of the binding agent composition in the binding agent dispersion liquid that applies is contained in respect to the atomic coated film of coated electroconductive oxide is 0.05～0.5 mass ratio (the atomic quality of quality/electroconductive oxide of the binding agent composition in the coated binding agent dispersion liquid).If less than lower limit, then be difficult to obtain sufficient close property, if greater than higher limit, sheet resistance is increased.Behind the impregnated with adhesive dispersion liquid,, form the electrically conducting transparent coated film with 20～120 ℃ of temperature, preferred 25～60 ℃ of dryings 1～30 minute, preferred 2～10 minutes.
After forming the electrically conducting transparent coated film on the light-to-current inversion layer 13, with above-mentioned first method similarly, under condition described later, the base material 11 with electrically conducting transparent coated film and conductivity reflection coated film is carried out sintering.Thus, the formation with conductive reflecting film 14b forms nesa coating 14a.
For conductive reflecting film 14b, have to make and do not absorbed and see through the light reflection of light-to-current inversion layer 13 and get back to the effect that light-to-current inversion layer 13 improves generating efficiency once more, thereby demanding diffuse reflectance.Therefore, the high metal of conductive reflecting film 14b preferred reflectance.As this metal, example illustrates the alloy or the alloys such as kuromore or stainless steel of metals such as silver, iron, chromium, tantalum, molybdenum, nickel, aluminium, cobalt or titanium or these metals.This conductive reflecting film 14b utilizes the conductive reflecting film used metal nanoparticle to be distributed to form in the decentralized medium to form with the wet type coating process of constituent.
The conductive reflecting film constituent is the constituent that is modulated in the decentralized medium by metal nanoparticle is distributed to.About above-mentioned metal nanoparticle, the ratio of the silver in the metallic element is more than the 75 quality %, is preferably more than the 80 quality %.Be because, then cause using the reflectivity of the conductive reflecting film 14b that this conductive reflecting film forms with constituent low with the ratio of the silver in the metallic element the scope more than the 75 quality % of being made as if less than 75 quality %.In addition, metal nanoparticle is the protective agent chemical modification of 1～3 organic molecule main chain by carbon number with carbon skeleton.1～3 the scope of will being located at the carbon number of carbon skeleton of organic molecule main chain that metal nanoparticle carries out the protective agent of chemical modification be because, if carbon number is more than 4, then protective agent is difficult to break away from or decompose (separate, burn) by heating, residual a lot of organic detritus in above-mentioned conductive reflecting film 14b, and go bad or deterioration, and the conductivity of conductive reflecting film 14b and reflectivity are reduced.
About metal nanoparticle, preferably with the metal nanoparticle in the scope that quantity on average contains more than 70%, preferred primary particle size more than 75% is 10～50nm.Primary particle size be the metal nanoparticle in the scope of 10～50nm amount if with quantity average then with respect to all metal nanoparticles 100% for less than 70 quality %, then the relative surface area of metal nanoparticle increases, the shared ratio of organic substance becomes big.Therefore, even the organic molecule of (separate, burning) easily takes place to break away from or decompose by heating, because the shared ratio of this organic molecule is many, so, also residual a lot of organic detritus in conductive reflecting film 14b.There is following danger in the rotten or deterioration of this residue: the conductivity of conductive reflecting film 14b and reflectivity descend or the particle size distribution of metal nanoparticle becomes wide, and the density of conductive reflecting film 14b descends.In addition, be because the conductivity of conductive reflecting film 14b and reflectivity descend.And then, according to the dependency relation of the time dependent stability (through stability for many years) of primary particle size and metal nanoparticle, the primary particle size of above-mentioned metal nanoparticle is located in the scope of 10～50nm.
Preferably use in the constituent, also comprise the additive of from the group that constitutes by organic polymer, metal oxide, metal hydroxides, organo-metallic compound and silicone oil, selecting more than a kind or 2 kinds at the conductive reflecting film that contains this metal nanoparticle.As additive, use conductive reflecting film with the organic polymer that comprises in the constituent, metal oxide, metal hydroxides, organo-metallic compound or silicone oil.Thus, seek to increase with the chemical bonding or the fixed effect of base material or improve metal nanoparticle in the operation of heat-agglomerating and the wetability of base material, under the situation of not damaging conductivity, can improve close property with base material.In addition, when using this conductive reflecting film to form conductive reflecting film 14b, can adjust the grain growth that causes by the sintering between metal nanoparticle with constituent.In having used of the formation of this conductive reflecting film,,, in addition, can significantly reduce the operating cost of manufacturing equipment so diminished by the restriction of technology owing to when film forming, do not need vacuum technology with the conductive reflecting film 14b of constituent.
The amount of additive for the quality of the Nano silver grain that constitutes metal nanoparticle 0.1～20%, be preferably 0.2～10%.If the danger that the density of big pore of average diameter or pore uprises, then can appear less than 0.1% in the amount of additive.If the amount of additive surpasses 20%, then produce following problem, that is, to the conductivity generation bad influence of formed conductive reflecting film 14b, specific insulation surpasses 2 * 10
-5Ω cm.
As the organic polymer of additive, can use from the group that copolymer and water-soluble cellulose by polyvinylpyrrolidone (Polyvinylpyrrolidone: hereinafter referred to as PVP), PVP constitute, select more than a kind or 2 kinds.Specifically, as the copolymer of PVP, can enumerate PVP-methacrylate copolymer, PVP-styrol copolymer, PVP-acetate ethylene copolymer etc.In addition, as water-soluble cellulose, can enumerate cellulose ethers such as hydroxypropyl methylcellulose, methylcellulose, HEMC.
Metal oxide as additive preferably includes at least a oxide or the composite oxides selected from the group that is made of aluminium, silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.Specifically, composite oxides are above-mentioned ITO, ATO, IZO, AZO etc.
As metal hydroxides, preferably include at least a hydroxide of from the group that aluminium, silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony constitute, selecting as additive.
Organo-metallic compound as additive preferably includes at least a metallic soap, metal fluor-complex or the metal alkoxide selected from the group that is made of silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin.For example, as metallic soap, can enumerate chromic acetate, formic acid manganese, ironic citrate, formic acid cobalt, nickel acetate, silver citrate, Schweinfurt green, copper citrate, tin acetate, zinc acetate, zinc oxalate, acetic acid molybdenum etc.In addition, as the metal fluor-complex, can enumerate zinc acetylacetonate fluor-complex, chromium acetylacetonate fluor-complex, nickel acetylacetonate fluor-complex etc.In addition, as metal alkoxide, can enumerate isopropyl titanate, methyl silicate, isocyanates propyl trimethoxy silicane, aminopropyl trimethoxysilane etc.
As the silicone oil of additive, can use pure silicon oil and modified silicon oil the two.Modified silicon oil can also use the part of the side chain of polysiloxanes import organic group silicone oil (side chain type), import the silicone oil (single tip type) of organic group and at a part and the two terminal silicone oil (the two tip type of side chain) that import organic groups of the side chain of polysiloxanes in two terminal any that import in the silicone oil (two tip type) of organic groups, two ends of polysiloxanes at polysiloxanes.Have reactive silicone oil and non-reactive silicone oil as modified silicon oil, but these two kinds can both be used as additive of the present invention.In addition, that reactive silicone oil is represented is amino modified, epoxy radicals modification, carboxy-modified, methyl alcohol modification, sulfhydryl modification and xenogenesis functional group modification (epoxy radicals, amino, polyether-based), and that non-reactive silicone oil is represented is polyether-modified, the modification of methyl styrene base, alkyl modification, higher fatty acids are ester modified, fluorine modification and hydrophilic special modification.
On the other hand, Nano silver grain in addition the metal nanoparticle of formation conductive reflecting film in the metal nanoparticle of constituent, preferably also comprise following metal nanoparticle, comprise that promptly a kind of particle or the mixing more than 2 kinds selected form or alloy composition from the group that is made of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese.Metal nanoparticle beyond this Nano silver grain is preferably more than 0.02 quality % with respect to all metal nanoparticle 100 quality % and less than 25 quality %, more preferably 0.03 quality %～20 quality %.Its reason is, the amount of the particle beyond the Nano silver grain is more than 0.02 quality % and in the scope less than 25 quality %, do not compare and can worsen before the conductivity of the conductive reflecting film 14b after atmospheric exposure test (test that keeps 1000 hours in the constant temperature and humidity cabinet of 100 ℃ of temperature and humidity 50%) and reflectivity and the atmospheric exposure test.
In addition, about the amount of conductive reflecting film with the metal nanoparticle that contains Nano silver grain in the constituent, with respect to the conductive reflecting film that constitutes by metal nanoparticle and decentralized medium constituent 100 quality %, contain 2.5～95.0 quality %, more preferably contain 3.5～90 quality %.If with containing of constituent 100 quality % of the proportional 95.0 quality % that surpass, then when conductive reflecting film applies with the wet type of constituent, lose flowability as necessity of printing ink or cream with respect to conductive reflecting film.
In addition, the conductive reflecting film that is configured for forming conductive reflecting film 14b preferably contains more than the 1 quality % more preferably the water more than the 2 quality % with the decentralized medium of constituent with respect to all decentralized media 100 quality % and solvent, for example alcohols molten with water more than the 3 quality % more preferably more than the 2 quality %.For example, under the situation that decentralized medium only is made of water and alcohols, when containing the water of 2 quality %, contain the alcohols of 98 quality %,, contain the water of 98 quality % at the pure time-like that contains 2 quality %.And then the protection molecule that decentralized medium promptly carries out chemical modification in surfaces of metal nanoparticles contains hydroxy (OH) or carboxyl (any C=O) or the two.The amount of preferred water is a scope more than the 1 quality % with respect to all decentralized media 100 quality %.Its reason is, if the amount of water then is difficult at low temperatures to carrying out sintering by wet type coating process coating electrically conductive sexual reflex film with the film that constituent obtains less than 2 quality %.Also because the conductivity of the conductive reflecting film 14b behind the sintering and reflectivity are descended.In addition, (OH) time, conductive reflecting film is good with the dispersion stabilization of constituent, also has useful effect in the low-temperature sintering of coated film when contain hydroxy in the protective agent that metal nanoparticles such as Nano silver grain is carried out chemical modification.In addition, when in the protective agent that metal nanoparticles such as Nano silver grain is carried out chemical modification, containing carboxyl (C=O) time, with similarly above-mentioned, conductive reflecting film is good with the dispersion stabilization of constituent, also has useful effect in the low-temperature sintering of coated film.As the solvent molten that uses at decentralized medium with water, preferred alcohols.Wherein, as above-mentioned alcohols, preferred especially use from the group that constitutes by methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, diethylene glycol (DEG), glycerol, isobornyl cyclohexanol and erythroglucin, select more than a kind or 2 kinds.
Manufacturing is used to form the conductive reflecting film that contains metal nanoparticle of conductive reflecting film 14b and uses the method for constituent as follows.
(a) be made as 3 o'clock at the carbon number of carbon skeleton of organic molecule main chain that will be used for Nano silver grain is carried out the protective agent of chemical modification, at first, silver nitrate be dissolved in the water such as deionized water the modulation aqueous metal salt.On the other hand, natrium citricum is dissolved in the water such as deionized water and the concentration that obtains is in 10～40% the sodium citrate aqueous solution, directly add ferrous sulfate granular or powdery and make its dissolving in the air-flow of non-active gas such as nitrogen, modulation contains the reducing agent aqueous solution of citrate ions and ferrous ion with the mol ratio of 3:2.Then, in above-mentioned non-active gas air-flow stir the above-mentioned reducing agent aqueous solution on one side, mix to this reducing agent aqueous solution above-mentioned aqueous metal salt that drips on one side.At this, be the concentration that the mode below 1/10 of the amount of the reducing agent aqueous solution is adjusted each solution preferably with the addition of aqueous metal salt, thereby even the aqueous metal salt of the room temperature of dripping, reaction temperature also is maintained at 30～60 ℃.In addition, the mixing ratio of above-mentioned two aqueous solution is adjusted into, and the equivalent of the ferrous ion that adds as reducing agent is 3 times of equivalent of metal ion.That is, adjust as follows: (molal quantity of the metal ion in the aqueous metal salt) * (valence mumber of metal ion)=3 * (molal quantity of the ferrous ion in the reducing agent aqueous solution).After dripping of aqueous metal salt finished, continue mixed liquor was stirred 10～300 minutes the dispersion liquid that modulation is made of metallic colloid.At room temperature place this dispersion liquid, after by decantation or centrifugal separation etc. the condensation product of the metal nanoparticle of precipitation being separated, in this separator, add water such as deionized water and form dispersion, carry out desalting processing by ultrafiltration.And then, then replace cleaning with alcohols, the amount that makes metal (silver) is 2.5～50 quality %.Then, use centrifugal separator, the centrifugal force of this centrifugal separator is adjusted, isolate corase particles, thereby Nano silver grain is modulated into: on average contain Nano silver grain in the scope that primary particle size more than 70% is 10～50nm with quantity.That is, adjust as follows: with the relative all Nano silver grain 100% shared ratios of the Nano silver grain in the scope of quantity average primary particle diameter 10～50nm is more than 70%.Thus, can access the carbon number of carbon skeleton of organic molecule main chain that Nano silver grain is carried out the protective agent of chemical modification is 3 dispersion.
Then, resulting dispersion is adjusted, made final metal amount (silver-colored amount) with respect to dispersion 100 quality % in the scope of 2.5～95 quality %.In addition, be when containing the aqueous solution of alcohols at decentralized medium, preferably water and the alcohols with solvent is adjusted into respectively more than 1% and more than 2%.In addition, also comprise under the situation of additive at conductive reflecting film, undertaken by in dispersion, adding the additive of from the group that constitutes by organic polymer, metal oxide, metal hydroxides, organo-metallic compound and silicone oil, selecting more than a kind or 2 kinds with desirable ratio with constituent.The amount of additive is adjusted into, and is in the scope of 0.1～20 quality % with respect to resulting conductive reflecting film with constituent 100 quality %.Thus, can access by the carbon number of carbon skeleton is that the Nano silver grain of the protective agent chemical modification of 3 organic molecule main chain is distributed to the conductive reflecting film constituent in the decentralized medium.
(b) under the carbon number of the carbon skeleton of the organic molecule main chain of the protective agent that will carry out chemical modification to Nano silver grain is made as 2 situation, except the natrium citricum that will use replaces to natrium malicum, similarly modulate dispersion with above-mentioned (a) when modulating the reducing agent aqueous solution.Thus, can access the carbon number of carbon skeleton that Nano silver grain is carried out the organic molecule main chain of chemical modification is 2 dispersion.
(c) under the carbon number of the carbon skeleton of the organic molecule main chain of the protective agent that will carry out chemical modification to Nano silver grain is made as 1 situation, the natrium citricum that uses except will modulate the reducing agent aqueous solution time is replaced and is the sodium glycollate, similarly modulates dispersion with above-mentioned (a).Thus, can access the carbon number of carbon skeleton that Nano silver grain is carried out the organic molecule main chain of chemical modification is 1 dispersion.
(d) under the carbon number of the carbon skeleton of the organic molecule main chain of the protective agent that the metal nanoparticle beyond the Nano silver grain is carried out chemical modification is 3 situation, as the metal that constitutes Nano silver grain metal nanoparticle in addition, can enumerate gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese.Except that the silver nitrate that will use replaces to gold chloride, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, stannous chloride, indium nitrate, zinc chloride, ferric sulfate, chromium sulfate or the manganese sulfate, similarly modulate dispersion with above-mentioned (a) when modulating aqueous metal salt.Thus, can access the carbon number of carbon skeleton of organic molecule main chain that the metal nanoparticle beyond the Nano silver grain is carried out the protective agent of chemical modification is 3 dispersion.
In addition, be under 1 or 2 the situation at the carbon number of the carbon skeleton of the organic molecule main chain of the protective agent that the metal nanoparticle beyond the Nano silver grain is carried out chemical modification, except the silver nitrate that will use replaces to the slaine of mentioned kind, similarly modulate dispersion with above-mentioned (b) or above-mentioned (c) when modulating aqueous metal salt.Thus, can access the carbon number of carbon skeleton of organic molecule main chain that the metal nanoparticle beyond the Nano silver grain is carried out the protective agent of chemical modification is 1 or 2 dispersion.
As metal nanoparticle, under the situation that contains Nano silver grain and Nano silver grain metal nanoparticle in addition, for example, when the dispersion that comprises Nano silver grain of method manufacturing that will be by above-mentioned (a) as first dispersion, the dispersion that comprises the metal nanoparticle beyond the Nano silver grain of method manufacturing that will be by above-mentioned (d) is during as second dispersion, is that the mode of 100 quality % is mixed with first dispersion more than the 75 quality % with less than second dispersion of 25 quality % with the total amount of first and second dispersion.In addition, first dispersion is not limited to the dispersion that comprises Nano silver grain by the method manufacturing of above-mentioned (a), also can use the dispersion that comprises Nano silver grain of the dispersion that comprises Nano silver grain of the method manufacturing by above-mentioned (b) or the method manufacturing by above-mentioned (c).
In order to use above-mentioned conductive reflecting film to form conductive reflecting film 14b with constituent, at first, by the wet type coating process above-mentioned conductive reflecting film is coated in constituent on the above-mentioned electrically conducting transparent coated film of carrying out before the sintering, is 0.05～2.0 μ m, is preferably the mode coating electrically conductive sexual reflex film constituent of the thickness of 0.1～1.5 μ m with the thickness behind the sintering.Then, it with 20～120 ℃ of temperature, preferred 25～60 ℃ of dryings 1～30 minute, preferred 2～10 minutes, is formed conductivity reflection coated film.At this, be that the mode of the scope of 0.05～2.0 μ m applies with the thickness of the conductive reflecting film 14b behind the sintering be because if less than 0.05 μ m, then the sheet resistance value of the needed electrode of solar cell is insufficient.In addition, about the wet type coating process, the same method of method in the time of can using and apply above-mentioned nesa coating with constituent etc.
After forming electrically conducting transparent coated film and conductivity reflection coated film as described above, the base material 11 that will have these coated film is in atmosphere or in the non-active gas environment such as nitrogen, argon gas, preferably 130～400 ℃, more preferably under 150～350 ℃ the temperature, the preferred maintenance 5～60 minutes, more preferably kept 15～40 minutes, and carried out sintering.Thus, form the composite membrane 14 that constitutes by nesa coating 14a and conductive reflecting film 14b.
If it is because less than 130 ℃, then produce the problem that the sheet resistance value of the nesa coating 14a that constitutes composite membrane 14 becomes too high that sintering temperature is located at 130～400 ℃ scope.Also because metal nanoparticle sintering each other becomes insufficient in conductive reflecting film 14b, and is difficult to take place to break away from or decomposition (separation, burning) by the heating of protective agent.That is, residual a lot of organic detritus in the conductive reflecting film 14b behind sintering, the rotten or deterioration of this residue causes the conductivity of conductive reflecting film 14b and reflectivity to descend.In addition, if surpass 400 ℃, then can not produce the advantage in the such production of low temperature process.That is, manufacturing cost increases and productivity descends, and especially the optical wavelength band that has used the light-to-current inversion in amorphous silicon, microcrystal silicon or the two the mixed type silicon solar cell is impacted.And then if will be made as the retention time 5～60 minutes was because less than 5 minutes, then produce the problem that the sheet resistance value of the nesa coating 14a that constitutes composite membrane 14 becomes too high.In addition, because the metal nanoparticle of conductive reflecting film 14b sintering to each other becomes insufficient, and be difficult to take place to break away from or decomposition (separate, burn) by the heating of protective agent, so, residual a lot of organic detritus in the conductive reflecting film 14b behind sintering, rotten or the deterioration of this residue causes the conductivity of conductive reflecting film 14b and reflectivity to descend.
By above operation, can on the light-to-current inversion layer 13 of solar cell, form the composite membrane that the solar cell that is made of nesa coating 14a and conductive reflecting film 14b is used.In the composite membrane 14 that forms by this method, in the formation of the nesa coating that constitutes composite membrane, electroconductive oxide particulate as the conductive particle dispersion liquid, use has the particle of aspheric anisotropy shape or a plurality of particle coacervation and the agglomerate with anisotropic structure that forms, so, compare with the atomic situation of electroconductive oxide that use in the past is spherical, can increase interparticle contact area, consequently, can form nesa coating with high conductivity.Therefore, the contact resistance between light-to-current inversion layer and the nesa coating, between nesa coating and the conductive reflecting film diminishes, and the series resistance in the solar cell when making generating reduces, so, can improve generating efficiency.
In addition, when like this forming composite membrane 14, with simple operation and finish at short notice, do not need vacuum technology during this external film forming,, can reduce the operating cost of manufacturing equipment significantly so be subjected to the restriction of technology little by the wet type coating process.In addition, in the composite membrane 14 that obtains by this method, in the average diameter of the pore that occurs from conductive reflecting film 14b and contact-making surface nesa coating 14a or with zone below the mean depth 100nm of the opposed surface of this contact-making surface be below the 100nm, the residing mean depth of pore is below the 100nm, the number density of pore is 30/μ m
2Below.Thus, when to use transmitance be light transmission base material more than 98%, in the scope of wavelength 500～1200nm, the higher diffuse reflectance more than 80% that can the realization theory reflectivity.When the scope of this wavelength 500～1200nm has almost been enlisted the services of polysilicon as the light-to-current inversion layer can conversion wavelength.In addition, above-mentioned conductive reflecting film 14b can access with constituting and be included in the approaching resistivity of resistivity that conductive reflecting film is had with the metal of the metal nanoparticle in the constituent itself.That is, demonstrate and the lower resistivity that can use the piece same degree of electrode as solar battery module.In addition, this conductive reflecting film 14b compares with the film that forms by sputtering method equal vacuum technology, and the long-time stability of the reflectivity of film, close property, resistivity etc. are good.As this reason, can enumerate: since in atmosphere film forming, so, compare with the film that forms in a vacuum, be difficult to be subjected to the influence that produces by the immersion of moisture or oxidation etc.
Also can be on conductive reflecting film 14b via not shown backplate strengthening membrane or do not form barrier film via the backplate strengthening membrane.
[embodiment]
Then, embodiments of the invention and comparative example are elaborated.
＜embodiment 1～10, comparative example 1,2 〉
As the composition shown in following table 1, the table 2, it is 60g that electroconductive oxide particulate, decentralized medium, binding agent, coupling agent are made total metering with the ratio shown in table 1, the table 2, they are put into the vial of 100cc, use zirconium oxide bead (ミ Network ロ Ha イ カ, the clear and シ ェ Le oil society manufacturing) 100g of diameter as 0.3mm, disperseed 6 hours with dispersion machine with test, thereby obtain the nesa coating constituent.
In addition, ATO particle in the electroconductive oxide particulate of above-mentioned use and ATO agglomerate are by following method manufacturing.At first, in 90 ℃ pure water 51, pH with system maintains 7～7.5 mode, stannic chloride pentahydrate 500g and trichloride antimony 10g are dissolved in the solution and the NaOH that obtain among the 3N aqueous hydrochloric acid solution 500ml generate coprecipitate through adding simultaneously in 20 minutes.Then, add hydrochloric acid to this, the pH of system is adjusted into 3 after, filter this sediment, wash then, be 15000 Ω cm up to the resistivity of filtrate.Then, resulting block after 12 hours, is added the borax of 136.5g with 110 ℃ of dryings in this drying shape thing, make both mix pulverizing equably.Then, with this mixture in electric furnace with 900 ℃ of sintering 1 hour.Then, utilize hydrofluoric acid aqueous solution that resulting sintering product is carried out impregnation process, remove the solubility salt, afterwards, carry out drying, pulverizing, the needle-like that obtains becoming target contains the tin oxide micropowder of conductivity antimony.
In addition, ITO particle and ITO agglomerate are following manufacturings: mix the indium trichloride aqueous solution (lnCl
3The aqueous solution) and the butter of tin aqueous solution (SnCl
4The aqueous solution), add the alkaline aqueous solution contain sodium acid carbonate in this mixed liquor, pH is adjusted into 5～10, reacted 30～300 minutes in 20～60 ℃ of liquid temperature, the sediment that is generated is carried out Separation of Solid and Liquid and reclaims, sintering is carried out in dry back under atmosphere.
In addition, SnO
2Particle and SnO
2Agglomerate is following manufacturing: add hydrochloric acid in the colloid that obtains with ammonia the stannic chloride aqueous solution being neutralized, make by the convert tin colloid freezing solution 5～120 minutes of the tin that the salt acidolysis contain 10 quality % coagulates of oxide, then, will carry out freeze-dried and the lepidiod oxidizing aqueous tin that obtains sintering 1～10 hour in 350～800 ℃.
In addition, in table 1 or table 2, first mixed liquor is isopropyl alcohol, ethanol and N, the decentralized medium that dinethylformamide mixes with mass ratio 4:2:1.In addition, second mixed liquor is the decentralized medium that ethanol and butanols are mixed with mass ratio 98:2.
Then, by following step, modulation conductive reflecting film constituent.At first, silver nitrate is dissolved in the deionized water modulation aqueous metal salt.In addition, natrium citricum is dissolved in the deionized water, modulation concentration is the sodium citrate aqueous solution of 26 quality %.In this sodium citrate aqueous solution, in remaining 35 ℃ stream of nitrogen gas, directly add granular ferrous sulfate and make its dissolving, modulation contains the reducing agent aqueous solution of citrate ions and ferrous ion with the mol ratio of 3:2.
Then, above-mentioned stream of nitrogen gas is being remained under 35 ℃ the state, the stirring parts of magnetic stirring apparatus is put into the reducing agent aqueous solution, stirring parts is rotated with the rotary speed of 100rpm, stir on one side the above-mentioned reducing agent aqueous solution, to this reducing agent aqueous solution drip above-mentioned aqueous metal salt mix on one side.At this, be the concentration that the mode below 1/10 of the amount of the reducing agent aqueous solution is adjusted each solution with addition, thereby even the aqueous metal salt of the room temperature of dripping also can remain on reaction temperature 40 ℃ at the aqueous metal salt of the reducing agent aqueous solution.In addition, about the mixing ratio of the above-mentioned reducing agent aqueous solution and aqueous metal salt, relatively the mol ratio of the citrate ions total atom valence mumber, the reducing agent aqueous solution of the metal ion in the aqueous metal salt and ferrous ion all is 3 times more than the mole.After the reducing agent aqueous solution drips the aqueous metal salt end, continued to mix liquid 15 minutes, thereby, obtain the metallic dispersion liquid that metallic disperses at the inner metallic that produces of mixed liquor.The pH of metallic dispersion liquid is 5.5, and the growing amount on the Chemical Measurement of the metallic in the dispersion liquid is the 5g/ liter.
Resulting dispersion liquid is at room temperature placed, thereby made metallic sedimentation in the dispersion liquid, the condensation product of the metallic by the decantation separate and subside.Add deionized water in the metal condensation product after this separation and form dispersion, carry out desalting processing by ultrafiltration after, and then replace cleaning with methyl alcohol, be 50 quality % thereby make the amount of metal (silver).Then, use centrifugal separator, adjust the centrifugal force of this centrifugal separator, isolate the bigger silver particles that particle diameter surpasses 100nm, thereby be adjusted into, on average contain Nano silver grain in the scope that 71% primary particle size is 10～50nm with quantity.That is, adjust as follows: with the average all relatively Nano silver grain 100% of quantity, primary particle size is that the shared ratio of Nano silver grain in the scope of 10～50nm is 71%.Resulting Nano silver grain is by the protective agent chemical modification of the organic molecule main chain of the carbon number 3 of carbon skeleton.
Then, resulting metal nanoparticle 10 Quality Mgmt Dept are added be mixed in mixed solution 90 Quality Mgmt Dept of containing water, ethanol and methyl alcohol and make its dispersion, and then, table 3 in this dispersion liquid below the adding of the ratio shown in table 3, the table 4, the additive shown in the table 4, thus the conductive reflecting film constituent obtained respectively.In addition, the formation conductive reflecting film contains the above Nano silver grain of 75 quality % with the metal nanoparticle of constituent.In addition, as metal nanoparticle, contain under the situation of Nano silver grain and Nano silver grain metal nanoparticle in addition, except the dispersion liquid of the Nano silver grain that will obtain by said method as first dispersion liquid, and replace silver nitrate and use following table 3, beyond the slaine of the kind of the metal nanoparticle beyond the formation Nano silver grain shown in the table 4, with the manufacture method of above-mentioned Nano silver grain similarly, the dispersion liquid of the metal nanoparticle beyond the modulation Nano silver grain, with the dispersion liquid of this metal nanoparticle as second dispersion liquid, before adding additive, with following table 3, the ratio of table 4, mix first dispersion liquid and second dispersion liquid, thereby obtain the conductive reflecting film constituent.
Then, on the light-to-current inversion layer of solar cell, form composite membrane, form solar cell.Specifically, at first, as shown in Figure 1, has the surface electrode 12(SnO that is texture structure
2Film) on the base material 11, by plasma CVD method, the microcrystal silicon layer that forms thickness 1.7 μ m is as light-to-current inversion layer 13.Then, with the thickness behind the sintering is the mode of the thickness shown in the following table 5, with the above-mentioned nesa coating constituent that is modulated into of various film build methods coatings shown in the following table 3,4, then, with 25 ℃ of dryings of temperature 5 minutes, form the transparent conductivity coated film.Then, with the various film build methods shown in the following table 3,4, with the thickness behind the sintering is the mode of the thickness shown in the following table 5, the above-mentioned conductive reflecting film constituent that is modulated into of coating on formed electrically conducting transparent coated film, then, with 25 ℃ of dryings of temperature 5 minutes, form conductivity reflection coated film.Then, under the heat-treat condition shown in following table 3, the table 4, carry out sintering, thereby on light-to-current inversion layer 13, form composite membrane 14, obtain the solar battery cell substrate.In addition, in table 3, table 4, PVP represents that Mw is 360,000 polyvinylpyrrolidone, and pet sheet shows PETG.
Table 1
Table 2
Table 3
Table 4
＜comparative test and evaluation 〉
About on the light-to-current inversion layer of embodiment 1～10 and comparative example 1,2, having formed the solar battery cell substrate of composite membrane, thickness, the gas cell distribution in the conductive reflecting film, the series resistance of nesa coating in the composite membrane and conductive reflecting film are estimated.These results shown in the table 5 below.
(1) thickness: use SEM(Ri Li System to make the electron microscope that society of institute makes: S800), to distinguish direct instrumentation three times, draw their mean value from the film section.
(2) gas cell distribution:, can use different assay methods from the nesa coating conductive reflecting film of tearing according to whether about the gas cell distribution of the contact surface side that contacts with ELD.
The example of conductive reflecting film of can tearing from nesa coating, at first, for the conductive reflecting film that is close on the nesa coating, apply binding material to anchor clamps, and it is pressed against on the conductive reflecting film, keep with level and smooth face, has high cohesive force up to the binding material intensive drying, then, use cupping machine (Island Jin System to do manufacturing: EZ-TEST) with these anchor clamps of base material pull-up vertically, from the nesa coating conductive reflecting film of tearing.
Then,, use atomic force microscope (AFM), observe the concavo-convex picture of this face for as tearing from nesa coating and exposing the face of conductive reflecting film and contact-making surface nesa coating on anchor clamps.Analyze observed concavo-convex picture, estimate average diameter, mean depth and the number density in the hole that occurs on the film surface.In addition, for average diameter, regard the shortest limit of the mean value hole more than the diameter 20nm in the image of being photographed has been measured the longest limit and to(for) 5 AMF images more than the visual field as.For mean depth, for 5 AMF images more than the visual field, the hole more than the diameter 20nm in the image of being photographed is fathomed, be changed to the mean depth in the circle of radius centered 10nm as deep-seated with the hole.
In addition,, also adopt simultaneously on conductive reflecting film, to attach two-sided tape as the additive method of the conductive reflecting film of tearing from nesa coating, pull-up one end, thereby from the tear method of conductive reflecting film of nesa coating.
The example of conductive reflecting film of can not tearing from nesa coating, at first,, process with focused ion beam (FIB) method for the conductive reflecting film that is close on the nesa coating, the sample section is exposed.(SEM) observes the section of this sample with scanning electron microscope, thereby observes the shape at the interface of nesa coating/conductive reflecting film.About this interface picture, estimate diameter, mean depth and the number density of peristome.For the diameter of peristome, regard the shortest limit of the mean value hole more than the diameter 20nm in the image of being photographed has been measured the longest limit and to(for) 5 SEM images more than the visual field as.For mean depth, for 5 SEM images more than the visual field, the hole more than the diameter 20nm in the image of being photographed is fathomed, be changed to the mean depth in the circle of radius centered 10nm as deep-seated with the hole.
(3) series resistance: configuration lead-in wire on the substrate after the line processing of solar battery cell, use solar simulator and digital source table, obtain shining AM1.5,100mW/cm
2The I-V(current-voltage of light time) curve.And then, by making resulting I-V(current-voltage) current value (I) in the curve is divided by the surface area of solar battery cell, thereby obtain J-V curve (current density-voltage), the inverse that will open near the slope of voltage (current value is 0 o'clock a voltage) is as series resistance.
Table 5
As known from Table 5, in comparative example 1,2, the series resistance when generating is shown is 40～50 Ω/cm
2Like this than higher value, and in the embodiment 1～10 with composite membrane that the present invention of utilizing forms, the series resistance when generating all is shown is 23 Ω/cm
2Below low-down like this value.
［ utilizability on the industry ］
The present invention extremely is suitable as the technology of the composite membrane that the solar cell that is used to make the generating efficiency when improving generating uses.In addition, the application of the invention can be replaced as coating, sintering process with the composite membrane that is made of nesa coating and conductive reflecting film that forms by the vacuum film formation method in the past, can expect to cut down significantly manufacturing cost.
Claims (9)
1. the formation method of the composite membrane used of a solar cell,
On the light-to-current inversion layer that is layered in the solar cell on the base material via surface electrode, utilize wet type coating process coating to contain the atomic dispersion liquid of electroconductive oxide and contain the dispersion liquid of binding agent composition or contain the electroconductive oxide particulate and the two nesa coating formation constituent of binding agent composition, form the electrically conducting transparent coated film
Utilize wet type coating process coating electrically conductive sexual reflex film constituent on described electrically conducting transparent coated film, form conductivity reflection coated film, afterwards,
Base material with described electrically conducting transparent coated film and conductivity reflection coated film is carried out sintering, and thus, the composite membrane that the solar cell that formation is made of nesa coating and conductive reflecting film is used the method is characterized in that,
Described electroconductive oxide particulate comprises particle with aspheric anisotropy shape or a plurality of particle coacervation and any one of the agglomerate with anisotropic structure that forms.
2. the formation method of the composite membrane that solar cell as claimed in claim 1 is used is characterized in that,
The aspect ratio of described anisotropy shaped particle or anisotropic structure agglomerate is more than 3.
3. the formation method of the composite membrane that solar cell as claimed in claim 1 is used is characterized in that,
When being tabular, the described tabular particle or the thickness of agglomerate are 50～1500nm at described anisotropy shaped particle or anisotropic structure agglomerate, and the width and thickness ratio is 2～100.
4. the formation method of the composite membrane of using as any described solar cell of claim 1～3 is characterized in that,
Described wet type coating process is any one in spraying process, distributor coating process, spin-coating method, scraper plate coating process, slit coating method, ink-jet coating method, silk screen print method, hectographic printing method or the mold coating process.
5. a nesa coating forms and uses constituent, and sintering forms the described nesa coating of the described solar cell of formation with composite membrane to be used for applying also by the wet type coating process, wherein,
Described constituent is made of atomic dispersion liquid of the electroconductive oxide that does not comprise the binding agent composition and the dispersion liquid that do not comprise the atomic described binding agent composition of described electroconductive oxide or constitutes by comprising the two dispersion liquid of described electroconductive oxide particulate and described binding agent composition
Described electroconductive oxide particulate comprises particle with aspheric anisotropy shape or a plurality of particle coacervation and any one of the agglomerate with anisotropic structure that forms.
6. nesa coating as claimed in claim 5 forms and uses constituent, it is characterized in that,
The aspect ratio of described anisotropy shaped particle or anisotropic structure agglomerate is more than 3.
7. nesa coating as claimed in claim 5 forms and uses constituent, it is characterized in that,
When being tabular, the described tabular particle or the thickness of agglomerate are 50～1500nm at described anisotropy shaped particle or anisotropic structure agglomerate, and the width and thickness ratio is 2～100.
8. the composite membrane that solar cell is used is characterized in that,
Constitute by the described nesa coating and the described conductive reflecting film that form by any described method in the claim 1 to 4.
9. a solar cell is characterized in that,
Has the composite membrane that the described solar cell of claim 8 is used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010-121557 | 2010-05-27 | ||
| JP2010121557 | 2010-05-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108335913A (en) * | 2017-11-29 | 2018-07-27 | 住华科技股份有限公司 | Solar optical film laminate and method for manufacturing same |
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| CN114534990B (en) * | 2022-01-11 | 2023-03-14 | 西安理工大学 | ITO thin film suitable for flexible device and preparation method thereof |
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|---|---|---|---|---|
| CN1362936A (en) * | 2000-02-04 | 2002-08-07 | 大塚化学株式会社 | Hexagonal lamellar compound based on indium-zinc oxide |
| CN101023498A (en) * | 2004-08-31 | 2007-08-22 | 住友金属矿山株式会社 | Conductive particle, visible light transmissive particle dispersed conductor, method for producing same, transparent conductive thin film, method for producing same, transparent conductive article usi |
| CN101134597A (en) * | 2006-08-28 | 2008-03-05 | 同和电子科技有限公司 | ITO powder and method for manufacturing same, coating material for electroconductive ITO film, and transparent electroconductive film |
| WO2009035112A1 (en) * | 2007-09-12 | 2009-03-19 | Mitsubishi Materials Corporation | Composite membrane for super straight solar cell, process for producing the composite membrane for super straight solar cell, composite membrane for substraight solar cell, and process for producing the composite membrane for substraight solar cell |
-
2011
- 2011-05-18 JP JP2011110969A patent/JP2012009840A/en not_active Withdrawn
- 2011-05-23 KR KR1020110048583A patent/KR20110130345A/en not_active Application Discontinuation
- 2011-05-24 CN CN2011101351035A patent/CN102263158A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362936A (en) * | 2000-02-04 | 2002-08-07 | 大塚化学株式会社 | Hexagonal lamellar compound based on indium-zinc oxide |
| CN101023498A (en) * | 2004-08-31 | 2007-08-22 | 住友金属矿山株式会社 | Conductive particle, visible light transmissive particle dispersed conductor, method for producing same, transparent conductive thin film, method for producing same, transparent conductive article usi |
| CN101134597A (en) * | 2006-08-28 | 2008-03-05 | 同和电子科技有限公司 | ITO powder and method for manufacturing same, coating material for electroconductive ITO film, and transparent electroconductive film |
| WO2009035112A1 (en) * | 2007-09-12 | 2009-03-19 | Mitsubishi Materials Corporation | Composite membrane for super straight solar cell, process for producing the composite membrane for super straight solar cell, composite membrane for substraight solar cell, and process for producing the composite membrane for substraight solar cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108335913A (en) * | 2017-11-29 | 2018-07-27 | 住华科技股份有限公司 | Solar optical film laminate and method for manufacturing same |
| CN108335913B (en) * | 2017-11-29 | 2019-11-08 | 住华科技股份有限公司 | Solar optical film laminate and method for manufacturing same |
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| JP2012009840A (en) | 2012-01-12 |
| KR20110130345A (en) | 2011-12-05 |
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