CN100524939C - Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same - Google Patents
Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same Download PDFInfo
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- CN100524939C CN100524939C CNB2005800037096A CN200580003709A CN100524939C CN 100524939 C CN100524939 C CN 100524939C CN B2005800037096 A CNB2005800037096 A CN B2005800037096A CN 200580003709 A CN200580003709 A CN 200580003709A CN 100524939 C CN100524939 C CN 100524939C
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- solar battery
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 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 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940062049 nitrogen 70 % Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229940062054 oxygen 30 % Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GPMKKHIGAJLBMZ-UHFFFAOYSA-J titanium(4+);tetraacetate Chemical compound [Ti+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O GPMKKHIGAJLBMZ-UHFFFAOYSA-J 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention uses provides a dye-sensitized solar cell with excellent adhesion between transparent conductive layer and porous semiconductor layer and exhibiting high photovoltaic performance by the use of a laminated film for dye-sensitized solar cell, characterized in that it comprises a polyester film, is superimposed on one major surface thereof, a transparent conductive layer, and the transparent conductive layer has a surface tension of >=40 mN/m.
Description
Technical field
The present invention relates to used by dye sensitization solar battery laminated film, used by dye sensitization solar battery electrode and manufacture method thereof.
Background technology
Since the scheme that has proposed to use the atomic photo-electric conversion element of dye-sensitized semiconductor (nature (Nature) the 353rd volume, the 737th～740 page (1991)), DSSC silicon as an alternative is the novel solar battery of solar cell and receiving much concern.Particularly use the DSSC of plastic film as carrier, can softnessization and lightweight, it has been carried out a large amount of research all the time.
Summary of the invention
When using plastic film as the DSSC of carrier, be difficult on transparency conducting layer, form porous semiconductor layer, be difficult to guarantee the good adaptation of transparency conducting layer and porous semiconductor layer.If do not guarantee good adaptation, then the light power generation performance of solar cell reduces.
The object of the present invention is to provide used by dye sensitization solar battery laminated film and used by dye sensitization solar battery electrode, described used by dye sensitization solar battery laminated film can be made the adaptation excellence of transparency conducting layer and porous semiconductor layer, the DSSC that the light power generation performance is high.
The present invention also aims to provide the manufacture method of used by dye sensitization solar battery electrode of the adaptation excellence of transparency conducting layer and porous semiconductor layer.
That is, the invention provides the used by dye sensitization solar battery laminated film, it is characterized by, the transparency conducting layer that contains polyester film and on its one side, be provided with, the surface tension of transparency conducting layer is more than the 40mN/m.
The present invention also provides the used by dye sensitization solar battery electrode, the porous semiconductor layer that it contains above-mentioned used by dye sensitization solar battery laminated film and is provided with on its transparency conducting layer.
The present invention also provides the manufacture method of used by dye sensitization solar battery electrode, it is characterized by, be to form transparency conducting layer on the one side of the polyester film below 0.8% at the absolute value of the thermal contraction rate variance of the length direction of 200 ℃ of films after down handling 10 minutes and cross direction, and by forming porous semiconductor layer thereon at 170～250 ℃ of following sintered metal oxides.
Below, describe the present invention in detail.
＜polyester film 〉
＜polyester 〉
In the present invention, the polyester of formation polyester film is by aromatic acid or its ester formation property derivative and dihydroxylic alcohols or the synthetic chain saturated polyester of its ester formation property derivative.
The object lesson of described polyester can example go out PETG, polyethylene glycol isophthalate, polybutylene terephthalate (PBT), gather (1,4-cyclohexene dimethylene terephthalate), gather-2, the 6-(ethylene naphthalate).Wherein, PETG, poly--2, the mechanics rerum natura and the optics rerum natura isoequilibrium of 6-(ethylene naphthalate) are good, are preferred therefore.Particularly poly--2, the 6-(ethylene naphthalate), its mechanical strength excellence, percent thermal shrinkage are little, the generation of oligomer is few during heating, is most preferred therefore.
Polyester can be a homopolymers, also can be copolymer, preferred homopolymers.When polyester was copolymer, with respect to total dicarboxylic acids composition or total glycol component, copolymer composition was preferably the following ratio of 3 moles of %.
When using copolymer composition, the dicarboxylic acids composition can example go out terephthalic acid (TPA), 2, the aromatic dicarboxylic acid of 6-naphthalenedicarboxylic acid, adipic acid, azelaic acid, decanedioic acid, 1, the aliphatic dicarboxylic acid of 10-ten carbon diacid.Glycol component can example go out 1,4-butanediol, 1, the aliphatic dihydroxy alcohol of 6-hexylene glycol, neopentyl glycol, 1, the alicyclic dihydroxylic alcohols of 4-cyclohexanedimethanol.
Polyester can be made with known method.For example, can utilize the method that makes dicarboxylic acids and diol reaction and directly obtain the low polymerization degree polyester to make.Can also utilize following method to make, that is, make the lower alkyl esters of dicarboxylic acids and dihydroxylic alcohols carry out ester exchange reaction, then under the condition that polymerization catalyst exists, carry out polymerization reaction, obtain polyester thus by ester exchange catalyst.At this moment, the catalyst of ester exchange reaction can use sodium, potassium, magnesium, calcium, zinc, strontium, titanium, zirconium, manganese, cobalt.Polymerization catalyst can use for example antimony trioxide, antimony pentaoxide, germanium dioxide, tetraethyl titanate, metatitanic acid orthocarbonate, metatitanic acid four phenyl esters, ammonium titanyl oxalate, titanium potassium oxalate, triacetyl acetate titanium.
Carry out ester exchange reaction, when then carrying out polymerization reaction, preferably before polymerization reaction, adding the phosphorus compound that is used to make the ester exchange catalyst inactivation.This phosphorus compound can use for example trimethyl phosphate, triethyl phosphate, TRI N BUTYL PHOSPHATE, orthophosphoric acid.
The intrinsic viscosity of polyester is preferably more than the 0.40dl/g, more preferably 0.40～0.90dl/g.During less than 0.40dl/g, process interruption often takes place; Then melt extrude difficulty when surpassing 0.9dl/g, polymerization time is long, and is uneconomical and not preferred.
Polyester film among the present invention preferably is substantially free of particle.When containing particle, high transparent can be impaired sometimes, perhaps surperficial sometimes roughening and make the processing of transparency conducting layer become difficult.
＜ultra-violet absorber 〉
Polyester film of the present invention preferably contains ultra-violet absorber.Ultra-violet absorber preferably uses the compound with following general formula (I) expression.
(in the formula, R is the aromatic hydrocarbons residue of divalent, Y
1, Y
2Be that carbon number is that 1～10 alkyl, carbon number are that 1～3 alkoxyl, halogen, carbon number are 2～4 acyl group.)
In compound, be preferably as follows compound as ultra-violet absorber with general formula (I) expression: 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-TOPOT 2,2 (6-methyl-3,1-benzoxazine-4-ketone), 2,2 '-TOPOT 2,2 (6-chloro-3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-diphenylene) two (3,1-benzoxazine-4-ketone) and 2,2 '-(2, the 6-naphthylene) two (3,1-benzoxazine-4-ketone).
With respect to the polyester 100 weight % of polyester film, the content of ultra-violet absorber is preferably 0.1～5 weight %, more preferably 0.2～3 weight %.During less than 0.1 weight %, can not fully reduce the light transmittance at wavelength 370nm place; When surpassing 5 weight %, can not fully improve the light transmittance at wavelength 400nm place, therefore not preferred.
For example, ultra-violet absorber is contained in the polyester film, that is, mixingly in the method for in the polymerization process of polyester, adding, the fusion operation before film system film goes into method in the polyester polymers, contain the method that is dipped in the film.Wherein, preferred mixing method of going in the polyester polymers in the fusion operation before film system film.When using this method, can prevent that the degree of polymerization of polyester from reducing.The mixing operation of going in the polyester polymers of ultra-violet absorber for example, can be undertaken by direct addition method, the masterbatch method of compound powder.
＜optical characteristics 〉
Polyester film of the present invention, its light transmittance at wavelength 370nm place is preferably below 3%, more preferably below 2%, and is preferably more than 70% at the light transmittance at wavelength 400nm place, more preferably more than 75%.The light transmittance at wavelength 370nm place surpasses at 3% o'clock, and it is insufficient that ultraviolet shielding effect becomes, and the visible light generating efficiency changed and reduces along with the time when making DSSC, thereby not preferred.The light transmittance at wavelength 400nm place is less than 70%, and then the visible light quantity brought of light generating reduces, and therefore can not obtain sufficient light generating efficiency and not preferred.
In order to carry out the light generating more efficiently, the substrate of polyester film of the present invention is preferably below 1.5%, more preferably below 1.0%, is preferably below 0.5% especially.
＜percent thermal shrinkage 〉
Polyester film of the present invention is preferably below 0.8% at the absolute value of the thermal contraction rate variance of length direction that carries out 10 minutes films after the processing under 200 ℃ and cross direction, more preferably below 0.5%, is preferably below 0.3% especially.The absolute value of thermal contraction rate variance surpasses at 0.8% o'clock, and then the adaptation of the transparency conducting layer of laminated film and the porous semi-conductor on it is understood variation, can not obtain sufficient light power generation performance when making DSSC and not preferred.
When polyester film of the present invention carried out handling in 10 minutes under 200 ℃, the percent thermal shrinkage of the length direction of film was preferably 0～0.5%, and more preferably 0～0.3%.If the percent thermal shrinkage of length direction surpasses 0.5%, when then utilizing heat treatment, the polyester film of laminated film and the adaptation of transparency conducting layer reduce, and perhaps the adaptation of transparency conducting layer and the porous semiconductor layer on it reduces, and is therefore not preferred.
＜surface roughness thickness 〉
The three-dimensional center line mean roughness of polyester film of the present invention, the two sides all is preferably 0.0001～0.02 μ m, and more preferably 0.0001～0.015 μ m is preferably 0.0001～0.010 μ m especially.And Yi Mian three-dimensional center line mean roughness is preferably 0.0001～0.005 μ m at least, more preferably 0.0005～0.004 μ m.And the thickness of polyester film is preferably 10～500 μ m, and more preferably 20～400 μ m are preferably 50～300 μ m especially.During scope, preferred for this reason owing to be easy to process transparency conducting layer.
The manufacture method of＜polyester film 〉
The polyester film that possesses above-mentioned characteristic for example can be made with the following method.It should be noted that glass transition temperature is abbreviated as Tg.
Polyester film of the present invention can obtain in order to following method: promptly, polyester is melt extruded into film like, make its cooling curing and form non-stretched film with pouring cylinder, under Tg～(Tg+60) ℃, stretching more than 1 time or 2 times on the length direction this non-stretched film, make and add up to multiplying power to reach 3 times～6 times, under Tg～(Tg+60) ℃, be stretched to 3～5 times of multiplying powers then, as required, further under 180 ℃～255 ℃, carry out heat treatment in 1～60 second at cross direction.
Particularly, can in heat treatment step, on length direction, make its contraction for the thermal contraction rate variance that fully reduces polyester film length direction and cross direction and the thermal contraction of length direction, perhaps can be under overhang to the film heat treatment that relaxes.The method of its contraction is described in the Japanese kokai publication hei 57-57628 communique, can uses this method.In addition, under overhang, the film heat-treating methods that relaxes is described in the Japanese kokai publication hei 1-275031 communique, can uses this method.
＜transparency conducting layer 〉
Transparency conducting layer can use the metal oxide of conductivity, for example fluorine doped tin oxide, indium-Xi composite oxides (ITO).Metallic film also can use for example platinum, gold, silver, copper, aluminium.Can use material with carbon element.
Transparency conducting layer can use a kind, also can lamination 2 kinds with on use, can also carry out compound back and use.Wherein, the light transmittance height of indium-Xi composite oxides (ITO), be low resistance, therefore preferred especially.
The surface tension of transparency conducting layer is more than the 40mM/m, to be preferably more than the 65mN/m.Surface tension is during less than 40mM/m, then the adaptation variation of transparency conducting layer and porous semi-conductor.It should be noted that surface tension is 65mN/m when above,, form porous semiconductor layer easily by coating water-based masking liquid, thus preferred.The capillary practical upper limit of transparency conducting layer is set as about the 75mN/m that complete water system paint is easy to be coated with.
The scope of the sheet resistance of transparency conducting layer is preferably below 100 Ω, more preferably below 40 Ω.When surpassing 100 Ω, inside battery resistance is excessive, and the light generating efficiency reduces, and is therefore not preferred.
The thickness of transparency conducting layer is preferably 100～500nm.During less than 100nm, can not fully reduce sheet resistance value; When surpassing 500nm, light transmittance reduces, and transparency conducting layer is easy to break, and is therefore not preferred.
Above-mentioned surface tension can obtain by the surface with following any one method activation transparency conducting layer.That is, handle the method that activates in acid or alkaline solution, the method that irradiation ultraviolet radiation or electron beam activate is implemented the method that corona treatment or plasma treatment activate.Wherein come the method for activating surface, particularly come the method for activating surface by plasma treatment by corona treatment or plasma treatment, preferred owing to can obtain high surface tension.When activating layer at transparent layer, can adopt following condition by plasma treatment.That is, use the atmospheric plasma surface processing device, under 1～200L/ minute air-flow of the mist of inert gas or inert gas and oxygen, layer at transparent layer is implemented plasma treatment with 0.1～10m/ minute speed.Inert gas can use for example nitrogen.
＜easy adhesion layer 〉
For laminated film of the present invention,, preferably between polyester film and transparency conducting layer, has easy adhesion layer in order to improve the adaptation of polyester film and the transparency conducting layer on it.Easily the thickness of adhesion layer is preferably 10～200nm, more preferably 20～150nm.When easily the thickness of adhesion layer is less than 10nm, lack the effect that improves adaptation; When surpassing 200nm, easily adhesion layer is easy to take place cohesion destruction, and adaptation can reduce sometimes, and is therefore not preferred.
Easily adhesion layer preferably is provided with by being coated with in the manufacture process of polyester film.Polyester film before this coating preferably finishes directional crystallization carries out.Polyester film before crystal orientation finishes comprises non-stretched film, non-stretched film is oriented to an oriented film of any one direction of longitudinal direction or transverse direction, stretch on longitudinal direction and transverse direction both direction low range ground and make its directed biaxially oriented film (finally stretch again and before finishing directional crystallization biaxially oriented film) on longitudinal direction or transverse direction.Wherein, the water-based masking liquid of the easy adhesion layer composition of coating on non-stretched film or oriented film, keeping intact indulge stretches and/or horizontal stretching, obtains biaxially oriented film, preferably to its enforcement heat fixation.
Easily adhesion layer is preferably by polyester film and transparency conducting layer both sides are shown that all excellent adhesive material constitutes.Material specifically can exemplify out mylar, acrylic resin, urethane acrylate resin, silicon acrylic resin, melamine resin, polyorganosiloxane resin.These resins can use separately, also can be using as mixture more than 2 kinds.
＜hard conating 〉
For laminated film of the present invention, owing to improved the adaptation of polyester film and the transparency conducting layer on it, particularly improved the persistence of adhering to, therefore preferably easily have hard conating between adhesion layer and the transparency conducting layer.Hard conating can be by being provided with its curing at the constituent material that is provided with coating hard conating on the polyester film of easy adhesion layer.The constituent material of hard conating can use commute adhesion layer and transparency conducting layer both sides all to show the material of adaptation.For example, can use the mixture of resin and inorganic particulate.It is that resin, silicon are that resin, UV curing are that resin, epoxy are resin that resin can use as acrylic resin, ammonia ester.Inorganic particulate can use as aluminium oxide, silicon dioxide, mica.The thickness that it should be noted that hard conating is preferably 0.01～20 μ m, more preferably 1～10 μ m.
＜anti-reflection layer 〉
For laminated film of the present invention, the light generating efficiency is improved, preferably with the one side of transparency conducting layer opposition side on have anti-reflection layer.
This anti-reflection layer can form the layer of feed stock material with the refractive index that is different from the polyester film refractive index by individual layer formation or multilayer and be provided with.During for the anti-reflection layer of individual layer, can use the raw material that have less than the refractive index of base film.During for the anti-reflection layer of multilayer, use the raw material that have greater than the refractive index N of polyester film with the optimal seeking of raw and processed materials of the layer of laminated film adjacency, the raw material that have less than the refractive index N ' of N are used in the optimal seeking of raw and processed materials of layer laminated thereon.
Constitute the raw material of anti-reflection layer, can use the organic material and/or the inorganic material that satisfy above-mentioned index of refraction relationship.For example, can example go out CaF
2, MgF
2, NaAlF
4, SiO
2, ThF
4, ZrO
2, Nd
2O
3, SnO
2, TiO
2, CeO
2, ZnS, In
2O
3Dielectric.
With the method for anti-reflection layer lamination, can use for example dry-coated method, the wet method that is coated with.Dry-coated method can be used for example vacuum vapour deposition, sputtering method, CVD method, ion plating method.Wet be coated with method and can use for example intaglio printing mode, reverse mode, die head mode.
And then, before the lamination of anti-reflection layer, can implement the pre-treatment of Corona discharge Treatment, plasma treatment, sputter etching processing, electron beam treatment with irradiation, ultraviolet irradiation processing, prime treatment, easy adhesion process etc. to the face that anti-reflection layer is set.
＜porous semiconductor layer 〉
The porous semiconductor layer that used by dye sensitization solar battery electrode of the present invention contains above-mentioned used by dye sensitization solar battery laminated film and is provided with on its transparency conducting layer.Porous semiconductor layer is by forming in 170～250 ℃ of following sintered metal oxides on transparency conducting layer.Metal oxide constitutes the porous semiconductor layer as the n N-type semiconductor N.The material that in addition, can use a plurality of these oxides compound and obtain.
In the present invention, in order to form porous semiconductor layer, on the transparency conducting layer that forms on the polyester film one side, by forming porous semiconductor layer at 170～250 ℃ of following sintered metal oxides.At this moment, preferably to use the absolute value at the thermal contraction rate variance of the length direction of 200 ℃ of films after carrying out handling in 10 minutes and cross direction be polyester film below 0.8% to polyester film.
Metal oxide preferably uses and is selected from titanium oxide (TiO
2), zinc oxide (ZnO) and tin oxide (SnO
2) at least a kind of metal oxide.
Sintering carries out for the reinforcement that improves the electronics contact between the semiconductor microactuator particle and with the adaptation of transparency conducting layer.Sintering condition be preferably 170～250 ℃ 1～120 minute down, more preferably 180～230 ℃ 3～90 minutes down, be preferably especially 190～220 ℃ 5～60 minutes down.By carrying out this sintering,, rise Yi Bian reduce the resistance of porous semiconductor layer on one side can prevent the distortion that polyester film causes because of heating.The temperature of sintering is during less than 170 ℃, and the contact of the electronics of semiconductor microactuator particle can not fully be strengthened, and makes DSSC time generating efficiency and reduces.When surpassing 250 ℃, the distortion that polyester film causes because of heating becomes significantly, and the adaptation of transparency conducting layer and porous semiconductor layer reduces.
This porous semiconductor layer presents the structure of semi-conductive ultramicron sintering or fusion.With regard to the particle diameter of this ultramicron, the average grain diameter of primary particle is preferably 5～100nm, is preferably 5～50nm especially.
As semi-conductive ultramicron, can be the different atomic mixture more than 2 kinds of particle size distribution.In order to make the incident light scattering improve the light catch rate, also can mix the big semiconductor particle of particle diameter.The semiconductor particle of the average grain diameter that this semiconductor particle can use primary particle for example about as 300nm.
The semi-conductive ultramicron that constitutes porous semiconductor layer can be prepared by the following method: promptly, known sol-gel process or vapour-phase pyrolysis method (repairing " basis of DSSC and application " with reference to the distribution of calendar year 2001 technical education publishing house, Shozo Yanagida prison, perhaps nineteen ninety-five technical information association distribution, " utilizing the film coated technology of sol-gel process ").
It should be noted that, in order to prepare the dispersion liquid of semi-conductive ultramicron, can to use method that particulate is separated out as the coprecipitated product of chemical reaction, utilizing ultrasonic irradiation or mechanical crushing and be ground into the method for ultramicron and then dispersion.
Porous semiconductor layer preferable use cloth method forms.That is, preferably, the dispersion liquid that will contain the semiconductor ultramicron is applied on the transparency conducting layer of laminated film, and heat drying is fixed on porous semiconductor layer on the transparency conducting layer thus.
Decentralized medium makes water or organic solvent.During dispersion, as required, for example can be with the polymer as polyethylene glycol, hydroxyethylcellulose, carboxymethyl cellulose, surfactant, acid or chelating agent add on a small quantity and make dispersion liquid as disperse additive.
For the dispersion liquid of semiconductor ultramicron, the semiconductor microactuator particle is with respect to carrier 1m
2, can be preferably with 0.5～20g/m
2, further preferably with 5～10g/m
2Amount be coated with.Coating can be carried out with any means that coating is in the past used always.For example, can use rolling method, dip coating, air knife knife coating, knife coating, ring rod method, sliding hopper method, extrusion molding, curtain formula method.In addition, can also use spin-coating method or the spraying process that is undertaken by universal machine.With relief printing plate, hectograph and heliogravure three big print processes is representative, can use the wet printing as intaglio plate, flexographic, silk screen printing to be coated with.Wherein, can select desirable film-forming method according to liquid viscosity and thickness of slab.
Porous semiconductor layer is preferably formed 1～30 μ m, further is preferably formed 2～10 μ m, is preferably formed the thickness of 2～6 μ m especially.As long as, just can obtain high transparency for this scope.
And then, by porous semiconductor layer being shone the strong light that absorbs of its ultramicron, irradiating ultraviolet light for example, perhaps irradiating microwaves also can be strengthened the processing of the physical engagement between the ultramicron.
It should be noted that the transparency conducting layer that supports porous semi-conductor in order to prevent and electrical short to electrode, can be provided with prime coat in advance on transparency conducting layer.In this case, the thickness of prime coat is preferably 5～1000nm, is preferably 10～500nm especially.TiO is used in the optimal seeking of raw and processed materials of prime coat
2, SnO
2, ZnO, Nb
2O
5, especially preferably use TiO
2Priming coat can be provided with by for example Electrochim, Acta40,643～652 (1995) spray pyrolysis, the sputtering methods of being put down in writing.
The manufacturing of＜DSSC "
In order to use used by dye sensitization solar battery electrode of the present invention to make DSSC, can use the known method relevant with the manufacturing of DSSC.This method can make with the following method.
(1) manufacturing of electrode A
Make the porous semiconductor layer absorbing dye of electrode of the present invention.Promptly, following dyestuff is dissolved in alcohol or the toluene equal solvent makes dye solution, in this dye solution, flood porous semiconductor layer, perhaps with the spraying of this dye solution or be applied on the porous semiconductor layer, described dyestuff be with ruthenium bipyridines complex (ruthenium complex) be representative Organometallic complexes dyestuff, cyanine class dyestuff, Coumarins dyestuff, xanthene class dyestuff, porphyrin class dyestuff etc., have the dyestuff of characteristic of the light of absorption visible-range and infrared light scope.
(2) manufacturing of electrode B (to electrode)
Forming thin platinum layer by sputtering method on transparency conducting layer one side of laminated film of the present invention makes electrode.
(3) crimping of electrode
Insert the flame type sept (thick 20 μ m) of the polyethylene film system of thermo-compressed, above-mentioned electrode A and electrode B are overlaped, sept partly is heated to 120 ℃, they are carried out crimping.The edge part of resulting structures body is sealed with epoxyn.
(4) electrolytical injection
The electrolyte in the bight by being located at the said structure body in advance injects use aperture, and injection contains lithium iodide and iodine (mol ratio 3:2) and is the electrolyte aqueous solution of the nylon beads 3 weight % of 20 μ m as the average grain diameter of sept.Then, fully carry out the inside degassing, use the epoxyn sealed aperture at last.
Use used by dye sensitization solar battery laminated film of the present invention and used by dye sensitization solar battery electrode, utilize as above method, can make DSSC.
Embodiment
Below, illustrate in greater detail the present invention by embodiment.
Each characteristic value in the example is measured with following method and is obtained.
(1) intrinsic viscosity
Intrinsic viscosity η (dl/g) measures in 35 ℃ o-chlorphenol solution and calculates.
(2) film thickness
Use micrometer (the K-402B type of ア Application リ Star (strain) system), measure with the sept of 10cm separately, all measure the film thickness of 300 positions at the continuous system film direction of film and cross direction.Calculate the mean value of the film thickness of 300 positions of gained, and as film thickness.
(3) percent thermal shrinkage
In the baking oven that is set at 200 ℃ of temperature, kept film 10 minutes with no tense situation, calculate the change in size of various heat treated front and back with following formula for film length direction (MD) and cross direction (TD), it as percent thermal shrinkage, is obtained the percent thermal shrinkage of length direction (MD) and cross direction (TD).
Percent thermal shrinkage (%)=((L0-L)/L0) * 100
L0: distance between the punctuate before the heat treatment, L: distance between the punctuate after the heat treatment
(4) thickness of coating layer
The small pieces of film are embedded in the epoxy resin (=リ Off ァ イ Application テ ッ Network (strain) system エ Port マ ウ Application ト), it is thick that the Microtome2050 of use Reichert-Jung corporate system is sliced into 50nm with each embeding resin, observe for 100,000 times with accelerating voltage 100KV, multiplying power with transmission electron microscope (LEM-2000), measure the thickness that is coated with rete.
(5) sheet resistance value
Use four point probe formula surface resistivity determinator (Mitsubishi Chemical's (strain) system, ロ レ ス GP), measure any 5 points, its mean value is used as typical value.
(6) surface tension
Use contact angle meter (consonance interface science corporate system CA-X type), under 25 ℃, the condition of 50%RH, measure contact angle θ w, θ y for the transparent conducting film of known water of surface tension and diiodomethane.Use these measured values, calculate the surface tension γ s of transparent conducting film as follows.
The surface tension γ s of transparent conducting film be dispersed composition γ sd and polar component γ sp and.That is,
γ s=γ sd+ γ sp (formula 1)
Perhaps, according to the Young formula,
γ s=γ sw+ γ wcos θ w (formula 2)
γ s=γ sy+ γ ycos θ y (formula 3)
At this, γ sw is the tension force that acts between transparent conducting film and the water, and γ sy is the tension force that acts between transparent conducting film and the diiodomethane, and γ w is the surface tension of water, and γ y is the surface tension of diiodomethane.
In addition, according to the Fowkes formula,
γ sw=γ s+ γ w-2 * (γ sd γ wd) 1/2-2 * (γ sp γ wp) 1/2 (formula 4)
γ sw=γ s+ γ y-2 * (γ sd γ yd) 1/2-2 * (γ sp γ yp) 1/2 (formula 5)
At this, γ wd is the capillary dispersed composition of water, and γ wP is the capillary polar component of water, and γ yd is the capillary dispersed composition of diiodomethane, and γ yP is the capillary polar component of diiodomethane.
By the associating equation of calculating formula 1～5, can calculate the surface tension γ s=γ sd+ γ sp of transparent conducting film.At this moment, the surface tension of water (γ w): 72.8mN/m, the surface tension of diiodomethane (γ y): 50.5mN/m, the capillary dispersed composition of water (γ wd): 21.8mN/m, the capillary polar component of water (γ wp): 51.0mN/m, the capillary dispersed composition of diiodomethane (γ yd): 49.5mN/m.The capillary polar component of diiodomethane (γ yP): 1.3mN/m.
(7) adaptation of porous semiconductor layer
On the porous semi-conductor laminar surface so that gauze is loaded 50g/cm
2Weight come and go 5 times, be that target is estimated with the extent of exfoliation.Do not see peel off be designated as zero, visible part is peeled off is designated as △, peel off fully be designated as *.
(8) light generating efficiency
Make 25mm
2Big DSSC is at AM1.5 simulated solar irradiation 100mV/cm
2Irradiation under carry out I-V and measure, obtain open circuit voltage, short-circuit current density, the curve factor, light generating efficiency thus.Use the CEP-2000 type beam split sensitometry device of beam split gauge system to measure.
(9) I-V characteristic (photoelectric current-voltage characteristic)
Make 25mm
2Big DSSC is calculated the light generating efficiency with following method.Go up installation sunlight simulation revisal filter (AM1.5Global of オ リ エ-Le corporate system) at the xenon lamp (ウ シ オ electric corporation system) of 500W, to above-mentioned light generating device, multiple change incident angle with respect to the horizontal plane, the irradiation incident intensity is 100mW/cm
2Simulated solar irradiation.That system is statically placed in is indoor, in the environment of 18 ℃ of temperature, humidity 50%.Use current/voltage determinator (ケ-ス レ-system ソ-ス メ ジ ヤ-ユ ニ ッ ト 238 types), put on the dc voltage of system with the constant speed scanning of 10mV/ second, the photoelectric current of measuring component output is measured photoelectric current-voltage characteristic thus, calculates the light generating efficiency.
(10) weather-proof promotion test
Use daylight type ageing tester (ス ガ testing machine (strain) system, WEL-SUN-HCL type),, promote test by shining to expose to the open air in 1000 hours according to JIS-K-6783.
Embodiment 1
(preparation of the aqueous dispersion of acrylic compounds)
In four-hole boiling flask, add dodecyl sodium sulfate 3 weight portions and ion exchange water 181 weight portions, under nitrogen current, be warmed up to 60 ℃ as surfactant.Then, interpolation is as ammonium persulfate 0.5 weight portion and nitrous acid hydrogen sodium 0.2 weight portion of polymerization initiator.Then, splash into the mixture of methyl methacrylate 30.1 weight portions, 2-isopropyl-2-oxazoline 21.9 weight portions, polyoxyethylene (n=10) methacrylic acid 39.4 weight portions and acrylamide 8.6 weight portions as monomer.The dropping process is, on one side adjust reaction system the liquid temperature reach 60～70 ℃, drip on one side, need 3 hours.After dripping end, further the liquid temperature of reaction system is remained on 60～70 ℃ scope,, reaction is continued Yi Bian stirred 2 hours.Then, cooling obtains the aqueous dispersion that solid constituent is the acrylic compounds of 35% weight.
(preparation of the aqueous dispersion of silica filler)
Make and contain silica filler (Misao Kusano's system, trade name ス ノ-テ ッ Network ス ZL, average grain diameter 100nm) 0.2 weight % and as polyoxyethylene (n=7) lauryl ether of the wetting agent (aqueous dispersion of the silica filler of 0.3 weight % of Sanyo Chemical Industries Co., Ltd.'s system, trade name Na ロ ア Network テ イ-N-70).
(preparation of paint A)
Mix aqueous dispersion 15 weight portions of acrylic compounds and aqueous dispersion 85 weight portions of silica filler, make paint A.
(the film preparation of polyester)
Use 2,6-naphthalene diformic acid dimethyl ester 100 weight portions and ethylene glycol 60 weight portions and as four water manganese acetates, 0.03 weight portion of catalyst for ester exchange reaction, to react on one side the temperature that is and slowly be warmed up to 238 ℃ from 150 ℃, generally carry out ester exchange reaction 120 minutes.In this process, the moment that reaches 170 ℃ in reaction temperature is added three amine-oxides, 0.024 weight portion.After ester exchange reaction finished, the ethylene glycol solution of trimethyl phosphate 0.023 weight portion being made trimethyl phosphate added.The ethylene glycol solution of trimethyl phosphate is under 135 ℃, the pressurized conditions of 0.11～0.16MPa trimethyl phosphate to be carried out heat treated to come ready-made in 5 hours in ethylene glycol.These substance transfer in polymer reactor, are warmed up to 290 ℃, and under the high vacuum below the 27Pa, carry out polycondensation reaction.Can obtain being substantially free of the poly--2 of particle, 6-(ethylene naphthalate) polymer (intrinsic viscosity 0.63dl/g).
(manufacturing of biaxially oriented film)
Should gather-2,6-(ethylene naphthalate) polymer is following dry 6 hours at 170 ℃ with the form of particle, supply in the extruder funnel, under 305 ℃ of melt temperatures, carry out fusion, with average slot is that the stainless steel fine rule filter of 17 μ m filters, and by the slot die of 3mm, is expressed into surface temperature and is on 60 ℃ the rotation cooling cylinder, carry out chilling, obtain non-stretched film.This non-stretched film is carried out preheating in 120 ℃, between low speed roller and the high speed roller above the 15mm IR heater with 850 ℃ heat, be drawn into 3.2 times at longitudinal direction, obtain vertical oriented film.On the one side of this vertical oriented film, be coated with ready-made paint A, form easy adhesion layer with roll coater.At this moment, regulate the coating weight of paint A, make the thickness of the easy adhesion layer in dry back reach 0.2 μ m.And then, with this membrane supplying tentering device, under 140 ℃, be drawn into 3.4 times, and then under 244 ℃, carried out heat fixation 5 seconds in transverse direction, obtain possessing the biaxially oriented film of easy adhesion layer.The intrinsic viscosity of this film is 0.59dl/g, and thickness is 125 μ m, and after heat-treating 10 minutes under 200 ℃, the percent thermal shrinkage of length direction is 0.58%, and the percent thermal shrinkage of cross direction is 0.12%, and the thermal contraction rate variance of length direction and cross direction is 0.46%.
(formation of hard conating)
Possess the hard paint of coating UV curable (JSR system, trade name デ ソ ラ イ ト R7501) on the easy adhesion layer of biaxially oriented film of easy adhesion layer at this, make thickness reach about 5 μ m, irradiation ultraviolet radiation makes its curing, forms hard conating.Obtain possessing the laminated film of hard conating.
(formation of transparency conducting layer)
On the hard conating of above-mentioned laminated film, forming thickness is the transparency conducting layer of the ITO of 400nm.The formation of transparency conducting layer is to be undertaken by the dc magnetron sputtering method of using ITO target (tin concentration is scaled 10 weight % by tin ash).Particularly, before plasma discharge, will be vented to 5 * 10 in the chamber
-4After the pa, in chamber, import the mist (oxygen concentration is 0.5 volume %) of argon and oxygen, make pressure reach 0.3Pa, the ITO target is applied the voltage of 1000W.The sheet resistance value of gained transparency conducting layer is 20 Ω.
Then, use atmospheric plasma surface processing device (AP-T03-L of ponding chemical industry system), under nitrogen current (60L/ minute), plasma treatment is carried out on the surface of transparency conducting layer with 1m/ minute speed.The sheet resistance value of the transparency conducting layer after the plasma treatment is 22 Ω, and surface tension is 72.3mN/m.
(formation of anti-reflection layer)
On the other one side (this face does not have transparency conducting layer) of laminated film, formation thickness is that 75nm, refractive index are 1.89 Y
2O
3Layer; Forming thickness thereon is that 120nm, refractive index are 2.3 TiO
2Layer; And then to form thickness thereon be that 90nm, refractive index are 1.46 SiO
2Layer.These layers work as anti-reflection layer.These layers form by various high-frequency sputtering methods, and vacuum degree all is 1 * 10
-3Torr, circulate as Ar:55sccm, the O of gas on one side
2: 5sccm, form on one side.During this period, promptly do not heat yet and do not cool off, keep room temperature.
(formation of porous semiconductor layer)
On the transparency conducting layer of laminated film, be coated with machine coating low temperature formation type poriferous titanium dioxide layer with rod and form with thickener (clear and electrician's system, trade name SP-200), in atmosphere, under 180 ℃, carry out 30 minutes heat treatment, form the poriferous titanium dioxide layer.At this moment, regulate coating weight, make the thickness of poriferous titanium dioxide layer reach 5 μ m.Obtain on the transparency conducting layer of laminated film, possessing the electrode of the DSSC of poriferous titanium dioxide layer.Carry out the adaptation evaluation of porous semiconductor layer for this electrode, the result loses fully and peels off, and is evaluated as zero.
(manufacturing of DSSC)
This electrode was flooded 24 hours in 300 μ M ethanolic solutions of ruthenium complex (Ru535bisTBA, Solaronix system), on the light action electrode surface, adsorb ruthenium complex.
On the other hand, on the transparency conducting layer of laminated film, utilize sputtering method to pile up the Pt film, obtain electrode.
The flame type sept (thick 20 μ m) of the polyethylene film system by thermo-compressed overlaps this electrode and this to electrode, sept partly is heated to 120 ℃, crimping electrode and to electrode.Then, with epoxyn sealing the margin portion.
And then, inject electrolyte solution (containing the lithium iodide of 0.5M and the iodine of 0.05M and the tert .-butylpyridine of 0.5M and the 3-methoxypropionitrile solution of the nylon beads 3 weight % that average grain diameter is 20 μ m), seal with the epoxies adhesive, obtain DSSC.This DSSC is estimated I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.72V, short-circuit current density are 6.3mA/cm
2, the curve factor is 0.72, the light generating efficiency is 3.2％。
Embodiment 2,3 and reference example 1
When making biaxially oriented film, except will indulge stretching ratio, horizontal stretching ratio, heat fixation temperature change become as shown in table 1, operate similarly to Example 1, obtain laminated film.Identical with embodiment 1, make electrode with it, and then make DSSC.Evaluation result is as shown in table 1.
Table 1
Embodiment 4
Make biaxially oriented film similarly to Example 1.Then, under 205 ℃ of relaxation rates 0.8%, temperature, make its heat lax with overhang film.Percent thermal shrinkage at the length direction that carries out 10 minutes films after the processing under 200 ℃ is 0.15%, the percent thermal shrinkage of cross direction is 0.02%, and the thermal contraction rate variance of length direction and cross direction is 0.13%.
Identical with embodiment 1, on this film, form hard conating and transparency conducting layer, obtain laminated film.On this laminated film, form porous semiconductor layer, thereby make the electrode of DSSC.In addition, the heat treatment temperature of the formation condition of this porous semiconductor layer after will being coated with the titanium dioxide thickener is made as 200 ℃, and be identical with embodiment 1.This electrode is carried out the adaptation evaluation of porous semiconductor layer, and the result loses fully and peels off, and is evaluated as zero.
Use this electrode, make DSSC similarly to Example 1.This DSSC is estimated I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.71V, short-circuit current density are 7.4mA/cm
2, the curve factor is 0.75, the light generating efficiency is 3.9％。
Embodiment 5,6 and comparative example 2,3
Except will carry out plasma treatment the time ratio of used the GN 2 and oxygen change over as shown in table 2, make laminated film similarly to Example 1.In comparative example 3, do not carry out plasma treatment.And then, operate similarly to Example 1, make electrode and DSSC, estimate the adaptation of porous semiconductor layer, the light generating efficiency of battery.The results are shown in the table 2.
Table 2
Embodiment 7
(preparation of the aqueous dispersion of polyester)
In reactor, add 2,6-(ethylene naphthalate) 48 weight portions, DMIP 14 weight portions, DMIP 5-sodium sulfonate 4 weight portions, ethylene glycol 31 weight portions, diethylene glycol 2 weight portions, after wherein adding four fourth oxygen titaniums, 0.05 weight portion, under blanket of nitrogen, temperature control is heated to 230 ℃, the methyl alcohol that is generated is removed in distillation on one side, generally carries out ester exchange reaction.Then, make the temperature of reaction system rise to 255 ℃ lentamente, the 1mmHg that reduces pressure in the system is carried out polycondensation reaction, obtain polyester.These polyester 25 weight portions are dissolved in oxolane 75 weight portions, make solution.In gained solution, under 10000 rev/mins high-speed stirred, splash into water 75 weight portions, obtain milky dispersion, then this dispersion of distillation under the reduced pressure of 20mmHg is distilled and is removed oxolane, obtains the aqueous dispersion that solid constituent is the polyester of 25 weight %.
(preparation of the aqueous dispersion of acrylic compounds)
Make the aqueous dispersion of acrylic compounds similarly to Example 1.
(preparation of the aqueous dispersion of silica filler)
Make the aqueous dispersion of silica filler similarly to Example 1.
(preparation of paint B)
Aqueous dispersion 85 weight portions of aqueous dispersion 10 weight portions of mixed polyester, aqueous dispersion 5 weight portions of acrylic compounds and silica filler are made paint B.
(manufacturing of biaxially oriented film)
Fusion contains the PETG (intrinsic viscosity 0.65dl/g) of the ultra-violet absorber 1 weight % shown in the following formula (A), is expressed on the rotation cooling cylinder that maintains 20 ℃, and chilling obtains non-stretched film.
This non-stretched film is drawn into 3.4 times in longitudinal direction under 100 ℃, is coated with paint B equably on its two sides, obtain possessing the vertical oriented film of the easy adhesion layer of paint B with roll coater.Then, should indulge oriented film and under 95 ℃, carry out drying, under 120 ℃, be stretched to 3.7 times, and then under 220 ℃, make it shrink 3%, carry out heat fixation, obtain possessing the biaxially oriented film of easy adhesion layer in cross direction in transverse direction.The thickness of gained biaxially oriented film is 125 μ m, and easily the thickness of adhesion layer is 0.08 μ m, and the light transmittance of film at wavelength 370nm place is 0.5%, and the light transmittance at the 400nm place is 83.9%.
(formation of hard conating)
The hard paint of coating UV curable on the easy adhesion layer of the biaxially oriented film that possesses this easy adhesion layer (JSR system, trade name デ ソ ラ イ ト 7501) makes thickness reach about 5 μ m, and irradiation ultraviolet radiation makes its curing, forms hard conating.Can obtain possessing the laminated film of hard conating.
(formation of transparency conducting layer)
Forming thickness on the hard conating of above-mentioned laminated film is the ITO transparency conducting layer of 400nm.The formation of transparency conducting layer is carried out in the same manner with embodiment 1.The sheet resistance value of gained transparency conducting layer is 15 Ω.
Then, the plasma treatment identical with embodiment 1 implemented on the surface of transparency conducting layer.The sheet resistance of the transparency conducting layer after the plasma treatment is that 16 Ω, surface tension are 70.5mN/m.
(formation of anti-reflection layer)
The last formation of other one side (this face does not have transparency conducting layer) thickness at laminated film is that 80nm, refractive index are 1.75 TiO
XLayer, forming thickness thereon is that 70nm, refractive index are 2.1 TiO
2Layer, further forming thickness thereon is that 95nm, refractive index are 1.45 SiO
2Layer.These layers play a role as anti-reflection layer.These layers form by various high-frequency sputtering methods, and vacuum degree all is 5 * 10
-4Torr, circulate as Ar:55sccm, the O of gas on one side
2: 5sccm, form on one side.During this period, promptly do not heat yet and do not cool off, keep room temperature.
(formation of porous semiconductor layer)
On the transparency conducting layer of laminated film, be coated with machine coating low temperature formation type poriferous titanium dioxide layer with rod and form with thickener (clear and electrician's system, trade name SP-200), in atmosphere, under 160 ℃, carry out 30 minutes heat treatment, form the poriferous titanium dioxide layer.At this moment, regulate coating weight, make the thickness of poriferous titanium dioxide layer reach 4 μ m.Obtain on the transparency conducting layer of laminated film, possessing the electrode of the DSSC of poriferous titanium dioxide layer.Carry out the adaptation evaluation of porous semiconductor layer for this electrode, the result loses fully and peels off, and is evaluated as zero.
(manufacturing of DSSC)
Use this electrode, make DSSC similarly to Example 1.The DSSC of gained is estimated I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.68V, short-circuit current density are 5.8mA/cm
2, the curve factor is 0.69, the light generating efficiency is 2.7%.
This DSSC is further carried out atmospheric exposure test, estimate I-V characteristic (effective area 25mm then
2), the result is that open circuit voltage is that 0.69V, short-circuit current density are 5.2mA/cm
2, the curve factor is 0.67, the light generating efficiency is 2.4%, the reduction of light generating efficiency is very little.
Embodiment 8
Fusion contains the PETG (intrinsic viscosity 0.61dl/g) of the ultra-violet absorber 2 weight % shown in the following formula (B), is expressed on the rotation cooling cylinder that maintains 60 ℃, and chilling obtains non-stretched film.
This non-stretched film is drawn into 3.3 times in longitudinal direction under 140 ℃, is coated with paint B equably on its two sides, obtain possessing the vertical oriented film of the easy adhesion layer of paint B with roll coater.Then, should indulge oriented film and under 120 ℃, carry out drying, under 145 ℃, be stretched to 3.5 times, and then under 240 ℃, make it shrink 2%, carry out heat fixation, obtain possessing the biaxially oriented film of easy adhesion layer in cross direction in transverse direction.The thickness of gained biaxially oriented film is 100 μ m, and easily the thickness of adhesion layer is 0.08 μ m, and the light transmittance of film at wavelength 370nm place is 0.5%, and the light transmittance at the 400nm place is 83.9%.
Hard conating and transparency conducting layer are set on above-mentioned biaxially oriented film similarly to Example 7.The sheet resistance value of gained transparency conducting layer is 18 Ω.
Then, use used atmospheric plasma surface processing device among the embodiment 7, (60L/ minute) carries out plasma treatment with 1m/ minute speed to layer at transparent layer under the mist air-flow of oxygen 5%, nitrogen 95%.The sheet resistance of gained transparency conducting layer is that 18 Ω, surface tension are 66.2mN/m.
And then, on transparency conducting layer, form anti-reflection layer and porous semiconductor layer similarly to Example 7.Can obtain on the transparency conducting layer of laminated film, possessing the electrode of the DSSC of poriferous titanium dioxide layer.This electrode is carried out the adaptation evaluation of porous semi-conductor, and the result loses fully and peels off, and is evaluated as zero.
Use this electrode, make DSSC similarly to Example 7.The DSSC of gained is estimated I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.65V, short-circuit current density are 5.4mA/cm
2, the curve factor is 0.70, the light generating efficiency is 2.5%.
This DSSC is further carried out atmospheric exposure test, estimate I-V characteristic (effective area 25mm then
2), the result is that open circuit voltage is that 0.64V, short-circuit current density are 5.2mA/cm
2, the curve factor is 0.69, the light generating efficiency is 2.3%, the reduction of light generating efficiency is very little.
Embodiment 9
Except the ultra-violet absorber that will contain PETG changes over compound shown in following formula (C), make the biaxially oriented film that possesses easy adhesion layer similarly to Example 7.The light transmittance of gained biaxially oriented film at wavelength 370nm place is 0.3%, and the light transmittance at the 400nm place is 81.2%.
Hard conating and transparency conducting layer are set on above-mentioned biaxially oriented film similarly to Example 7.The sheet resistance value of gained transparency conducting layer is 20 Ω.
Then, use used atmospheric plasma surface processing device among the embodiment 7, (60L/ minute) carries out plasma treatment with 1m/ minute speed to layer at transparent layer under the mist air-flow of oxygen 30%, nitrogen 70%.The sheet resistance of gained transparency conducting layer is that 21 Ω, surface tension are 43.2mN/m.
And then, on transparency conducting layer, form anti-reflection layer and porous semiconductor layer similarly to Example 7, make electrode.Adaptation to porous semi-conductor is estimated, and the result loses fully and peels off, and is evaluated as zero.
Use this electrode, make DSSC similarly to Example 7.The DSSC of gained is estimated I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.66V, short-circuit current density are 5.0mA/cm
2, the curve factor is 0.65, the light generating efficiency is 2.1%.
This DSSC is further carried out atmospheric exposure test, estimate I-V characteristic (effective area 25mm then
2), the result is that open circuit voltage is that 0.66V, short-circuit current density are 4.7mA/cm
2, the curve factor is 0.63, the light generating efficiency is 2.0%, the reduction of light generating efficiency is very little.
Reference example 4
Except in PETG, not cooperating the ultra-violet absorber, make DSSC similarly to Example 7.The light transmittance of biaxially oriented film at wavelength 370nm place of this moment is 84.6%, and the light transmittance at the 400nm place is 87.7%.
Use this electrode, make DSSC similarly to Example 7, estimate I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.69V, short-circuit current density are 6.2mA/cm
2, the curve factor is 0.68, the light generating efficiency is 2.9%.
This DSSC is further carried out atmospheric exposure test, estimate I-V characteristic (effective area 25mm then
2), the result is that open circuit voltage is that 0.63V, short-circuit current density are 2.2mA/cm
2, the curve factor is 0.58, the light generating efficiency is 0.8%.
Reference example 5
Except the ultra-violet absorber that will be contained is made as 6 weight %, make DSSC similarly to Example 7 in PETG.The light transmittance of biaxially oriented film at wavelength 370nm place of this moment is 0.1%, and the light transmittance at the 400nm place is 66.2%.
Use this electrode, make DSSC similarly to Example 7.Estimate I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.62V, short-circuit current density are 4.1mA/cm
2, the curve factor is 0.64, the light generating efficiency is 1.6%.
Comparative example 6
The nitrogen of used gas and the ratio of oxygen are made as the 50%:50% except with plasma treatment the time, make electrode similarly to Example 7.The surface tension of the transparency conducting layer after the plasma treatment is 37.8mN/m.Estimate the adaptation of the porous semiconductor layer of electrode, the result observes part and peels off, and is evaluated as △.
Use this electrode, make DSSC similarly to Example 7.Estimate I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.58V, short-circuit current density are 4.2mA/cm
2, the curve factor is 0.59, the light generating efficiency is low to moderate 1.4%.
Embodiment 10
(preparation of the aqueous dispersion of polyester)
In reactor, add dimethyl terephthalate (DMT) 92 weight portions, DMIP 12 weight portions, DMIP 5-sodium sulfonate 17 weight portions, ethylene glycol 54 weight portions and diethylene glycol 62 weight portions, after wherein adding four fourth oxygen titaniums, 0.05 weight portion, under blanket of nitrogen, temperature control is heated to 230 ℃, the methyl alcohol that is generated is removed in distillation on one side, generally carries out ester exchange reaction.Then, make the temperature of reaction system rise to 255 ℃ lentamente, the 1mmHg that reduces pressure in the system is carried out polycondensation reaction, obtain polyester.These polyester 25 weight portions are dissolved in oxolane 75 weight portions, make solution.In gained solution, under 10000 rev/mins high-speed stirred, splash into water 75 weight portions, obtain milky dispersion, then this dispersion of distillation under the reduced pressure of 20mmHg is distilled and is removed oxolane, obtains the aqueous dispersion that solid constituent is the polyester of 25 weight %.
(preparation of the aqueous dispersion of acrylic compounds)
In four-hole boiling flask, add dodecyl sodium sulfate 3 weight portions and ion exchange water 181 weight portions, under nitrogen current, be warmed up to 60 ℃ as surfactant.Then, interpolation is as ammonium persulfate 0.5 weight portion and nitrous acid hydrogen sodium 0.2 weight portion of polymerization initiator.Then, splash into the mixture of methyl methacrylate 70 weight portions, ethyl acrylate 25 weight portions and N hydroxymethyl acrylamide 5 weight portions as monomer.The dropping process is, on one side adjust reaction system the liquid temperature reach 60～70 ℃, drip on one side, need 3 hours.After dripping end, further the liquid temperature of reaction system is remained on 60～70 ℃ scope,, reaction is continued Yi Bian stirred 2 hours.Then, cooling obtains the aqueous dispersion that solid constituent is the acrylic compounds of 35% weight.
(preparation of the aqueous dispersion of silica filler)
Make and be added with silica filler (average grain diameter 100nm) (Misao Kusano's system, trade name ス ノ-テ ッ Network ス ZL) 0.3 weight % and as the aqueous dispersion of polyoxyethylene (n=9) lauryl ether (Kao Corp's system, trade name エ マ Le ゲ Application 109P) the 0.4 weight % of wetting agent.
(preparation of paint C)
Mix aqueous dispersion 10 weight portions of above-mentioned polyester, aqueous dispersion 3 weight portions of acrylic compounds and aqueous dispersion 87 weight portions of silica filler, make paint C.
(preparation of the aqueous dispersion of polyester)
In reactor, add 2,6-(ethylene naphthalate) 66 weight portions, DMIP 47 weight portions, DMIP 5-sodium sulfonate 8 weight portions, ethylene glycol 54 weight portions, diethylene glycol 62 weight portions, after wherein adding four fourth oxygen titaniums, 0.05 weight portion, under blanket of nitrogen, temperature control is heated to 230 ℃, the methyl alcohol that is generated is removed in distillation on one side, generally carries out ester exchange reaction.Then, make the temperature of reaction system rise to 255 ℃ lentamente, the 1mmHg that reduces pressure in the system is carried out polycondensation reaction, obtain polyester.These polyester 25 weight portions are dissolved in oxolane 75 weight portions, make solution.In gained solution, under 10000 rev/mins high-speed stirred, splash into water 75 weight portions, obtain milky dispersion, then this dispersion of distillation under the reduced pressure of 20mmHg is distilled and is removed oxolane, obtains the aqueous dispersion that solid constituent is the polyester of 25 weight %.
(preparation of the aqueous dispersion of acrylic compounds)
Make the aqueous dispersion of acrylic compounds similarly to Example 1.
(preparation of the aqueous dispersion of silica filler)
Make the aqueous dispersion of silica filler similarly to Example 1.
(preparation of paint D)
Mix aqueous dispersion 8 weight portions of above-mentioned polyester, aqueous dispersion 7 weight portions of acrylic compounds and aqueous dispersion 85 weight portions of silica filler, make paint D.
(the film manufacturing of polyester)
Identical with embodiment 1, what be made as film usefulness polyester gathers-2,6-(ethylene naphthalate) polymer.Should gather-2, the intrinsic viscosity of 6-(ethylene naphthalate) is 0.62dl/g, is the polymer that is substantially free of particle.
(manufacturing of biaxially oriented film)
Should gather-2,6-(ethylene naphthalate) polymer is following dry 6 hours at 170 ℃ with the form of particle, supply in the extruder funnel, under 305 ℃ of melt temperatures, carry out fusion, with average slot is that the stainless steel fine rule filter of 17 μ m filters, and by the slot die of 3mm, is expressed into surface temperature and is on 60 ℃ the rotation cooling cylinder, carry out chilling, obtain non-stretched film.
This non-stretched film is carried out preheating in 120 ℃, between low speed roller and the high speed roller above the 15mm IR heater with 850 ℃ heat, be drawn into 3.2 times at longitudinal direction, obtain vertical oriented film.On the one side of this vertical oriented film, be coated with ready-made paint C, form easy adhesion layer with roll coater.At this moment, regulate the coating weight of paint A, make the thickness of the easy adhesion layer in dry back reach 0.08 μ m.And then, with this membrane supplying tentering device, under 140 ℃, be drawn into 3.3 times, and then under 244 ℃, carried out heat fixation 5 seconds in transverse direction, obtain possessing the biaxially oriented film of easy adhesion layer.The intrinsic viscosity of this film is 0.58dl/g, and thickness is 125 μ m, and when heat-treating 10 minutes under 200 ℃, the percent thermal shrinkage of length direction is 0.58%, and the percent thermal shrinkage of cross direction is 0.12%, and the thermal contraction rate variance of length direction and cross direction is 0.46%.
(formation of transparency conducting layer)
On the other one side (this face does not have transparency conducting layer) of biaxially oriented film, the method for utilizing the embodiment 6 of Japanese kokai publication sho 63-908 communique to be put down in writing forms and contains the transparency conducting layer that thickness is the ITO of 280nm.Can obtain possessing the biaxially oriented film of transparency conducting layer.The sheet resistance value of this transparency conducting layer is 18 Ω.
Then, use atmospheric plasma surface processing device (AP-T03-L of ponding chemical industry system), under nitrogen current (60L/ minute), plasma treatment is carried out on the surface of transparency conducting layer with 1m/ minute speed.The sheet resistance value of the transparency conducting layer after the plasma treatment is 18 Ω, and surface tension is 71.5mN/m.
(formation of anti-reflection layer)
Form anti-reflection layer similarly to Example 1.
(formation of porous semiconductor layer)
On the transparency conducting layer of laminated film, be coated with machine coating low temperature formation type poriferous titanium dioxide layer with rod and form with thickener (clear and electrician's system, trade name SP-200), in atmosphere, under 200 ℃, carry out 30 minutes heat treatment, form the poriferous titanium dioxide layer.At this moment, regulate coating weight, make the thickness of poriferous titanium dioxide layer reach 5 μ m.Obtain on the transparency conducting layer of laminated film, possessing the electrode of the DSSC of poriferous titanium dioxide layer.Carry out the adaptation evaluation of porous semiconductor layer for this electrode, the result loses fully and peels off, and is evaluated as zero.
(manufacturing of DSSC)
This electrode was flooded 24 hours in 300 μ M ethanolic solutions of ruthenium complex (Ru535bisTBA, Solaronix system), on the light action electrode surface, adsorb ruthenium complex.
On the other hand, on the transparency conducting layer of above-mentioned biaxially oriented film, utilize sputtering method to pile up the Pt film, make electrode.
Use this electrode and this to electrode, operation obtains DSSC similarly to Example 1.The DSSC of gained is estimated I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.71V, short-circuit current density are 7.1mA/cm
2, the curve factor is 0.68, the light generating efficiency is 3.4%.
Embodiment 11,12 and reference example 7
When making biaxially oriented film, except will indulge stretching ratio, horizontal stretching ratio, heat fixation temperature change become as shown in table 3, operate similarly to Example 10, obtain biaxially oriented film.Identical with embodiment 10, make electrode and DSSC with it.The longitudinal direction of biaxially oriented film, transverse direction are as shown in table 3 200 ℃ of percent thermal shrinkage and light generating efficiencies of the adaptation of poor, porous semiconductor layer, DSSC thereof after carrying out handling in 10 minutes.
Table 3
Embodiment 13
(manufacturing of biaxially oriented film)
Except the paint that will be used to form easy adhesion layer changes over paint D, make biaxially oriented film similarly to Example 10, the condition with 205 ℃ of relaxation rates 0.9%, temperature makes film heat lax under overhang then.After heat-treating 10 minutes under 200 ℃, the percent thermal shrinkage of length direction is 0.13% with the gained biaxially oriented film, and the percent thermal shrinkage of cross direction is 0.03%, and the thermal contraction rate variance of length direction and cross direction is 0.10%.
(formation of hard conating)
On this biaxially oriented film, form hard conating similarly to Example 1, obtain having the laminated film of hard conating.
(formation of transparency conducting layer)
On the hard conating of laminated film, transparency conducting layer is set similarly to Example 1.The sheet resistance of gained transparency conducting layer is 19 Ω.
Then, similarly to Example 1 plasma treatment is implemented on the surface of gained transparency conducting layer.The sheet resistance value of the transparency conducting layer after the plasma treatment is 20 Ω, and surface tension is 71.8mN/m.
(formation of anti-reflection layer)
On the other one side (this face does not have transparency conducting layer) of laminated film, form anti-reflection layer similarly to Example 10.
(formation of porous semiconductor layer)
Heat treatment temperature after will smearing the titanium dioxide thickener is made as 220 ℃, forms porous semiconductor layer similarly to Example 10, makes the electrode of DSSC.Carry out the adaptation evaluation, the result loses fully and peels off, and is evaluated as zero.
(manufacturing of DSSC)
Use this electrode, DSSC is made in operation similarly to Example 10.The DSSC of gained is estimated I-V characteristic (effective area 25mm
2), the result is that open circuit voltage is that 0.70V, short-circuit current density are 8.SmA/cm
2, the curve factor is 0.72, the light generating efficiency is 4.3%.
Embodiment 14,15 and reference example 8,9
Except the heat treatment temperature with the porous semiconductor layer among the embodiment 13 change over as shown in table 4, operate similarly to Example 13, make electrode.The adaptation of porous semiconductor layer and utilize the light generating efficiency of the DSSC that this electrode makes as shown in table 4.
Table 4
| Embodiment 13 | Embodiment 14 | Embodiment 15 | Comparative example 8 | Comparative example 9 | |
| The heat treatment temperature of porous semi-conductor ℃ | 220 | 180 | 240 | 160 | 255 |
| Adaptation is estimated | ○ | ○ | ○ | ○ | × |
| Light generating efficiency % | 4.3 | 3.4 | 4.0 | 1.9 | ＊ |
*The distortion of electrode is remarkable, can not make battery.
The invention effect
By the present invention, used by dye sensitization solar battery laminated film, used by dye sensitization solar battery electrode and manufacture method thereof can be provided, and described used by dye sensitization solar battery laminated film can be made the DSSC that adaptation is excellent, the light power generation performance is high of transparency conducting layer and porous semiconductor layer. Utilize the solar cell of this used by dye sensitization solar battery laminated film and used by dye sensitization solar battery electrode, also can keep high light generating efficiency in the sunshine even be exposed to for a long time as DSSC. In addition, by manufacture method of the present invention, can also make the used by dye sensitization solar battery electrode of the adaptation excellence of transparency conducting layer and porous semi-conductor.
Claims (12)
1. used by dye sensitization solar battery laminated film, it is characterized by, the transparency conducting layer that contains polyester film and on its one side, be provided with, the surface tension of transparency conducting layer is more than the 40mN/m, the polyester that constitutes polyester film is to be selected from PETG, polyethylene glycol isophthalate, polybutylene terephthalate (PBT), poly-(1,4-cyclohexene dimethylene terephthalate), gather-2, any chain saturated polyester in the 6-(ethylene naphthalate).
2. used by dye sensitization solar battery laminated film as claimed in claim 1, wherein, the surface tension of transparency conducting layer is more than the 65mN/m.
3. used by dye sensitization solar battery laminated film as claimed in claim 1, wherein, the light transmittance of polyester film at wavelength 370nm place is below 3%, and the light transmittance at 400nm wavelength place is more than 70%.
4. used by dye sensitization solar battery laminated film as claimed in claim 1, wherein, polyester film is below 0.8% at the absolute value of the difference of the percent thermal shrinkage of length direction that carries out 10 minutes films after the processing under 200 ℃ and cross direction.
5. used by dye sensitization solar battery laminated film as claimed in claim 1, wherein, polyester film is 0～0.5% at the percent thermal shrinkage of the length direction that carries out 10 minutes films after the processing under 200 ℃.
6. used by dye sensitization solar battery laminated film as claimed in claim 1, wherein, between polyester film and transparency conducting layer, further containing bed thickness is the easy adhesion layer of 10～200nm.
7. used by dye sensitization solar battery laminated film as claimed in claim 6 wherein, is easily further containing hard conating between adhesion layer and the transparency conducting layer.
8. used by dye sensitization solar battery laminated film as claimed in claim 1, wherein, with the face of the transparency conducting layer opposite side of laminated film on further contain anti-reflection layer.
9. the used by dye sensitization solar battery electrode wherein, contains the described dye sensitization of solar of claim 1 and reach the porous semiconductor layer that is provided with laminated film on its transparency conducting layer.
10. used by dye sensitization solar battery electrode as claimed in claim 9, wherein, porous semiconductor layer contains at least a kind of metal oxide that is selected from titanium oxide, zinc oxide and the tin oxide.
11. the manufacture method of used by dye sensitization solar battery electrode, it is characterized by, on the one side of polyester film, form transparency conducting layer, by under 170～250 ℃ thereon sintered metal oxide form porous semiconductor layer, wherein said polyester film is below 0.8% at the absolute value of the difference of the percent thermal shrinkage of length direction that carries out 10 minutes films after the processing under 200 ℃ and cross direction, the polyester that constitutes polyester film is to be selected from PETG, polyethylene glycol isophthalate, polybutylene terephthalate (PBT), poly-(1,4-cyclohexene dimethylene terephthalate), gather-2, any chain saturated polyester in the 6-(ethylene naphthalate).
12. the manufacture method of used by dye sensitization solar battery electrode as claimed in claim 11, wherein, metal oxide is at least a kind of metal oxide that is selected from titanium oxide, zinc oxide and the tin oxide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004022840A JP4456883B2 (en) | 2004-01-30 | 2004-01-30 | Dye-sensitized solar cell laminate film and dye-sensitized solar cell electrode using the same |
| JP022840/2004 | 2004-01-30 | ||
| JP058734/2004 | 2004-03-03 | ||
| JP158976/2004 | 2004-05-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1914762A CN1914762A (en) | 2007-02-14 |
| CN100524939C true CN100524939C (en) | 2009-08-05 |
Family
ID=34906052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800037096A Active CN100524939C (en) | 2004-01-30 | 2005-01-28 | Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4456883B2 (en) |
| CN (1) | CN100524939C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104969305A (en) * | 2013-02-06 | 2015-10-07 | 三菱树脂株式会社 | Transparent stacked film, transparent conductive film, and gas barrier stacked film |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008039803A (en) * | 2006-08-01 | 2008-02-21 | Teijin Dupont Films Japan Ltd | Antireflection film |
| CN103833994B (en) * | 2012-11-22 | 2016-12-28 | 东丽纤维研究所（中国）有限公司 | A kind of alkali soluble copolymer polyester and its production and use |
| CN103903865A (en) * | 2012-12-27 | 2014-07-02 | 中国科学院上海硅酸盐研究所 | Dye-sensitized solar cell |
| JP6565683B2 (en) | 2014-11-28 | 2019-08-28 | 東レ株式会社 | Polyester film |
| JP7144318B2 (en) * | 2017-03-29 | 2022-09-29 | 積水化学工業株式会社 | Transparent conductive film for light control film and light control film |
-
2004
- 2004-01-30 JP JP2004022840A patent/JP4456883B2/en not_active Expired - Lifetime
-
2005
- 2005-01-28 CN CNB2005800037096A patent/CN100524939C/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104969305A (en) * | 2013-02-06 | 2015-10-07 | 三菱树脂株式会社 | Transparent stacked film, transparent conductive film, and gas barrier stacked film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1914762A (en) | 2007-02-14 |
| JP4456883B2 (en) | 2010-04-28 |
| JP2005216706A (en) | 2005-08-11 |
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