CN101312096B - Electrode substrate and photoelectric conversion element - Google Patents

Electrode substrate and photoelectric conversion element Download PDF

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Publication number
CN101312096B
CN101312096B CN 200810126942 CN200810126942A CN101312096B CN 101312096 B CN101312096 B CN 101312096B CN 200810126942 CN200810126942 CN 200810126942 CN 200810126942 A CN200810126942 A CN 200810126942A CN 101312096 B CN101312096 B CN 101312096B
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layer
metal wiring
wiring layer
base board
electrode base
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CN101312096A (en
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松井浩志
冈田显一
川岛卓也
田辺信夫
江连哲也
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Fujikura Ltd
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Fujikura Ltd
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Priority claimed from JP2002306723A external-priority patent/JP4503226B2/en
Priority claimed from JP2002328566A external-priority patent/JP2004164970A/en
Priority claimed from JP2002328109A external-priority patent/JP4416997B2/en
Priority claimed from JP2003305269A external-priority patent/JP4515061B2/en
Application filed by Fujikura Ltd filed Critical Fujikura Ltd
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    • 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
    • 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
    • Y02E10/549—Organic PV cells

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  • Surface Treatment Of Glass (AREA)
  • Photovoltaic Devices (AREA)

Abstract

This invention refers to an electrode substrate and a photoelectric conversion element. In an electrode substrate (1), the surface of a metal circuit layer (12) is covered and insulated by an insulating layer (14). In a photoelectric conversion element that uses this electrode substrate (1), the metal circuit layer (12) is reliably shielded from an electrolyte solution or the like so that corrosion and leak current thereof is effectively prevented, and the photoelectric conversion efficiency can be improved. The insulating layer (14) is preferably made of a material that contains a glass component, and is particularly preferably formed by printing a paste that contains glass frit. The metal circuit layer (12) is preferably formed using a printing method.

Description

The electrode base board and the components of photo-electric conversion
Technical field
The present invention relates to be used for electrode base board and conductive glass substrate, the components of photo-electric conversion and the dye-sensitized solar cells of components of photo-electric conversion etc.
Background technology
Dye-sensitized solar cells, as cheap and can obtain the components of photo-electric conversion of high conversion efficiency and gazed at (reference example as: the spy opens flat 01-220380 communique and M.Graetzel etc., Nature Journal (Nature), (Britain), 1991, No. 737, p.353).General, in this components of photo-electric conversion, on transparent conductive board, form the perforated membrane that has used oxide semiconductor nano particles such as titanium dioxide, make this perforated membrane support sensitizing dyestuff and constitute semi-conducting electrode.This semi-conducting electrode and sputter conductive glass etc. electrode is made up mutually of platinum, between two electrodes, fill containing oxidations such as iodine, iodide ion, go back the organic electrolyte of original seed as charge transport layer.
By being made, semi-conducting electrode has by roughness factor to be 1000 or the perforated membrane structure of above big specific area, absorptivity is improved.Absorptivity 10% or above light-to-current inversion efficient report is also arranged.Dye-sensitized solar cells, aspect cost, also measurable is that existing silicon is about 1/2～1/6 of solar cell.Dye-sensitized solar cells because not necessarily must use complicated, large-scale manufacturing equipment, and does not contain hazardous substance, and as being fit to a large amount of cheap, a large amount of type of production solar cells of popularizing, very high possibility is arranged.
As transparent conductive board, general used is to coat tin-doped indium oxide (ITO), fluorine doped tin oxide nesa coatings such as (FTO) by methods such as sputtering method or CVD methods in advance at glass baseplate surface.But the resistivity of ITO or FTO is 10 -4～10 -3About Ω cm, be about 100 times of resistivity of silver, golden and so on metal.Therefore, the transparent conducting glass resistance value height that sell in market, when being used for solar cell, in the time of especially for large-area battery unit, the decline of light-to-current inversion efficient is remarkable.
As the method for the resistance that reduces transparent conducting glass, can consider to improve the formation thickness of transparency conducting layer (ITO, FTO etc.).But if form the film of the thickness that can obtain enough resistance values, the light absorption that is caused by transparency conducting layer will become greatly, and the window material transmitance of incident light will significantly reduce.Its result still makes the light-to-current inversion efficient of solar cell reduce.
At suchlike way to solve the problem, for example studied, surface at the substrate that has transparency conducting layer that uses as the window utmost point of solar cell etc., under the situation of its aperture opening ratio of not appreciable impact, metal wiring layer is set, with the method for the resistance that reduces substrate (reference example: special be willing to 2001-400593 number).So, when substrate surface is provided with metal wiring layer,,, be necessary to be protected by shielding layer at least at the surface portion of metal wiring layer for the reverse electron transfer of the burn into of the metal line that prevents to cause by metal line course electrolyte by electrolyte.This shielding layer must coat circuit surface densely.
Figure 26 A and Figure 26 B represent an example of dye-sensitized solar cells.This dye-sensitized solar cells, on electrode base board 61, be provided with have by the work electrode 63 of oxide semiconductor particulates such as titanium oxide oxide semiconductor perforated membrane 62 that form, that supported photosensitive dye and and setting relative with this work electrode to electrode 64.At work electrode 63 and to 64 at electrode, form dielectric substrate 65 by filling electrolyte.
Electrode base board 61 is to have formed the electrode base board that contains tin-doped indium oxide (ITO), mixes the transparency conducting layer 611 of fluoric acid tin (FTO) etc. on base materials such as glass plate 610.In order to improve current collecting efficiency, on transparency conducting layer 611, the clathrate metal wiring layer 612 that contains gold, platinum, silver etc. is set from oxide semiconductor perforated membrane 62.In addition, for the unfavorable conditions such as output reduction that suppress to cause by the short circuit of 65 of the burn into of metal wiring layer 612 and dielectric substrates and leakage current (reverse electron transfer) etc., on the surface of metal wiring layer 612, transparency conducting layer 611, coat the shielding layer 613 that contains oxide semiconductors such as ITO, FTO, titanium oxide, zinc oxide.Replace dielectric substrate 65, also can use the charge transport layer 66 that contains p N-type semiconductor N etc.In a single day inject from the light of base material 610 sides such as sunlight etc., produce electromotive force at work electrode 63 and to 64 at electrode.
The formation of shielding layer 613 is the film forming methods that adopt sputtering method or spray heating decomposition (SPD) method etc., is undertaken by the semi-conductive film of formation oxycompound on metal wiring layer 612.But, because transparency conducting layer 611 or metal wiring layer 612 surfaces present small concavo-convex (profile) in space, be full of cracks, grain etc., it is very difficult being formed uniformly fine and close shielding layer 613, because the formation of shielding layer 613 is bad, can produce the part that is not capped of exposing metal wiring layer 612.In this case, just may reduce the effect of the unfavorable conditions such as output reduction that leakage current that the burn into that suppresses metal wiring layer 612 produces to the reverse electron transfer of dielectric substrate 65 grades by metal wiring layer 612 etc. causes, the characteristic of solar cell (battery unit) is significantly descended.
Bad for the formation that suppresses shielding layer 613, and increase the coating thickness of shielding layer 613, owing to can hinder photoelectronic migration, reduce light transmission rate, might reduce its light-to-current inversion efficient on the contrary.
For example, employing is that the conductive paste of main component is when carrying out the formation of metal wiring layer 612 with the bond of the electroconductive particle of metal particle etc. and frit etc., consider from the conductance aspect of metal wiring layer 612, the mixing ratio of bond is the smaller the better, but inside or surface at metal wiring layer 612 form small and high and steep concavo-convex and shadow parts such as space or pin hole easily, thereby are difficult to form shielding layer.If increase the mixing ratio of bond, owing to can reduce the conductance of metal wiring layer 612, thus might reduce the characteristic of current collecting efficiency and remarkable infringement battery unit.
If metal wiring layer 612 is not set on electrode base board 61, when only implementing current collection from oxide semiconductor perforated membrane 62, make the semi-conductive resistivity of the FTO that constitutes transparency conducting layer 611 etc. be in 10 by transparency conducting layer 611 -4～10 -3The scope of Ω cm promptly is about 100 times of resistivity of metals such as gold, silver, so particularly under the situation of area battery unit, the reduction of light-to-current inversion efficient clearly.Increase its thickness for the resistance that reduces transparency conducting layer 611, the photopermeability of transparency conducting layer 611 will significantly descend, and its result still causes the reduction of light-to-current inversion efficient.
From the film forming direction, when metallic circuit surface shaded portion (for example, circuit wall pierce etc.), might generate the part that crested layer not coats.Because this will cause the corrosion of circuit and to the reverse electron transfer of electrolyte etc., will significantly damage the characteristic of battery unit.Particularly, about shielding layer, conduct is such as FTO, ITO, TiO usually 2The forming method of film, suitablely adopt sputtering method, spray heating decomposition (SPD), but adopt such method, be difficulty very to the even film forming of shadow part.For example, when forming circuit, the tapered phenomenon of circuit wall shape that is caused by the characteristic of preventing coating (め つ I レ ジ ス ト) is arranged by additional coating process (ァ デ イ テ イ Off め つ I method).If the bottom (full front of a Chinese gown draws I) of hauling-out is arranged in anti-plating pattern (レ ジ ス ト パ タ one Application) bottom, after circuit forms, just becomes the shadow part that pierces shape.So, be difficult to form fine and close shielding layer film on the metallic circuit surface.
As will keep the aperture opening ratio that does not damage light transmission rate and give enough conductivity the time, metal wiring layer must have height to a certain degree.So, form metal wiring layer after, substrate surface just become have a plurality of concavo-convex.Therefore, produce following problems:, become the uniformity of destroying thickness easily, produce the be full of cracks of film, the reason of peeling off etc. at jog such as when forming the multichip semiconductor pore membrane that dye-sensitized solar cells uses.
For example, to with conducting particles and frit bond be the paste printing of main component and at 500 ℃ of left and right sides sintering the situation of circuit under, obtain high conductivity in order not hinder each other molten sticking of conducting particles, the use level of frit reduces, therefore general on the coated film surface, the inner generation as precipitous concavo-convex and shades such as space or pin holes, make the formation of shielding layer very difficult.On the contrary, in order to suppress the defective on this type of coated film surface, when increasing the use level of the frit that constitutes bond, the coated film conductance significantly reduces, and the tendency that can not bring into play the function of circuit own is arranged.
As shown in figure 27,, form acidifying tin (FTO) equal thickness mix indium tin oxide (ITO), doped with fluorine and be the nesa coating 72 about 1 μ m, constitute conductive glass 73 in the one side of the glass plate shown in the symbol 71.On the nesa coating 72 of this conductive glass 73, formed the oxide semiconductor perforated membrane 74 oxide semiconductor particulate, that support photosensitive dye that contains titanium oxide, niobium oxide (acidifying ニ ォ ジ ゥ system) etc.The 75th, constitute conductive glass to electrode, its with oxide semiconductor perforated membrane 74 between, fill up the electrolyte of the non-aqueous solution that comprises the redox couple that contains iodine/iodide ion etc., thus formation dielectric substrate 76.Replace dielectric substrate 76, also have hole transmission layer that the p N-type semiconductor N that contains solids such as cupric iodide, copper rhodanide is set.About this dye-sensitized solar cells, when the light of sunlight etc. when conductive glass 73 sides are injected, at nesa coating 72 with between, produce electromotive force to electrode 75.
Yet, in the dye-sensitized solar cells of reality, on nesa coating, form circuit electrode, and then the oxide semiconductor perforated membrane is set thereon, because filling contains the electrolyte of iodine etc., and owing to circuit electrode is contacted with electrolyte by the oxide semiconductor perforated membrane, so there is electronics to go out phenomenon to the leakage current of electrolyte reverse flow from circuit electrode.When the energy level between comparison circuit electrode and electrolyte, find that this is lower the causing of energy level owing to electrolyte.At this,, form barrier layer (the バ リ ヤ one that contains semi-conducting material or insulating material at the interface of circuit electrode and electrolyte
Figure S2008101269429D00051
), in case the leak-stopping electric current.But barrier layer forms by various film formation methods, therefore newly produces the pin hole problem.Underway about the research that solves this pin hole problem, how to avoid becoming the manufacture method that causes the costliness that significantly raises the cost in this case, very important in actual applications (with reference to special fair 8-15097 communique).
Summary of the invention
Electrode base board of the present invention is to have metal wiring layer and transparency conducting layer on base material, the electrode base board that metal wiring layer is electrically connected with transparency conducting layer.At least the surface of metal wiring layer is insulated layer insulation coating.
By this class electrode base board, metal wiring layer is positively covered to avoid electrolyte solution etc., can suppress its corrosion or leakage current effectively.Thereby, form electrode base board with excellent electric conductivity.
Insulating barrier is preferably formed by the material that contains glass ingredient, and especially preferably the paste that contains frit by printing forms.Thus, can easily form the insulating barrier that metal wiring layer is covered in insulation positively.
Metal wiring layer preferably forms by print process.Thus, can easily form metal wiring layer with required pattern.
The components of photo-electric conversion that an embodiment of the invention relate to or dye-sensitized solar cells have above-mentioned electrode base board.Thus, can suppress to reduce, improve light-to-current inversion efficient owing to the output that the corrosion of the metal wiring layer of electrode base board or leakage current etc. cause.
The electrode base board that another embodiment of the invention relates to has metal wiring layer and transparency conducting layer on transparency carrier, and metal wiring layer is made of for 2 layers internal layer and skin at least.
Above-mentioned skin preferably forms by print process.The specific insulation of above-mentioned internal layer is preferably less than outer field specific insulation.Above-mentioned skin is formed by the paste composition that contains conducting particles and bond at least, the mixing ratio of the bond material of paste composition, and preferably the mixing ratio than the bond material in the composition of other layers that form metal wiring layer is big.
The composition that forms above-mentioned metal wiring layer preferably contains silver or nickel.On the surface of the conductive layer that contains above-mentioned metal wiring layer and/or transparency conducting layer, also can have shielding layer.
The components of photo-electric conversion of another embodiment of the invention or dye-sensitized solar cells have above-mentioned electrode base board.
The electrode base board of another embodiment of the invention has metal wiring layer and transparency conducting layer on transparency carrier.Metal wiring layer forms along carried out the wiring pattern of groove processing on transparency carrier, and at least a portion of metal wiring layer reaches transparency carrier surface or its following height.
At least the surface of metal wiring layer preferably coats by shielding layer.Above-mentioned shielding layer preferably contains and is selected from least a in glass ingredient, metal oxide composition and the electrochemistry inert plastic composition.
The components of photo-electric conversion of the present invention or dye-sensitized solar cells have above-mentioned electrode base board.
The conductive glass substrate of another embodiment of the invention; have the glass plate that applied nesa coating, be arranged at the electroconductive circuit layer on the glass plate and be formed on the circuit protecting layer of the insulating properties on the above-mentioned electroconductive circuit layer, described electroconductive circuit layer has the material that passive metal is had metal catalytic action or substitutional or has aforementioned metal.Form passive metal in the pin hole portion that the foregoing circuit protective layer is produced.
The aperture opening ratio of above-mentioned electroconductive circuit layer is preferably 75% or more, also can be 90～99%.This is applicable to all execution modes.
Above-mentioned electroconductive circuit layer also can be selected from gold, silver, platinum, palladium, copper by containing, reach at least a conductive paste formation in the aluminium.
The circuit protecting layer of above-mentioned insulating properties also can be formed by insulating properties paste material.
Above-mentioned passive metal also can handle forming by no electrolytic metal coating.Above-mentioned no electrolytic metal coating processing also can be no electrolytic nickel plating, the plating of no electrolytic cobalt or do not have the electrolytic tin plating.
The dye-sensitized solar cells of another embodiment of the invention has above-mentioned conductive glass substrate.
The manufacture method of the conductive glass substrate of another embodiment of the invention is; form transparent conductive film layer in glass pane surface; use thereon catalytic action arranged or substitutional metal or contain the material of above-mentioned metal; form the electroconductive circuit layer by coating process or silk screen print method; then more thereon by the paste formation circuit protecting layer of insulating properties, then handle and form passive metal by the electroless plating layer of nickel, cobalt or tin metal.
The electrode base board of another embodiment of the invention has base material, the metal wiring layer that is provided with and and the transparency conducting layer that is electrically connected of this metal wiring layer on base material.Above-mentioned metal wiring layer is by being coated by the insulating barrier insulation that with the heat-stable ceramic is main component.
As above-mentioned heat-stable ceramic, can adopt and for example contain the material that is selected from least a composition in aluminium oxide, zirconia, the silica.
As above-mentioned insulating barrier, can adopt for example to contain handlebar and be selected from least a material in silicate, phosphate, cabosil, alkyl silicate, the metal alkoxide as bond.Above-mentioned insulating barrier preferably forms by print process.Above-mentioned metal wiring layer preferably forms by print process.
At least a portion of above-mentioned metal wiring layer can be placed in the recess that forms on the substrate surface.
The components of photo-electric conversion of another embodiment of the invention and dye-sensitized solar cells have above-mentioned electrode base board.
By above-mentioned electrode base board, can positively carry out covering of metal wiring layer, the burn into that solves metal wiring layer is by the problems such as electrolytical rotten and leakage current that cause with the Metal Contact that constitutes metal wiring layer, can higher performance as the function of the transparent electrode substrate of high conductivity.Thereby, with regard to the area battery unit of square (100mm angle level) that for example length of side is the 100mm degree, compare with having not the battery unit of circuit board, can increase light-to-current inversion efficient.
Description of drawings
Figure 1A is the profile of an execution mode of the expression components of photo-electric conversion of the present invention.
Figure 1B is the profile of an example of expression electrode base board.
Fig. 2 is the plane graph of an example of expression metal wiring layer.
Fig. 3～Fig. 7 is other the profile of execution mode of representing electrode base board of the present invention respectively.
Fig. 8～Figure 11 is the profile of the another execution mode of expression electrode base board of the present invention.
Figure 12 A～Figure 12 C is the profile of the another execution mode of expression electrode base board of the present invention.
Figure 12 D is other the profile of execution mode of the expression components of photo-electric conversion.
Figure 13 is the profile of an execution mode of expression conducting glass substrate of the present invention.
Figure 14 is other the profile of execution mode of expression conducting glass substrate of the present invention.
Figure 15 is the plane graph of an example of the flat shape of expression metal wiring layer.
Figure 16～Figure 24 is other the profile of execution mode of expression electrode base board of the present invention.
Figure 25 is other the profile of execution mode of the expression components of photo-electric conversion of the present invention.
Figure 26 A and Figure 26 B are the profiles of representing an example of the components of photo-electric conversion before.
Figure 27 is a profile of representing dye-sensitized solar cells before.
Embodiment
Below, with reference to figure, preferred embodiment of the present invention is described.But the present invention is not limited in following each embodiment, for example, also can carry out suitable combination each other to the inscape of these embodiment.
Figure 1A represents the profile of an example of the components of photo-electric conversion of the present invention, and Figure 1B is the profile that expression is used for the electrode base board 1 of these components of photo-electric conversion.
These components of photo-electric conversion are dye-sensitized cells, and promptly when the light time of injecting sunlight etc. from base material 10 sides, work electrode 3 and 4 at electrode produced electromotive force obtains electric power therefrom.
The components of photo-electric conversion of this execution mode shown in Figure 1B, on the base material 10 of electrode base board 1, have transparency conducting layer 11, the metal wiring layer 12 that forms and an insulating barrier 14 that only coats these metal wiring layer 12 surfaces on this transparency conducting layer 11.By insulating barrier 14, all faces except following of clad metal wiring layer 12.In this embodiment, the surface at metal wiring layer 12 transparency conducting layer 11 does not each other form insulating barrier 14.
The material of base material 10 preferably has the material of high photopermeability on purposes.Be specially, can use glass, polyethylene terephthalate (PET), poly-naphthalenedicarboxylic acid second diester (PEN), Merlon (PC), polyether sulfone transparent plastic sheets such as (PES), and ceramic polished plates such as titanium oxide, aluminium oxide etc.
Transparency conducting layer 11, on base material 10 than forming in the wider zone, the formation zone of metal wiring layer 12.There is no particular limitation for the material of transparency conducting layer 11, can list tin-doped indium oxide (ITO), tin oxide (SnO 2), fluorine doped tin oxide conductive metal oxides such as (FTO).
Formation method as transparency conducting layer 11 can adopt the proper method that is suitable for transparency conducting layer 11 materials.Can enumerate as, sputtering method, vapour deposition method, SPD method, CVD method etc.Consider its photopermeability and conductivity, the thickness of transparency conducting layer 11 is generally about 0.001 μ m～10 μ m.Just, be not limited in this scope.
Metal wiring layer 12 is the distributions that form patterns such as formation clathrate, striated or pectination as shown in Figure 2 with metals such as gold, silver, platinum, aluminium, nickel, titaniums.In order significantly not damage the photopermeability of electrode base board 1, the wiring width of metal wiring layer 12 preferably at 1000 μ m or still less.The thickness of each distribution of metal wiring layer 12 (highly) is not particularly limited, but preferable range is at 0.1～10 μ m.
Formation method as metal wiring layer 12, can list, employing mixes the bond as the metal powder of conducting particles and glass granules etc., make it form pasty state, with this bond by print processes such as silk screen print method, metal mask method (metal mask), ink-jet method form the form of fixed pattern film, and burn till by heating, make the molten sticking method of conducting particles.As firing temperature, for example, be under the situation of glass at base material 10, preferred temperature is 600 ℃ or lower, more is preferably 550 ℃ or lower.In addition, also can use formation methods such as sputtering method, vapour deposition method, coating process.
From the angle of conductivity, the specific insulation of metal wiring layer 12 is preferably 10 -5Ω cm or still less.The surperficial preferred smooth of metal wiring layer 12, but have a bit rise and fall or concavo-convex etc. existence also harmless.
Insulating barrier 14 is to use one or more in the insulating material such as resin, pottery, glass, makes one or more layers, overlapping and film forming on the formation zone of metal wiring layer 12.The zone that insulating barrier 14 forms in the incident that does not very hinder light or under the situation of the charge migration of transparency conducting layer 11, also can be exposed around the pattern of metal wiring layer 12.
Formation method as insulating barrier 14 does not have absolute restriction.For example, also can adopt the glass paste that generates to the suitable thickener of frit fusion, bond, dispersant, solvent etc., by print processes such as silk screen print method, metal mask method, ink-jet methods, film, heat and burn till in the mode on the pattern that overlaps metal wiring layer 12.This method, viewpoints such as the easiness that forms from pattern, cost aspect are suitable.As firing temperature, be preferably 600 ℃ or lower, more be preferably 550 ℃ or lower.
About the glass that can burn till under such temperature, as noncrystalline or crystallinity glass system, can adopt the leaded of markets sale such as lead oxide system, lead borate system, lead borate bismuth system is the glass welding agent, and the glass welding agent of non-plumbous system in addition etc.The number of plies of insulating barrier 14 can be that one deck also can be a multilayer, under the situation of multilayer, can carry out 2 times or a kind of more frequently film forming of glass paste, perhaps also can use the glass paste of different two or more of melt temperature.
On the surface of electrode base board 1, form the oxide semiconductor film 2 that supports sensitizing dyestuff, constitute the work electrode 3 of the components of photo-electric conversion by electrode base board 1 and oxide semiconductor film porous 2.
Oxide semiconductor perforated membrane 2 has comprised titanium oxide (TiO compound 2), tin oxide (SnO 2), tungsten oxide (WO 3), zinc oxide (ZnO), niobium oxide (Nb 2O 5) a kind of in waiting or two or more, average grain diameter is at the oxide semiconductor particulate of 1～1000nm, for example is the porous membrane of thickness about 0.5～50 μ m.But not only be defined in this scope.
For forming oxide semiconductor film perforated membrane 2, can make with the following method and carry out, as: the oxide semiconductor microparticulate that the market is sold in required decentralized medium and the colloidal solution that the dispersion liquid that forms maybe can be adjusted by sol-gel method, after having added desired additives on demand, the method that applies by well-known coatings such as silk screen print method, ink-jet coating method, roller coating process, scraper plate finishing, whirl coating, spraying processes; In colloidal solution, soak electrode base board 1, by electrophoresis with the oxide semiconductor particulate attached to the electrophoretic deposition on the electrode base board 1; Mix to add in colloidal solution or dispersion liquid after blowing agent applies, sintering also carries out the method for porous; After mixing adding polymer microballoon applies, by heat treated or chemical treatment this polymer microballoon is removed and interstitial porous method etc. again.
The sensitizing dyestuff that oxide semiconductor perforated membrane 2 is supported has no particular limits.Can be from the ruthenium complex that for example has the ligand that contains bipyridine structure, three pyridine structures etc., iron complex compound, porphyrin system or phthalein green grass or young crops be organic dyestuff such as metal complex, eosin, base rhodamine, part cyanines etc., carry out suitable selection and used at purposes and oxide semiconductor porous film material.
As the electrolyte that forms dielectric substrate 5 usefulness, can use the organic solvent that contains redox couple or room temperature fuse salt etc.As organic solvent, can list acetonitrile, methoxyacetonitrile, propionitrile, ethylene carbonate, propene carbonate, diethyl carbonate, γ one butyrolactone etc.As the room temperature fuse salt, can list by season imidazoles cation and the salt that constitutes such as iodide ion or two fluoroform sulphonyl imido anion.
The redox couple that contains in the electrolyte has no particular limits.For example, also iodine/iodide ion, bromine/bromide ion etc. right.As the supply source of iodide ion or bromide ion, can independent or compound use lithium salts, season imidazole salts, 4-butyl ammonium etc.
In this electrolyte, can add additives such as tert .-butylpyridine as required.Thereby also can use suitable gelling agent to make its gelation suppress its flowability.
Replace dielectric substrate 5, also can use the charge transport layer 6 of the solid that contains p N-type semiconductor N etc.As the p N-type semiconductor N, for example, can suitably use monovalence copper compounds such as cupric iodide, copper rhodanide.The formation method of charge transport layer 6 has no particular limits, and can use well-known method, can list casting method, sputtering method, vapour deposition method etc.In this charge transport layer 6, also can contain additive according to the needs of layer formation.
As to electrode 4, can use as, on the substrate of non-conductive materials such as glass, form contain the semi-conductive films of electroconductive oxide such as ITO or FTO to electrode; Perhaps, on substrate with conductive materials such as gold, platinum, carbon-based material by evaporation, coating etc. form electrodes to electrode.Also on the semi-conductive film of electroconductive oxides such as ITO or FTO, formed layers such as platinum, carbon to electrode.
As making this method, for example can enumerate the method that behind the coating chloroplatinic acid, forms platinum layer by heat treated to electrode 4.Perhaps also can on substrate, form electrode by evaporation or sputtering method.
When replacing dielectric substrate 5, also can use on charge transport layer 6 and will carry out the method that layer forms by direct sputtering method or coating process the conductive material as electrode of electrode 4 with charge transport layer 6.
Electrode base board according to this execution mode, because transparency conducting layer 11 directly contacts and is electrically connected with metal wiring layer 12, so the electronics that flows out from oxide semiconductor perforated membrane 2 can be carried out current collection by transparency conducting layer 11, improve current collecting efficiency by metal wiring layer 12 again.Metal wiring layer 12 is positively covered solution to avoid dielectric substrate 5 etc., can suppress its corrosion or leakage current effectively.So can obtain having the electrode base board 1 of superior conductive characteristic, therefore, use the electrode base board of this execution mode, by constituting the work electrode in the components of photo-electric conversion, prevent contacting of metal wiring layer 12 and dielectric substrate 5, inhibition is reduced by the output that the burn into leakage current causes, and then can make the components of photo-electric conversion of high light-to-current inversion efficient.
Fig. 3 is the simple and clear profile of the 2nd execution mode of expression electrode base board of the present invention.In this routine electrode base board 1, metal wiring layer 12 is arranged on the base material 10, and transparency conducting layer 11 is promptly crossed over than metal wiring layer wider zone, 12 formed zones and formed on metal wiring layer 12.Insulating barrier 14 overlaps with the pattern of metal wiring layer 12 on transparency conducting layer 11 and forms in the mode of above the clad metal wiring layer 12 and side.That is, insulating barrier 14 is to be intermediary with transparency conducting layer 11, is arranged on the metal wiring layer 12.
Electrode base board according to this type of electrode base board 1 and above-mentioned first kind of execution mode is same, can insulate with 14 pairs of metal wiring layers 12 of insulating barrier and cover, and therefore can suppress the generation of leakage current, and then can obtain the superior electrode base board of conductive characteristic 1.Use this electrode base board, also can make the components of photo-electric conversion with high light-to-current inversion efficient.
Below provide other execution mode of electrode base board of the present invention.
In the execution mode that Fig. 4 represents, form transparency conducting layer 11 on base material 10, on transparency conducting layer 11, metal wiring layer 12 forms as the pattern of clathrate etc.On transparency conducting layer 11, the shielding layer 13 of the semi-conductive film of oxycompound is set, on metal wiring layer 12, form insulating barrier 14.
In the execution mode of Fig. 5, on base material 10, form metal wiring layer 12, on this metal wiring layer 12, cross over, form transparency conducting layer 11 than wider zone, metal wiring layer 12 formed zones as the pattern of clathrate etc.On transparency conducting layer 11, the shielding layer 13 of the semi-conductive film of oxycompound is set.Then, insulating barrier 14 overlaps with the pattern of metal wiring layer 12 on shielding layer 13, and forms in the mode of the top and side of clad metal wiring layer 12.
Though to compare problem smaller with metal wiring layer 12, owing to pointed out the problem of the reverse electron transfer that takes place from transparency conducting layer 11, so, as Fig. 4 or shown in Figure 5, by shielding layer 13 is set on transparency conducting layer 11, can obtain higher screening effect.
Material as shielding layer 13, select with the electrolyte that contains the redox kind between electron transfer speed low and photopermeability, compound that the photoelectron-transfer energy is high, exemplify as titanium oxide, zinc oxide, niobium oxide, tin oxide, fluorine doped tin oxide (FTO), tin-doped indium oxide (ITO) etc.
Shielding layer 13 need form thinly not hindering under the degree of the electron transfer of transparency conducting layer 11, and preferred thickness is about 10～3000nm.As the formation method of shielding layer 13, can enumerate sputtering method, vapour deposition method, SPD method, whirl coating, infusion process, scraper plate finishing etc.But, use these methods, the density of shielding layer 13, and can't say the surface configuration adaptability of base material 10 very abundant, so be difficult to sufficiently obtain the screening performance of metal wiring layer 12.Therefore, under the situation that has formed shielding layer 13, also being necessary on metal wiring layer 12, is intermediary directly or with transparency conducting layer 11 or shielding layer 13 etc., forms insulating barrier 14.Thus, the insulation of carrying out metal wiring layer 12 is fully covered.
Formation method as shielding layer 13 has no particular limits, can list, with purpose compound oxides semiconductor or its precursor by dry process (vapor phase method) such as sputtering method, vapour deposition method, CVD method the method for film forming.For example, after with precursor film forming such as metals, can make its oxidation obtain shielding layer 13 by heat treated or chemical treatment etc.
Under the situation of damp process, after the liquid that contains purpose compound or its precursor can being applied by methods such as whirl coating, infusion process, scraper plate finishings, by heat treated or chemical treatment etc., carry out chemical change to the purpose compound, obtain shielding layer 13 therefrom.As precursor, enumerate salt as the formation metallic element that contains the purpose compound, complex etc.In order to obtain fine and close film, compared with dispersion liquid, more preferably solution.
Other formation method as shielding layer 13, for example, also can adopt by using spray heating decomposition (SPD), under the state that has heated base material 10 with transparency conducting layer 11, spray with the material of the precursor of formation shielding layer 13 to this base material 10, make its thermal decomposition, and be changed to the purpose oxide semiconductor, thus the method for formation shielding layer 13.
According to above-mentioned way, by being provided for covering the shielding layer 13 of transparency conducting layer 11, can suppress the reverse electron transfer of coming out, therefore from transparency conducting layer 11, by using the electrode base board of this execution mode, can prepare the components of photo-electric conversion with high light-to-current inversion efficient.
For shielding layer 13, according to the needs on the characteristic, for example, can make its have as with the effect of the protective layer of insulating barrier 14 various objectives.
For example, in the execution mode of Fig. 6, shielding layer 13 not only is formed on the transparency conducting layer 11, and is formed on metal wiring layer 12 or the insulating barrier 14.Thus, also can be with the protective layer of shielding layer 13 as metal wiring layer 12 or insulating barrier 14.
The electrode base board 1 of the execution mode of Fig. 7 on the 1st transparency conducting layer 11a, forms the metal wiring layer 12 as cloth wire pattern such as clathrate, line shape, pectination, on this metal wiring layer 12, is provided for covering the insulating barrier 14 of metal wiring layer 12.Then, on metal wiring layer 12, insulating barrier 14, form the 2nd transparency conducting layer 11b.That is, metal wiring layer 12, insulating barrier 14 are clipped between the 1st transparency conducting layer 11a and the 2nd transparency conducting layer 11b.The the 1st and the 2nd transparency conducting layer 11a, 11b are identical with above-mentioned transparency conducting layer 11, are the films that contains conductive metal oxides such as ITO, FTO.
According to such electrode base board 1, cover by the insulation that insulating barrier 14 carries out metal wiring layer 12, simultaneously, can protect metal wiring layer 12 or insulating barrier 14 by the 2nd transparency conducting layer 11b.By having the 1st transparency conducting layer 11a and the 2nd transparency conducting layer 11b simultaneously, can improve current collecting efficiency.
The electrode base board of this execution mode also can be applicable to solar cells such as photochemical cell or the optical sensor components of photo-electric conversion in addition.In this case, because the metal wiring layer 12 of electrode base board 1 is insulated layer 14 and coats, and prevent contacting of electrolyte solution etc. and metal wiring layer 12, so, bad phenomenon such as burn into short circuit can be suppressed, the reduction of quality deterioration, photoelectricity variation characteristic, light responsiveness etc. can be suppressed.
Corresponding embodiment is illustrated for above-mentioned execution mode.
Embodiment A 1
The preparation of electrode base board
As transparency conducting layer 11 (11a) and base material 10, use the glass substrate of the subsidiary FTO film of 100mm * 100mm, on its surface, will print that (specific insulation behind the sintering is 3 * 10 with silver-colored paste -6Ω) silk screen printing becomes clathrate.After 10 minutes leveling, 135 ℃ were descended dry 20 minutes in hot-air drying stove, burnt till 15 minutes at 550 ℃, had just formed the metal wiring layer 12 of argentiferous circuit.The circuit width of metal wiring layer 12 is 150 μ m, and thickness is 5 μ m.
On one side by CCD camera adjusting position, on one side by silk screen print method, with glass paste and metal wiring layer 12 overlapping printings, after 10 minutes leveling, 135 ℃ were descended dry 20 minutes in hot-air drying stove, burnt till 15 minutes at 550 ℃, had just formed insulating barrier 14.The width of the insulating barrier 14 of gained is 250 μ m, the thickness of counting from glass baseplate surface is 10 μ m, thereby, on metal wiring layer 12, formed the insulating barrier 14 that thickness is approximately 5 μ m.
Observe the surface of this insulating barrier 14 by scanning electron microscopy (SEM) and find, frit pellet melting and molten each other sticking together, the surface of insulating barrier 14 is very fine and close, does not have defectives such as tangible pin hole.
Then, to cross over the form of metal wiring layer 12 or insulating barrier 14, form the FTO film of conduct the 2nd transparency conducting layer 11b that has protective layer and shielding layer 13 concurrently, prepared the electrode base board 1 of structure shown in Fig. 6 (and Fig. 7) by the SPD method.
The preparation of the components of photo-electric conversion
On the electrode base board 1 of gained, the aqueous dispersion of coating titanium oxide (average grain diameter 25nm), dry after 450 ℃ of following 1 hour heat treated, having formed thickness is the oxide semiconductor perforated membrane 2 of 10 μ m.Then, it is flooded in the ethanolic solution of ruthenium bipyridine complex (N3 dyestuff) carried out dyestuff in 8 hours and support, prepared work electrode 3.
As to electrode 4, use the FTO glass electrode substrate of platinum sputter, this to electrode 4 and work electrode 3, is oppositely arranged under the state that with the thick thermoplastic polyolefin resin's plate of 50 μ m is the dividing plate intervention, fix two electrodes 3 and 4 by the heat fusing of resin plate.At this moment, as electrolytical inlet, will vacate the part of electrode 4.The methoxyacetonitrile solution that is 0.5M iodide salt and 0.05M iodine by this inlet injection principal component has formed dielectric substrate 5, is that potting resin encapsulates with its periphery and inlet with epoxy, has made the components of photo-electric conversion that become the Experimental cell unit after curren-collecting part silver coating paste.
The light-to-signal transfer characteristic of this Experimental cell unit is that the result that 1.5 simulated solar irradiation detects shows that its conversion efficiency is 3.0% (AM) by air mass (ェ ァ マ ス).
Embodiment A 2
The preparation of electrode base board
As base material 10, use the heat resistant glass substrate of 100mm * 100mm, on its surface, according to the step same with embodiment A 1, use the silver-colored paste of printing, forming circuit width is that 50 μ m, thickness are the metal wiring layer 12 of 5 μ m, then on this metal wiring layer 12, forms FTO film as transparency conducting layer 11 by the SPD method.Then, use the method same with embodiment A 1, by the printing of glass paste, the pattern of contrast metal wiring layer 12 forms insulating barrier 14, has prepared the electrode base board 1 of structure as shown in Figure 3.
The preparation of the components of photo-electric conversion
Use this electrode base board 1, the step according to same with embodiment A 1 has prepared the components of photo-electric conversion that become the Experimental cell unit.The light-to-signal transfer characteristic of this Experimental cell unit is that the result that 1.5 simulated solar irradiation detects shows that its conversion efficiency is 2.5% by air mass (AM).
Embodiment A 3
The preparation of electrode base board
As transparency conducting layer 11 and base material 10, use the glass substrate of the subsidiary FTO film of 100mm * 100mm, on its surface, formed by additional coating process that to contain circuit width be that 50 μ m, thickness are the metal wiring layer 12 of the golden circuit of 5 μ m.On this metal wiring layer 12, adopt the method same with embodiment A 1, by the printing of glass paste, the pattern of contrast metal wiring layer 12 forms insulating barrier 14, has prepared the electrode base board 1 of structure shown in Figure 1B.
The preparation of the components of photo-electric conversion
Use this electrode base board 1, the step according to same with embodiment A 1 has prepared the components of photo-electric conversion that become the Experimental cell unit.The light-to-signal transfer characteristic of this Experimental cell unit is that the result that 1.5 simulated solar irradiation detects shows that its conversion efficiency is 3.3% by air mass (AM).
Comparative examples A 1
The preparation of electrode base board
As base material 10, use the heat resistant glass substrate of 100mm * 100mm, on its surface, according to the step same with embodiment A 1, forming circuit width with printing with silver-colored paste is that 100 μ m, thickness are the metal wiring layer 12 of 5 μ m, follows at this above metal wiring layer 12, according to the step identical with embodiment A 2, formed FTO film, prepared electrode base board 1 as transparency conducting layer 11 and shielding layer 13.
The preparation of the components of photo-electric conversion
Use this electrode base board 1, the step according to same with embodiment A 1 has prepared the components of photo-electric conversion as the Experimental cell unit.Observe the electrolyte that injects this Experimental cell unit and find, when this liquid just has been injected into, be dark brown,, become almost transparent through after a few minutes.This can think the I in the electrolyte 3 -Ion because covering of silver-colored circuit is not very abundant, is given birth to reaction with the silver hair that exposes, and is reduced to I -Cause.The light-to-signal transfer characteristic of this Experimental cell unit is that the result that 1.5 simulated solar irradiation detects shows that its conversion efficiency is 0.24% by air mass (AM).
Can learn that thus under the situation that insulating barrier 14 is not set, covering of silver-colored circuit is abundant inadequately, the light-to-current inversion efficient of the components of photo-electric conversion is reduced.
Comparative examples A 2
The preparation of electrode base board
As transparency conducting layer 11 and base material 10, use the glass substrate of the subsidiary FTO film of 100mm * 100mm, on its surface, formed by additional coating process that to contain circuit width be 50 μ m, thickness is the metal wiring layer 12 of the golden circuit of 5 μ m.On this metal wiring layer 12, adopt the method same with embodiment A 2, having formed as the thickness of transparency conducting layer 11 and shielding layer 13 is the FTO film of 300nm, has prepared electrode base board 1.
Observe the surface of the electrode base board 1 that so forms by SEM, EDX and find,, have the part that pierces that the hauling-out bottom that is considered to by anti-coating caused, pierce the coating that does not form FTO on the dash area partly at this in the bottom of metal wiring layer 12.
The preparation of the components of photo-electric conversion
Use this electrode base board 1, the step according to same with embodiment A 1 has prepared the components of photo-electric conversion as the Experimental cell unit.The light-to-signal transfer characteristic of this Experimental cell unit is that the result that 1.5 simulated solar irradiation detects shows that its conversion efficiency is 0.30% by air mass (AM).Hence one can see that, for shield conductive layer, insulating barrier 14 is not set and only is provided with under the situation of shielding layer 13, and metal wiring layer 12 becomes and exposes easily; Under the situation that metal wiring layer 12 exposes, the light-to-current inversion efficient of the components of photo-electric conversion significantly reduces.
Comparative examples A 3
The preparation of electrode base board
As transparency conducting layer 11 and base material 10, use the glass substrate of the subsidiary FTO film of 100mm * 100mm, on its surface metal wiring layer 12 is not set, but the glass substrate that will attach the FTO film directly is used as electrode base board 1, step according to same with embodiment A 1 has prepared the components of photo-electric conversion that become the Experimental cell unit.The light-to-signal transfer characteristic of this Experimental cell unit is that the result that 1.5 simulated solar irradiation detects shows that its conversion efficiency is 0.11% by air mass (AM).Hence one can see that, under the situation that metal wiring layer 12 is not set, causes the light-to-current inversion efficient reduction of the components of photo-electric conversion greatly owing to the resistance of electrode base board.
The electrode base board of another embodiment of the present invention has metal wiring layer and transparency conducting layer on transparency carrier, metal wiring layer is made of for 2 layers internal layer and skin at least.Concrete condition also disposes the structure of metal wiring layer 24 as shown in Figure 8 on the transparency conducting layer 23 that is formed at transparency carrier 22 one sides.Perhaps, as shown in Figure 9, also on the transparency carrier 22 that has disposed metal wiring layer 24, form the structure of transparency conducting layer 23.Symbolic representation identical among Fig. 9 and the identical structure of structure of Fig. 8 with Fig. 8.
As the material of transparency carrier 22, can be identical with above-mentioned base material 10.The material that the preferred light transmitance is high.
As the material that forms transparency conducting layer 23, can be identical with above-mentioned transparency conducting layer 11.Preferred form by the high combination of materials of light transmission rate as far as possible or carry out suitable selection according to purposes.
Can from as well-known methods such as sputtering method, vapour deposition methods,, select the suitable method of employing as the method that on transparency carrier 22, forms transparency conducting layer 23 etc. corresponding to the material that forms transparency conducting layer 23.
Material as the 24a of the internal layer that forms metal wiring layer 24 has no particular limits, and for example, can use gold, silver, platinum, aluminium, nickel, titanium etc.Wherein, as general print paste,, can suitably use silver or nickel from relatively cheap and be easy to obtain this and consider on the one hand.
In the scope of not damaging characteristics such as conductance, can add bond or proper additive etc.
Formation method as internal layer 24a has no particular limits, and can list print process, sputtering method, vapour deposition method, coating process etc., preferred especially print process in these methods.
So the internal layer 24a specific insulation that forms is preferably less than the specific insulation of outer 24b.In the present embodiment, the film coated surface preferred smooth surface of internal layer 24a, but this layer forms for metal wiring layer 24 these the original purposes as the resistance that reduces electrode base board 21, so its high conductivity is top-priority.In addition, though the outer 24b of following explanation is a conductive layer, its main purpose is to make the wiring smooth surface and shielding layer 25 is formed easily, thus compare with internal layer 24a, even specific insulation more also has no relations.
As the specific insulation of internal layer 24a, preferably at least 5 * 10 -5Ω or still less.If satisfy this condition,, can be revised by outer 24b, so can not have problems even produce some pin holes or be full of cracks on the film surface.In metal wiring layer 24, if having this layer, for certain purpose, other layers different with outer 24b in the inside and outside formation of internal layer 24a also are fine.
The outer 24b of metal wiring layer 24 is preferably formed by the paste composition that contains conducting particles and bond at least.As conducting particles, have no particular limits, can list as silver, nickel, platinum etc.Wherein, as general print paste, from relatively cheap and be easy to acquisition aspect, use silver or nickel that can be suitable.
As bond, have no particular limits, for example, consider the heat treatment that contains in the manufacture process about 400～500 ℃ as in the electrode base board 21 of dye-sensitized solar cells, paste composition is selected the material of slug type, for example preferred glass material etc.As the frit of bond, there is no particular limitation, so long as at above-mentioned firing temperature or the material that more low temperature can fusion get final product.
Form the mixing ratio of the bond in the paste composition of outer 24b, preferably than the bond material mixing in the composition that forms other layers in the metal wiring layer 24 than big.So by adjusting the mixing ratio of bond material, make outer 24b film coated surface not contain pin hole or be full of cracks etc., inhibition becomes the remarkable concavo-convex generation of shade when seeing from above, can be easy to form shielding layer 25.
Form the mixing ratio of the bond in the paste composition of outer 24b, for conducting particles, preferred mass is than 10% or more, and more preferred 20% or more.Just, be accompanied by the increase of the mixing ratio of bond material, the conductance of film (outer 24b) significantly descends, therefore in surface state satisfies the scope of above-mentioned requirements, the mixing ratio of bond is less to be suitable, preferred 90% or still less, more preferred 70% or still less.
As the method that forms outer 24b, preferred print process.So long as print process has no particular limits, can list as silk screen print method, ink-jet method, metal mask method etc.
So, by formed outer 24b by print process, (roughness) is little for surface roughness, and does not produce be full of cracks or pin hole, so that the smooth surface of metal wiring layer 24, thereby can be easy to form shielding layer 25.
And, use print process, can reduce manufacturing cost and improve manufacturing efficient.
Outer 24b in this specification is expressed as above-mentioned purpose and by the printed layers that print process forms, not necessarily must be configured in the most surperficial of metal wiring layer 24, can form for other layers of some purpose in its more lateral as required.
When comparing the thickness of filming of internal layer 24a and outer 24b, the thickness of outer 24b preferably is no more than 100% of internal layer 24a thickness.If the thickness of outer 24b surpasses 100% of internal layer 24a thickness, the volume conductivity of circuit reduces, thereby is easy to generate condition of poor such as the blocked up or conductance of circuit thickness is insufficient.
No matter be internal layer 24a or outer 24b, for example waiting with conducting particles molten sticking is purpose need carry out firing process the time, as considering the adaptability of glass substrate is then preferably obtained down at 600 ℃ (suitable is 550 ℃) or lower firing temperature the characteristic of necessity.
In the present embodiment, preferably on the surface of the conductive layer of containing metal wiring layer 24 and/or transparency conducting layer 23, has shielding layer 25.
As the material that forms shielding layer 25, have no particular limits, so long as it is the time, slow-paced with the electron transfer reactions between the electrolyte that contains redox couple that is contacted, photopermeability is good and material that have the characteristic that does not hinder the photoelectronic migration that is produced gets final product as solar cell.For example can enumerate: titanium oxide, zinc oxide, niobium oxide, tin oxide, fluorine doped tin oxide (FTO), tin-doped indium oxide (ITO) etc.
Method as forming shielding layer 25 has no particular limits, and for example can enumerate purpose compound or its precursor are passed through the method that dry processes (vapor phase method) such as sputtering method, vapour deposition method, CVD method are made films.Before with metal etc., behind the system film, can make its oxidation form shielding layer 25 by heat treated or chemical treatment etc.
During damp process, after purpose compound or its precursor can being applied through solution that dissolving disperses, by methods such as whirl coating, infusion process, scraper plate coating processs, by heat treated or chemical treatment etc., it is chemically converted to the purpose compound, thereby forms shielding layer 25.As precursor, can exemplify salt, complex of the formation metallic element that contains the purpose compound etc.From obtaining fine and close film (shielding layer 25) this purpose, compare the preferred dissolution state with dispersity.
Under the spraying thermal decomposition situations such as (SPD), under the state that has heated transparency carrier, spray with material facing to this substrate, by with its thermal decomposition as the precursor of shielding layer 25 with transparency conducting layer 23, become the purpose oxide semiconductor, thereby form shielding layer 25.
The thickness of shielding layer 25 is not particularly limited, and preferably approaches in the scope of performance effect, about preferred 10～3000mm.
For the electrode base board 21 of present embodiment, as shown in Figure 9, after forming metal wiring layer 24, on substrate, form in the structure of transparency conducting layer 23, transparency conducting layer 23 can double as shielding layer 25.
As described above, the electrode base board 21 of present embodiment, on the surface of the outer 24b of metal wiring layer 24, owing to do not produce the part that becomes shade of pin hole or be full of cracks etc., so its surface can be coated densely by shielding layer 25.
Then, the dye-sensitized solar cells that uses above-mentioned electrode base board 21 is illustrated.
The dye-sensitized solar cells of present embodiment, on above-mentioned electrode base board 21, have the work electrode that possesses the oxide semiconductor perforated membrane that has supported dyestuff and with this work electrode be oppositely arranged to electrode, the dielectric substrate that contains redox couple is set at work electrode and between to electrode.
As the material of multichip semiconductor pore membrane, can enumerate as titanium oxide (TiO 2), tin oxide (SnO 2), tungsten oxide (WO 3), zinc oxide (ZnO 2), niobium oxide (Nb 2O 5) etc., can be individually or make up more than 2 kinds or 2 kinds and use with these materials.Also obtain colloidal solution that can obtain etc. from the particulate of market sale or by sol-gel process.
Manufacture method as the multichip semiconductor pore membrane, for example, except that colloidal solution or dispersion liquid (containing additive as required) being adopted various coating methods such as silk screen print method, ink jet printing method, roller coating process, scraper plate finishing, whirl coating, spraying process apply, the electrophoretic deposition of applicable particulate, with blowing agent and with and with compoundization methods such as (only removing the template composition then) such as polymer drops.
Dyestuff as the multichip semiconductor pore membrane is supported has no particular limits, and can select to contain in the ligand ruthenium complex of bipyridine structure, three pyridines etc., contains metal complexes such as porphyrin, phthalein green grass or young crops; Organic dyestuff such as eosin, base rhodamine, part cyanines etc. can be selected to be adapted to purposes, reach the semi-conductive material that excites behavior that uses.
As the electrolyte that forms dielectric substrate, can use the organic solvent that contains redox couple, room temperature fuse salt etc.Can enumerate as, organic solvents such as acetonitrile, methoxyacetonitrile, propionitrile, propene carbonate, diethyl carbonate, gamma-butyrolacton, by season imidazoles cation and the room temperature fuse salt that constitutes such as iodide ion or two fluoroform sulphonyl imido anion etc.
Also can use by in this class electrolyte, adding the class solid, shaped material that suitable gelling agent forms, promptly so-called gel electrolyte.
As redox couple, have no particular limits, can enumerate for example iodine/iodide ion, bromine/bromide ion etc., for example, can enumerate by the combination of iodide salt (can be individually or compoundly use lithium salts, season imidazole salts, 4-butyl ammonium etc.) with iodine as the former particular content.In electrolyte, can add various additives such as tert .-butylpyridine further as required.
The dielectric substrate that replacement is formed by electrolyte also can use p N-type semiconductor N etc. as charge transport layer.As the p N-type semiconductor N, have no particular limits, for example, monovalence copper compounds such as use cupric iodide that can be suitable, copper rhodanide.Requirement according on the function, on the system film can contain various additives.
Method as forming charge transport layer has no particular limits, and for example can enumerate film-forming methods such as casting method, sputtering method, vapour deposition method.
To electrode, can be by for example on conductivity or dielectric substrate, various carbon-based materials, platinum, gold etc. being formed through methods such as vapour deposition method, sputtering methods.
When using the charge transport layer of solid,, also can adopt methods such as direct sputter or coating on its surface.
The dye-sensitized solar cells of present embodiment, because have electrode base board 21, suppressed the burn into of the metal line that produces by electrolyte and from the reverse electron transfer of metal wiring layer 24, thereby further improved the output effect of the components of photo-electric conversion to electrolyte.
Then, the embodiment to above-mentioned execution mode is illustrated.
Embodiment B 1
At the glass surface of the subsidiary FTO film of 100 * 100mm, silver-colored paste (silver granuel 92/ frit 8 (the mass ratio)) silk screen printing that forms internal layer 24a has been become clathrate.Through 10 minutes leveling time, under 135 ℃, in the hot-air drying stove, carry out 20 minutes dryings after, burn till through 15 minutes at 550 ℃.Then, in the time of by use CCD camera adjusting position, overlapping being coated with applies the silver-colored paste (silver granuel 55/ frit 45 (mass ratio)) that forms outer 24b, through 10 minutes leveling time,, after 135 ℃, 20 minutes dryings, burnt till through 15 minutes and formed silver-colored circuit at hot-air drying stove at 550 ℃.Circuit width is 250 μ m (outer 24b), 150 μ m (internal layer 24a), and thickness is 8 μ m (outer 3 μ m+ internal layers, 5 μ m).
On the prepared surface that has the substrate of wiring like this, form the thick FTO layer of 300nm as shielding layer 25 by spray heating decomposition, obtained electrode base board (i).
Observed the surface and the surface of outer 24b of internal layer 24a of the silver-colored circuit of electrode base board (i) respectively finds by SEM, surface at internal layer 24a, observe a lot of frits and do not have the part of inflow and the aperture of about 1～8 μ m, on the contrary, aperture is not almost found on surface at outer 24b, and has obtained the face of the smoother of Ra0.4 μ m.
On electrode base board (i), the coating average grain diameter be the titanium oxide dispersion liquid of 25nm, drying, 450 ℃ of heat-agglomeratings 1 hour.Place it in that dipping supports to carry out dyestuff for one night in the ethanolic solution of ruthenium bipyridine complex (N3 dyestuff).With it by the thick thermoplastic polyolefin resin's plate of 50 μ m, with sputter the FTO substrate of platinum relative and be provided with, with the resin plate heat fusing, and fixed two electrodes.In advance, offer electrolytical inlet, between electrode, inject principal component and be the methoxyacetonitrile solution of the iodine of the iodide of 0.5M and 0.05M in platinum sputtering electrode side.Is that potting resin encapsulates with its periphery and electrolyte inlet with epoxy, at current-collecting terminals portion silver coating paste, has made cloth line style battery unit (i).
By AM is 1.5 simulated solar irradiation, and the result who detects light-to-signal transfer characteristic shows that the conversion efficiency of this cloth line style battery unit (i) is 2.7%.
Embodiment B 2
On the heat resistant glass substrate, be identically formed silver-colored circuit with Embodiment B 1, formed the FTO film on the surface of this substrate.It as transparency conducting layer 23 double shielding layers 25, has been made electrode base board (ii).
Use this electrode base board (ii), made cloth line style battery unit (ii) according to the main points identical with Embodiment B 1.By AM is 1.5 simulated solar irradiation, and the result who detects light-to-signal transfer characteristic shows that this cloth line style battery unit conversion efficiency (ii) is 2.5%.
Embodiment B 3
In the length of side is on the square FTO glass substrate of 100mm, has formed golden circuit by the extra play coating process.The gold circuit forms clathrate on substrate surface, circuit width is 50 μ m.From it, as the overlapping printed silver printed circuit of outer 24b,, carried out drying and sintering according to the main points identical with Embodiment B 1.The silver paste uses the material that contains silver particles 55/ frit 45 (mass ratio), and the thickness of film is 8 μ m (outer 3 μ m+ internal layers, 5 μ m).On its surface, the FTO layer that is identically formed 300nm with Embodiment B 1 has made electrode base board (iii) as shielding layer 25.
Use this electrode base board (iii), the main points according to identical with Embodiment B 1 have made cloth line style battery unit (iii).By AM is 1.5 simulated solar irradiation, and the result who detects light-to-signal transfer characteristic shows that this cloth line style battery unit conversion efficiency (iii) is 3.1%.
Comparative example B1
In the length of side is on the square FTO glass substrate of 100mm, and it is 250 μ m that silver-colored paste (silver granuel 92/ frit 8 (mass ratio)) is applied as circuit width, and thickness is the film of 8 μ m, will put drying and sintering according to identical with Embodiment B 1.On its surface, the FTO layer of identical formation 300nm with Embodiment B 1 has made electrode base board (iv) as shielding layer 25.
Use this electrode base board (iv), made cloth line style battery unit (iv) according to the main points identical with Embodiment B 1.Observe to inject this cloth line style battery unit electrolyte (iv) and find, when this liquid just has been injected into, be dark brown, but through after a few minutes, change almost transparent.This can think, because the I in the electrolyte 3 -The silver hair that ion exposes with crested is not given birth to reaction, is reduced to I -Cause.
By AM is that the result that 1.5 simulated solar irradiation detects light-to-signal transfer characteristic shows that this cloth line style battery unit conversion efficiency (iv) is 0.29%.
Comparative example B2
In the length of side is on the square FTO glass substrate of 100mm, and it is 250 μ m that silver-colored paste (silver granuel 55/ frit 45 (mass ratio)) is printed as circuit width, and thickness is the film of 8 μ m, will put drying and sintering according to identical with Embodiment B 1.On its surface, the FTO layer that is identically formed 300nm with Embodiment B 1 has made electrode base board (v) as shielding layer 25.
(v), the main points according to identical with Embodiment B 1 have made cloth line style battery unit (v) to use this electrode base board.By AM is that 1.5 simulated solar irradiation detects, and the result of light-to-signal transfer characteristic shows that (conversion efficiency v) is 0.18% to this cloth line style battery unit.
Comparative example B3
In the length of side is on the square FTO glass substrate of 100mm, forms golden circuit by additional coating process.The gold circuit forms clathrate on substrate surface, circuit width is 50 μ m, and film thickness is 5 μ m.On its surface, the FTO layer that is identically formed 300nm with Embodiment B 1 has made electrode base board (vi) as shielding layer 25.(vi) section finds, the part that pierces that the hauling-out bottom that is considered to by anti-coating causes is arranged in the bottom of circuit (wiring), at dash area FTO in the coating not to observe this electrode base board by SEM, EDX.
(vi), the main points according to identical with Embodiment B 1 have made cloth line style battery unit (vi) to use this electrode base board.By AM is that the result that 1.5 simulated solar irradiation detects light-to-signal transfer characteristic shows that (conversion efficiency vi) is 0.3% to this cloth line style battery unit.
Comparative example B4
Use the square FTO glass substrate of the length of side as 100mm, without wiring, the method according to identical with Embodiment B 1 has made the Experimental cell unit (vii).By AM is that the result that 1.5 simulated solar irradiation detects light-to-signal transfer characteristic shows that (conversion efficiency vii) is 0.11% in this Experimental cell unit.
About Embodiment B 1～B3 cloth line style battery, though the light-to-current inversion efficient of its all batteries is all very superior, relative therewith, the cloth line style battery unit of comparative example B1 metal wiring layer 24 (iv) is made of one deck, because covering of shielding layer 25 is not really abundant, therefore can not bring into play the characteristic of electrode base board, conversion efficiency is bad.The cloth line style battery unit of comparative example B2 (v), metal wiring layer 24 is to be made of one deck, because its specific insulation height, so can not reduce the resistance of electrode base board, and owing to can not get high output, so its conversion efficiency is bad.(vi), metal wiring layer 24 is to be made of one deck to the cloth line style battery unit of comparative example B3, because covering of shielding layer 25 is not very abundant, so can not bring into play the characteristic of electrode base board, conversion efficiency is bad.
Electrode base board 21 provides substrate surface surface roughness, that can form the shielding layer 25 of the densification that does not have pin hole etc. that reduces metal wiring layer 24.Dye-sensitized solar cells with such electrode base board 21 suppresses the corrosion of the metal line that caused by electrolyte, and from the reverse electron transfer of metal wiring layer 24 to electrolyte, thereby further improves the output effect of the components of photo-electric conversion.
Figure 10 is expression other the summary section of execution mode of the present invention.
Transparency carrier 32 has by methods such as laser, corrosion and carries out the wiring pattern that ditch processing gets.By the concave shaped portion that ditch is processed to form, mean the subsurface state that arrives transparency carrier 32, its shape is not limited to lenticular, concavity, V-type ditch shape etc.Said surface has been meant formation in substrate surface multichip semiconductor pore membrane etc. and with and face that be provided with relative to electrode.
As transparency carrier 32, usually use glass such as heat resistant glass, but except glass, can enumerate for example polyethylene terephthalate (PET), poly-to naphthalenedicarboxylic acid second diester (PEN), Merlon (PC), polyether sulfone transparent plastic sheets such as (PES), and ceramic polished plate such as titanium oxide, aluminium oxide, the material that the preferred light permeability is high.
Metal wiring layer 33 forms along the wiring pattern that has carried out ditch processing on transparency carrier 32, as long as at least a portion of metal wiring layer 33 is the structure that reaches the surperficial following height of transparency carrier 32, does not have other particular restriction.For example, as shown in figure 10, the surface of metal wiring layer 33 has identical height with the surface of transparency carrier 32; As shown in figure 11, the surface of metal wiring layer 33 reaches than higher position, transparency carrier 32 surfaces; And metal wiring layer 33 also can all be formed on the surface following (figure slightly) of transparency carrier 32.In any one execution mode, from the formation direction of shielding layer 35, preferred significantly not concavo-convex as far as possible, become piercing or the smooth shape in space etc. of shade.For the difference in height between the surface of the surface of metal wiring layer 33 and transparency carrier 32, the preferred heights difference is little.
The material that forms metal wiring layer 33 has no particular limits, and for example, can use gold, silver, platinum, aluminium, nickel, titanium etc.
The formation method of metal wiring layer 33 has no particular limits, for example, can use with headed by the print processes such as silk screen printing, metal mask, ink-jet and the whole bag of tricks such as coating process, sputtering method, vapour deposition method.Specially suitable any one the method that can select to comprise in coating process, the print process.The height on the surface of metal wiring layer 33 can be adjusted to apparent height Xiang Qi with transparency carrier 32 etc. by grinding.
Metal wiring layer 33 concerns that with the position of transparency conducting layer 34 there is no particular limitation.In the execution mode of Figure 10, metal wiring layer 33 is embedded on the surface of substrate 32 in the formed ditch, forms transparency conducting layer 34 whole of substrate 32.In this case, the lower surface conducting of whole of the upper surface of metal wiring layer 33 and transparency conducting layer 34.
In the execution mode of Figure 11, formed transparency conducting layer 34, and formed the ditch that constitutes wiring pattern, in this ditch, buried metal wiring layer 33 underground whole of substrate 32.In the case, in order to make metal wiring layer 33 and transparency conducting layer 34 conductings really, the upper end of preferable alloy wiring layer 33 bloats from transparency conducting layer 34, and the edge of adjacent transparency conducting layer 34 is covered in certain width.By this cantilever portion 33A conducting positively.Then, whole of substrate 32, form shielding layer 35.As shown in figure 11, shielding layer 35 can exceed one section on metal wiring layer 33, also can be to spread all over whole tabular surface.
In the execution mode of Figure 12 A, formed the ditch that constitutes Wiring pattern on the surface of substrate 32 after, form transparency conducting layer 34 surperficial whole of the substrate 32 that comprised this ditch inside, then formation metal wiring layer 33 in ditch.In this case, for positively conducting transparency conducting layer 34 and metal wiring layer 33, the upper end of preferable alloy wiring layer 33 bloats from transparency conducting layer 34, and with the edge of adjacent transparency conducting layer 34 in certain width, cover.By this cantilever portion 33A conducting positively.Then, whole with metal wiring layer 33 and substrate 32 forms shielding layer 35.As shown in figure 12, shielding layer 35 can exceed one section on metal wiring layer 33, also can be to spread all over whole tabular surface.
The execution mode of Figure 12 B is the distortion of the execution mode of Figure 11, it is characterized in that 35 of shielding layers are covering the position formation of metal wiring layer 33.Shown in Figure 12 C, the upper surface of metal wiring layer 33 can be concave surface, and this concave surface is that the volume contraction when forming metal wiring layer 33 produces.
Figure 12 D is, used the profile of an example of the dye-sensitized solar cells of the electrode base board 31 among Figure 12 B.Symbol in addition identical with Figure 1A identical construction omits explanation.
Form the material of transparency conducting layer 34, have no particular limits, can list as tin-doped indium oxide (ITO), tin oxide (SnO 2), fluorine doped tin oxide (FTO) etc., preferred as far as possible according to the combination or the purposes of material, the suitable high material of selective light transmitance.
The formation method of transparency conducting layer 34 has no particular limits, for example can be from well-known method such as sputtering method, vapour deposition method, CVD and SPD method, according to the material that forms transparency conducting layer 34 etc., adopt proper method.
In the electrode base board 31 of this execution mode, when on the substrate that has disposed metal wiring layer 33, having formed transparency conducting layer 34, but transparency conducting layer 34 double as shielding layers 35.
Conductive layer surface at containing metal wiring layer 33 and/or transparency conducting layer 34 forms shielding layer 35.Shielding layer 35 preferably contains and is selected from least a in glass ingredient, metal oxide composition and the electrochemistry inert plastic composition.As glass ingredient, can enumerate with low-melting amorphism or crystallinity glass ingredient headed by lead oxide system or the lead borate system etc.; As the metal oxide composition, can enumerate titanium oxide, zinc oxide, fluorine doped tin oxide (FTO), tin-doped indium oxide (ITO) etc.; As the electrochemistry inert plastic, can enumerate polyolefin-based resins, polyimides is that resin, polybenzoxazole are resin, polyurethane series resin etc., these can be used individually, or will use in combination more than 2 kinds or 2 kinds.
The formation scope of shielding layer 35 is when containing metal wiring layer 33 surface and having disposed the wider scope of transparent part of transparency conducting layer 34, select significantly not damage photopermeability, from the material and the thickness of the electron transfer (that is, significantly not reducing the battery unit characteristic) of multichip semiconductor pore membrane.If the shielding layer 35 of more detailed elaboration about constituting by metal oxide composition (oxide semiconductor), its material requires to have following characteristic, that is, as behind the dye-sensitized solar cells with contacted, and contain that electron transfer reactions speed between the electrolyte of redox couple is slow, photopermeability is superior and do not hinder the photoelectronic migration that is produced.As long as satisfied so desired characteristic, there is not any restriction about concrete material, for example can enumerate titanium oxide, zinc oxide, niobium oxide, tin oxide, FTO, ITO etc.
Formation scope as shielding layer 35, so long as comprise the scope on the surface of metal wiring layer 33 at least, just have no particular limits, also can be the surface that only is defined as metal wiring layer 33, also can be than containing metal wiring layer 33 surface and having disposed the wider scope of the transparent part of transparency conducting layer 34.Though to compare problem relative less with metal wiring layer 33, but owing to the phenomenon of being pointed out from the reverse electron transfer of transparency conducting layer 34, therefore, by form shielding layer 35 on than the wider scope of the transparent part that has disposed transparency conducting layer 34, tighter covering is possible.
The formation method of shielding layer 35 has no particular limits, can list as, purpose compound or its precursor are made the method for film by dry processes (vapor phase method) such as sputtering method, vapour deposition method, CVD methods.When the precursor of metal etc. has been carried out the system film, can carry out oxidation by heat treated or chemical treatment etc. and form shielding layer 35.
Under the situation of damp process, to dissolve, disperse the solution of purpose compound or its precursor, after the coating of methods such as whirl coating, infusion process, scraper plate coating process, be the purpose compound by heat treated or chemical treatment chemical transformation, thereby form shielding layer 35.As precursor, for example contain salt, complex of the formation metallic element of purpose compound etc.In order to obtain fine and close film (shielding layer 35), than dispersity and the preferred dissolution state.
Under the spray heating decomposition situations such as (SPD), can have under the state of transparency carrier 32 of transparency conducting layer 34 in heating, spray with material facing to this substrate, by thermal decomposition as the precursor of shielding layer 35, be transformed into the purpose oxide semiconductor, thereby form shielding layer 35.
In present embodiment, inverted cone-shaped structure, the bottom that has suppressed metal wiring layer 33 pierces etc. and to form covering of dash area during the system film bad, the reduction of the battery unit characteristic that can suppress to cause thus.About the concaveconvex structure on electrode base board 31 surfaces, increase circuit thickness owing to can not strengthening difference in height, thus can increase the aperture opening ratio (ratio of non-wiring portion) of electrode base board 31, and can realize low resistanceization.
Then, the dye-sensitized solar cells that has used above-mentioned electrode base board 31 is illustrated.
The dye-sensitized solar cells of present embodiment, on above-mentioned electrode base board 31, possesses work electrode with the oxide semiconductor perforated membrane that has supported dyestuff, and with this work electrode be oppositely arranged to electrode, at work electrode and between, the dielectric substrate that contains redox couple is set to electrode.
The material of multichip semiconductor pore membrane can be identical with above-mentioned execution mode.Manufacture method as the multichip semiconductor pore membrane, for example, except that colloidal solution or dispersion liquid (containing additive as required) are applied by various coating methods such as silk screen coating process, ink-jet coating method, roller coating process, scraper plate finishing, whirl coating, spraying processes, the electrophoretic deposition of particulate, with blowing agent and with, also applicable with the compoundization methods such as (only removing the template composition then) of polymer drops etc.
The dyestuff that supports for the multichip semiconductor pore membrane, form the electrolyte of dielectric substrate, can be identical with above-mentioned execution mode.By adding suitable gelling agent in the electrolyte, also can use class solid, shaped material, promptly so-called gel electrolyte.Redox couple also can be identical with above-mentioned execution mode.
The dielectric substrate that replacement is formed by electrolyte also can use p N-type semiconductor N etc. as charge transport layer.As the p N-type semiconductor N, have no particular limits, for example, monovalence copper compounds such as use cupric iodide that can be suitable, copper rhodanide.Needs according on the function, on the system film can contain various additives.Formation method as charge transport layer has no particular limits, and for example can enumerate film-forming methods such as casting method, sputtering method, vapour deposition method.
To electrode, for example, can on conductivity or dielectric substrate, various carbon-based materials, platinum, gold etc. be formed by methods such as vapour deposition method, sputtering methods.
Under the situation of the charge transport layer that uses solid system,, can adopt methods such as direct sputter or coating on its surface.
The dye-sensitized solar cells of present embodiment, because have above-mentioned electrode base board 31, so inhibition is reached from the reverse electron transfer of metal wiring layer 33 to electrolyte by the burn into of the metal line that electrolyte produces, thereby further improve the output effect of the components of photo-electric conversion.
Then, the embodiment to above-mentioned example is illustrated.
Embodiment C 1
At the glass surface of the subsidiary FTO film of 100 * 100mm, formed the ditch of dark 5 μ m with being grid circuit shape pattern.,, formed metal conducting layer (Seed Layer (シ one De layer)) thereon, further formed metal wiring layer 33 by additional coating process by sputtering method in order to implement to electroplate.Metal wiring layer 33 is lens-shaped ground from transparency carrier surface 32 and forms 3 μ m height.Circuit width is 60 μ m.,, form the thick FTO film of 400nm then thereon, obtained electrode base board (i) by the SPD method as shielding layer 35.The section shape of electrode base board (i) is standard with Figure 11.
On electrode base board (i), coating is dry, and average grain diameter is the titanium oxide dispersion liquid of 25nm, 450 ℃ of heat-agglomeratings 1 hour.Place it in the ethanolic solution of ruthenium bipyridine complex (N3 dyestuff) one night of dipping, carried out dyestuff and supported.Its with the thick thermoplastic polyolefin resin's plate of 50 μ m be intermediary and with sputter the FTO substrate of platinum be oppositely arranged, make resin board heat fusing, fix two battery lead plates.In advance, at the inlet of platinum sputtering electrode side electrolyte, inject between electrode that to contain with 0.5M iodide and 0.05M iodine be the methoxyacetonitrile solution of main component.Is that potting resin encapsulates with periphery and electrolyte inlet with epoxy, at current-collecting terminals portion silver coating paste, has made Experimental cell unit (i).By AM is 1.5 simulated solar irradiation, and the result who detects light-to-signal transfer characteristic shows that the conversion efficiency of this Experimental cell unit (i) is 2.8%.
Embodiment C 2
On the heat resistant glass surface of 100 * 100mm, carve circuit pattern with laser engraving machine, formed the metal wiring layer 33 identical with Embodiment C 1.Formed as the hold concurrently thick FTO film of 1000nm of shielding layers 35 of transparency conducting layer 34 by the SPD method thereon, made electrode base board (ii).Formed electrode base board section shape (ii), except transparency conducting layer 34 had reached on the metal line, other were standard with Figure 11.
Use this electrode base board (ii), the main points according to identical with Embodiment C 1 have made the Experimental cell unit (ii).By AM is that the result that 1.5 simulated solar irradiation detects light-to-signal transfer characteristic shows that this Experimental cell unit conversion efficiency (ii) is 3.0%.
Embodiment C 3
On the heat resistant glass surface, formed the metal wiring layer 33 identical with Embodiment C 1 after, by the wafer grinding machine metal wiring layer 33 is ground to roughly identical with substrate surface height.Thereon, formed as the hold concurrently thick FTO film of 1000nm of shielding layers 35 of transparency conducting layer 34 by the SPD method.Then, form the thick oxidation titanium film of 30nm as shielding layer 35 by sputtering method thereon, formed electrode base board (iii).Electrode base board section shape (iii) is standard with Figure 10.
Use this electrode base board (iii), made the Experimental cell unit (iii) according to the main points identical with Embodiment C 1.By AM is that the result that 1.5 simulated solar irradiation detects light-to-signal transfer characteristic shows that this Experimental cell unit conversion efficiency (iii) is 3.1%.
Comparative example C1
In the length of side is on the square FTO glass substrate of 100mm, has formed metal wiring layer 33 (golden circuit) by additional coating process.Metal wiring layer 33 (golden circuit) is formed on substrate surface with clathrate, and circuit width is 50 μ m, and film thickness is 5 μ m.On its surface, formed the thick FTO film of 300nm as shielding layer 35 by the SPD method, made electrode base board (iv).Observe this electrode base board section (iv) by SEM, EDX and find, the part that pierces that the hauling-out bottom that is considered to by anti-coating causes is arranged in the wiring bottom, do not coat FTO at dash area.
Use this electrode base board (iv), made the Experimental cell unit (iv) according to the main points identical with Embodiment C 1.By AM is that the result that 1.5 simulated solar irradiation detects light-to-signal transfer characteristic shows that this Experimental cell unit conversion efficiency (iv) is 0.3%.
Comparative example C2
Use the square FTO glass substrate of the length of side, made the Experimental cell unit (v) without wiring ground according to the method identical as a comparison with Embodiment C 1 as 100mm.By AM is 1.5 simulated solar irradiation, and (result of light-to-signal transfer characteristic v) shows that (conversion efficiency v) is 0.11% in this Experimental cell unit to the test experience battery unit.
Can find by above result, the light-to-current inversion efficient of any one all is very superior in the Experimental cell unit (i)～(iii) of Embodiment C 1～3 gained, relative therewith, the Experimental cell unit of comparative example C1 gained (iv), covering of its shielding layer 35 is not very abundant, fail to have given play to the characteristic of electrode base board, so conversion efficiency is bad.
From finding that with comparative example C2 contrast used the Experimental cell unit of relevant electrode base board in the embodiments of the present invention, the length of side is the square area battery unit of 100mm degree, its light-to-current inversion efficient can be largely increased.
Other execution mode of the present invention is a conductive glass substrate; wherein on the glass plate of having implemented nesa coating; have contain with passive metal catalytic action arranged contain substitutional metal or have the material of above-mentioned metal the electroconductive circuit layer, and above-mentioned electroconductive circuit layer on the circuit protecting layer of the insulating properties that forms, this conductive glass substrate forms the conducting glass substrate that the components of photo-electric conversion of passive metal are used as the pin hole portion that produces in above-mentioned circuit protecting layer.In this case, obtained the conductive glass substrate that the superior components of photo-electric conversion of transparent height, resistance to chemical reagents, leakage current and conductivity are used.
Describe with Figure 13, the 41st, glass plate, adopting thickness usually is alkali glass, heat resistant glass about 1～5mm etc.The 42nd, the nesa coating that on glass plate 41, is provided with, normally thickness is the transparent conductive membrane of mixing indium tin oxide (ITO) or fluorine doped tin oxide etc. containing about 0.2～1 μ m.On nesa coating 42, form electroconductive circuit 44.Electroconductive circuit 44 has been to use to be had catalytic action or substitutional metal or has the material of above-mentioned metal and the electroconductive circuit that forms its after-applied passive metal.Electroconductive circuit 44 is by formation such as coating process or silk screen coating processs, and the hem width that forms is about 10～1000 μ m.Usually flat shape is clathrate or broach shape.But the present invention is not only limited to this.The aperture opening ratio of electroconductive circuit 44 preferred 75% or more also can be 90～99%.During aperture opening ratio less than 75%, light penetration reduces, and then incident light quantity is insufficient.Surpass at 99% o'clock, conductivity might be insufficient.For example, aperture opening ratio can be 75%～85%, but is not only limited to this scope.Aperture opening ratio is recently defining with the gross area of foregoing circuit shared in unit are.
Above-mentioned electroconductive circuit is by gold, silver, platinum, palladium, copper or aluminum metal, or at least a conductive paste that contains in these metals forms.Above-mentioned conductive paste contains the frit as bonding composition, and contain electrically conductive microparticle, it has been metal catalyst action or substitutional that but this electrically conductive microparticle can contain for the passive metal of implementing thereafter simultaneously, preferably contain at least a material in gold, silver, platinum, palladium, copper or the aluminum metal, preferably wherein add silver-colored particulate.
On electroconductive circuit 44, form the circuit protecting layer 45 of insulating properties.The circuit protecting layer 45 of this insulating properties forms from the leakage current of electroconductive circuit 44 electronics reverse flow to electrolyte in order to prevent, is circuit 41 to be insulated fully coat and form.Usually, consider and the problems such as adherence of circuit 41, use the paste material of bonding composition as frit.But with regard to this insulating properties paste material, under the situation that electroconductive circuit 44 forms by conductive paste, preferably can burn till the material of processing under than the also low temperature of conductive paste.Concrete, can use plumbous pyrex material, inorganic adhesive, organic adhesive etc.This insulating properties paste by the silk screen coating, forms in the mode of complete coating circuit on circuit 41.Preferred this coating formation processing can repeatedly be carried out.Originally; this stage preferably as circuit protecting layer 45 performance functions with enough insulating properties; but,, can produce the problem of leakage current in this case so be easy to generate pin hole in this circuit protecting layer 45 because this protective layer is the layer of thin layer and the type that burns till that is to use frit.
In order to solve this pin hole problem, form passive metal at insulating properties circuit protecting layer 45.Concrete, form by no electrolytic metal coating processing.Use is confirmed as and be can be used as the passive metals such as nickel, copper or aluminium that the low resistance circuit uses, and from making purposes such as cheap for manufacturing cost, selects material by no electrolytic metal plating can formation passive metal for well.That is, above-mentioned no electrolytic metal coating is no electrolytic nickel plating, no electrolytic cobalt is electroplated or do not have the electrolytic tin plating.By implementing so no electrolytic nickel plating, plating of no electrolytic cobalt or not having the electrolytic tin plating and handle, partly separate out the passive metal of nickel, cobalt or tin etc. at pin hole, thereby form passive metal, the conducting between blocking-up electroconductive circuit 44 and electrolyte.To form as 46 described states among Figure 13.This phenomenon is owing to will be selected from the metal that is used to form foregoing circuit 41: a kind of in palladium, platinum, gold, silver, copper or the aluminum metal, add and the effect that produces as catalyst metals or displaced type metal.That is, not have that electrolytic metal coating handles be for precipitating metal coating on above-mentioned metal with catalytic action for above-mentioned catalytic type or above-mentioned displaced type.Because any one of these catalytic types or displaced type metal all is the element of conductivity, can adds in the conductive paste that circuit forms usefulness and utilize.No electrolytic metal coating as formation passive metal like this is handled; do not have electrolytic nickel plating, the plating of no electrolytic cobalt or do not have electrolytic tin plating processing by suitable employing, can have been prevented the conductive glass substrate 43 that the components of photo-electric conversion of the pin hole in the circuit protecting layer are used fully.The conductive glass substrate that such components of photo-electric conversion are used is high transparent, aspect leakage current characteristic and conductivity very superior substrate, and the resistance to chemical reagents aspect is also very superior.
Then, the dye-sensitized solar cells that uses above-mentioned conductive glass substrate is illustrated.On the glass plate that has applied nesa coating; be provided with by passive metal being had catalytic action or substitutional metal or having the electroconductive circuit layer that the material of above-mentioned metal forms; the circuit protecting layer of insulating properties; and passive metal with the pin hole that is formed on described circuit protecting layer; on the conductive glass substrate that the components of photo-electric conversion that so form are used; formation thickness is the oxide semiconductor perforated membrane about 5～50 μ m; and then be provided as telegraph circuit above it to electrode; filling electrolyte between this is to electrode and aforesaid oxides multichip semiconductor pore membrane, aforesaid oxides multichip semiconductor pore membrane are by at titanium oxide; tin oxide; tungsten oxide; zinc oxide; zirconia; support on the metal oxide microparticles such as niobium oxide and to be called as photosensitive dye; has the bipyridine structure; the ruthenium complex of the ligand of three pyridine structures etc.; metal complexes such as porphyrin system or phthalein green grass or young crops; eosin; the base rhodamine; organic dyestuff such as part cyanines and the material that obtains is formed.This electrolyte uses the non-aqueous electrolyte that contains redox couple usually.Yet, replace electrolyte, also can use the hole transmission layer that forms by the p N-type semiconductor N.If use this class hole transmission layer, will there be the leakage problem of electrolyte.Gou Zao dye-sensitized solar cells by no electrolytic metal coating, stops up the pin hole that generates in the circuit protecting layer fully like this, therefore, does not have the problem of leakage current fully, and electrolyte can not take place the corrosion of electroconductive circuit yet.And this solar cell can be with low relatively cost manufacturing, can practical application.Then, the manufacture method to this execution mode is illustrated.Form transparent conductive film layer in glass pane surface; use thereon then have a catalytic action or substitutional metal or have the material of aforesaid metal; form the electroconductive circuit layer by coating process or silk screen print method; and then thereon; for example use the insulating properties paste to form thinly circuit protecting layer is set by coating methods such as silk screen print method or whirl coating, scraper plate finishings; then handle by the electroless plating layer of nickel, cobalt or tin, the pin hole in described circuit protecting layer partly forms passive metal.By this method, formed have high transparent, conductive glass substrate that the components of photo-electric conversion of superior leakage current characteristic and conductivity and superior resistance to chemical reagents are used, and can make the conductive glass substrate that these components of photo-electric conversion are used at an easy rate.Promptly; use gold, silver, platinum, palladium, copper, aluminium or contain conductive paste at least a in these metals; by coating or silk screen print method; form purpose electroconductive circuit 41; further use the insulating properties paste to form thinly thereon circuit protecting layer is set by coating methods such as silk screen coating process or whirl coating, scraper plate finishings; then; preferably carry out the electroless plating layer of nickel, cobalt or tin and handle, thereby can make the conductive glass substrate that the high performance components of photo-electric conversion are used by fairly simple method.The conductive glass substrate that the components of photo-electric conversion of gained are used because the pin hole in described circuit protecting layer has partly stopped up passive metal by no electrolytic metal coating, can make pin hole disappear, thereby can fully interdict electroconductive circuit layer and electrolyte.
Embodiment D1
Provide embodiment D1 for example, its effect is illustrated corresponding to this execution mode.Having formed on the glass plate (manufacturing of Asahi Glass society) of mixing fluoric acid tin (FTO) layer, use the silver-colored paste of slug type printing, by silk screen print method, having formed live width is 100 μ m, aperture opening ratio is 3 kinds of clathrate electroconductive circuits of 90%, 95% and 99%.Then, on foregoing circuit, contain the low-temperature sintering type paste of plumbous borosilicate glass frit with hem width 200 μ m silk screen printings after, 550 ℃ of sintering 1 hour.Repeat this operation 2 times, formed the circuit protecting layer of insulating properties.Then; with the glass substrate that forms this circuit protecting layer 90 ℃ no electrolytic nickel plating bath (the difficult to understand wild drugmaker of TOP Nicoron TOM-S makes), no electrolytic cobalt plating bath (constituting) and do not have in the electrolytic tin plating bath and flooded 5 minutes by cobaltous sulfate, glycine, ammonium citrate and dimethyamine borane; form nickel, cobalt, tin metal respectively, obtain the conductive glass substrate that the components of photo-electric conversion are used.Then, after this conductive glass substrate cleaned, be immersed in the iodine electrolyte 60 minutes, after the drying, the state of described circuit protecting layer observed by SEM (scanning electron microscopy).
Comparative Example D 1
D1 will flood in iodine electrolyte with embodiment D1 equally up to the substrate that has formed the described insulating properties circuit protecting layer stage as a comparative example, has carried out same observation.
As a result, plating processing and not having the conductive glass substrate that the electrolytic tin plating is handled through no electrolytic nickel plating processing, no electrolytic cobalt among the embodiment D1 on described insulating properties circuit protecting layer, do not detect silver, cobalt and the tin metal of needle-like fully.The leakage current of any one all is at 0.1mA/cm 2Or following kilter.Relative therewith, the substrate of Comparative Example D 1 detects the part of separating out of a lot of needle-like silver on described circuit protecting layer.Leakage current is also at 0.5mA/cm 2More than.
So, form passive metal on the substrate that has formed circuit protecting layer, by stopping up pin hole, the conductive glass substrate that the components of photo-electric conversion are used does not almost have leakage current, and has superior conductivity, and has high transparent and resistance to chemical reagents.And its manufacture method is by implementing the fairly simple manufacture method that no electrolytic metal coating is handled, the conductive glass substrate that can provide the cheap components of photo-electric conversion to use.
The conductive glass electrode base board of aforesaid this execution mode; on the glass plate that has applied nesa coating; having to contain has metal catalytic action or substitutional with passive metal or have the electroconductive circuit layer of material of aforementioned metal and the insulator chain protective layer that forms on described electroconductive circuit layer; owing to form passive metal in the pin hole portion that results from described circuit protecting layer, therefore can further alleviate leakage problem.The substrate conducting that makes is superior, and has high transparent and superior resistance to chemical reagents.
When having formed passive metal by no electrolytic metal coating processing, the pin hole that generates in the insulating properties circuit protecting layer is stopped up fully.And, that manufacturing that can be fairly simple and cheap has superior conductivity and high transparent, and the conductive glass substrate with superior resistance to chemical reagents.
The dye-sensitized solar cells of the conductive glass substrate that the use components of photo-electric conversion are used; stopped up fully by the pin hole of no electrolytic metal coating processing in the circuit protecting layer generation of insulating properties; therefore, can make the dye-sensitized solar cells that does not almost have leakage problem less expensively.The manufacture method of the conductive glass substrate of this execution mode is; form nesa coating at glass baseplate surface; use thereon then have a catalytic action or substitutional metal or have the material of aforesaid metal; form the electroconductive circuit layer by coating process or silk screen print method; and then use the paste of insulating properties to form circuit protecting layer thereon; then, handle the formation passive metal by the electroless plating layer of nickel, cobalt or tin.By this method, can make does not have leakage problem less expensively, and the conductive glass substrate used of the conductivity superior components of photo-electric conversion.
According to using as passive metal is had the metal of catalyst action or the gold of displaced type metal; silver; platinum; palladium; copper; aluminum metal or contain the manufacture method that conductive paste at least a in these metals is made the conductive glass substrate that the components of photo-electric conversion of described electroconductive circuit use; and further according to handling with no electrolytic nickel plating; no electrolytic cobalt plating is handled; or do not have the manufacture method that the conductive glass substrate of using as the components of photo-electric conversion of described no electrolytic metal coating processing is handled in the electrolytic tin plating, handle making that the pin hole part that results from the described circuit protecting layer is fully stopped up by aforementioned electroless plating layer.Therefore, can make does not almost have leakage problem less expensively, and the superior and transparent height of conductivity also has the conductive glass substrate that the components of photo-electric conversion of superior resistance to chemical reagents are used, and this method is practical manufacture method.
Below, other execution modes of the present invention are illustrated.Figure 14 is the profile of an execution mode of expression electrode base board 51 of the present invention.
As shown in figure 14, the electrode base board 51 of this execution mode is at metal wiring layer 512 that has transparency conducting layer 511 on the base material 510, forms on this transparency conducting layer 511 and the insulating barrier 514 that covers these metal wiring layer 512 surfaces.That is, by this insulating barrier 514, metal wiring layer 512 is insulated coating.
The material of base material 510 is identical with the material of base material 10.
Transparency conducting layer 511 is, on base material 510, forms in the zone wider than the formation zone of metal wiring layer 512, and its material has no particular limits, and considers photopermeability and conductivity etc., can select to be fit to the combination of material or the material of purposes.As object lesson, can enumerate as tin-doped indium oxide (ITO), tin oxide (SnO 2), fluorine doped tin oxide conductive metal oxides such as (FTO).
As the method that forms transparency conducting layer 511, can use well-known suitable method corresponding to the material of transparency conducting layer 511, for example, can enumerate as sputtering method, vapour deposition method, SPD method, CVD method etc.Consider photopermeability and conductivity, form thickness usually and be the film about 0.001～10 μ m.
Metal wiring layer 512 forms metals such as gold, silver, platinum, aluminium, nickel, titanium as wiring.The wiring pattern of metal wiring layer 512 has no particular limits, can form as shown in figure 15 clathrate, other can be patterns such as striated, oblong-shaped, pectination.
In order significantly not damage the photopermeability of electrode base board 51, though there is no particular limitation, for example, preferably each wiring width is careful at 1000 μ m or still less and make it very thin.The thickness (highly) of each wiring of metal wiring layer 512 has no particular limits, but preferred 0.1～10 μ m.
Formation method as metal wiring layer 512, can list, will be as bonds such as the metal powder of conducting particles and the glass granules formation paste that matches, with this paste with the mode that forms required pattern by print processes such as silk screen print method, metal mask method, ink-jet methods film, by heating, burn till the molten sticking method of conducting particles that makes.As firing temperature, for example, be under the situation of glass at base material 510, preferred temperature is 600 ℃ or lower, more preferred 550 ℃ or lower.In addition, also can use formation methods such as sputtering method, vapour deposition method, coating process.
The surperficial preferred smooth surface of metal wiring layer 512, but more preferentially have high conductivity with respect to this has a bit to rise and fall or concavo-convexly also do not hinder.
The resistivity of metal wiring layer 512 is preferably at least 9 * 10 -5Ω cm or still less under, more preferred 5 * 10 -5Ω cm or still less.
Insulating barrier 514 is that by containing the insulating material of heat-stable ceramic, overlapping one or more layers carries out film forming on the formation zone of metal wiring layer 512, thereby the metal wiring layer insulation is coated.
As heat-stable ceramic, for example can use to be selected from a kind of in aluminium oxide, zirconia, the silica, or also can be with multiple compound use.The thermal endurance of heat-stable ceramic preferably can be born the thermal history history when making electrode base board.
More detailed, preferably use to contain to form gathering materials of heat-stable ceramic with containing at least a or multiple bond in silicate, phosphate, cabosil, alkyl silicate, the metal alkoxide.
Such insulating barrier 514 can obtain with containing the adhesive composition (diaphragm material) of bond, curing agent etc. by constituting gathering materials of principal component.Described adhesive composition is, reaction by hydrolysis, condensation reaction, polymerization reaction etc. can obtain heat-stable ceramics such as aluminium oxide, zirconia, silica or be the material of the sclerosis epithelium (reactive inorganic coating layer) of the insulating properties of principal component with inorganic polymers such as polysiloxanes, polysilanes, for example, can use the reactive inorganic bonding agent of market sale.
The film build method of diaphragm material is considered engineering aspect and cost aspect, preferred print process.But, be not limited to print process, also can use sputtering method, infusion process, scraper plate finishing etc.
Above-mentioned insulating barrier 514 does not preferably have layers defective, fine and close such as significant pin hole.Insulating barrier 514 can be an individual layer, also can be multilayer.
Insulating barrier 514 is under the situation about being made of multilayer, also is used in combination multiple above-mentioned insulating material.And, have one deck in the insulating barrier of multilayer or more multi-layered, can be by for example PbO or PbO-B 2O 3Lead be low-melting glass, or be that low-melting glass etc. constitutes by non-lead.But insulating barrier contains under the situation of multilayer, at least one deck must be by above-mentioned heat-stable ceramic be principal component form the layer.
Above-mentioned insulating barrier 514 is compared with the insulating barrier that only uses low-melting glass to form, and is more superior at aspects such as acid resistances.
The electrode base board of this execution mode, insulating barrier 514 are principal component with the heat-stable ceramic, therefore have superior thermal endurance and acid resistance etc.Therefore, can the thermal history when making not produce deterioration.Thereby metal wiring layer 512 is positively covered to avoid electrolyte etc., and the burn into that can suppress metal wiring layer 512 effectively reacts with the metal that constitutes metal wiring layer 512 and the problems such as electrolytical rotten, leakage current that cause.
So, dielectric film can be brought into play its performance unchangeably, and superior performance can obtain the maintenance of longer time.
Below, the Change Example of electrode base board of the present invention is described.In the electrode base board of following Change Example, marked the symbol identical with Figure 14, the electrode base board of expression and the 1st kind of execution mode shown in Figure 14 is identical or have a same structure, the omission that has repeat specification.
Figure 16 is other the summary section of execution mode of expression electrode base board.
This routine electrode base board 51 is provided with metal wiring layer 512 on base material 510, transparency conducting layer 511 is crossed on the metal wiring layer 512, is formed at the wider zone, zone that forms than described metal wiring layer 512.Insulating barrier 514, on transparency conducting layer 511, the mode that covers the top and side of metal wiring layer 512 with the pattern that is overlapped in metal wiring layer 512 forms.That is, insulating barrier 514 is to be intermediary with transparency conducting layer 511, is provided with on metal wiring layer 512.
Such electrode base board 51, the same with the electrode base board 51 of first kind of execution mode shown in Figure 14, can be insulated by 514 pairs of metal wiring layers 512 of insulating barrier and be covered, thereby be suppressed the generation of leakage current, become electrode base board 51 with advantageous characteristic.
Described electrode base board, metal wiring layer 512 are to be formed directly on the base material 510, or are that intermediary forms on the height that is higher than base material 510 surfaces with the transparency conducting layer, and still, electrode base board of the present invention not merely is defined in this.
As Figure 16～shown in Figure 19, its structure is that to be located in the recess 510a that forms on the base material 510 also be possible at least a portion of metal wiring layer 512.
Substrate surface 510b is the face that forms the side of transparency conducting layer 511 and metal wiring layer 512.When electrode base board 51 was used for dye-sensitized solar cells, oxide semiconductor perforated membrane and to electrode etc. was configured in substrate surface 510b one side.
Recess 510a as the concave shaped portion of ditch or hollow etc., forms along wiring pattern.The formation of concave shaped portion can be processed by the processing method corresponding to the material of base material 510, for example, and can be by processing such as laser or corrosion.It can be lenticular, semicircle shape, U word shape, V-arrangement trough shape, square etc. that the section shape of recess 510a has no particular limits.The material of metal wiring layer 512 and formation method can be identical with above-mentioned material and formation method.
In this embodiment, the structure of metal wiring layer 512 has no particular limits, as long as its at least a portion is positioned at the recess 510a (reaching substrate surface 510b or the height below it) that forms through recessed processing on the substrate surface 510b of base material 510.For example, as shown in figure 17, the surface of metal wiring layer 512 has identical height with substrate surface 510b; As Figure 18 and shown in Figure 19, the surface of metal wiring layer 512 has reached the height higher than substrate surface 510b; Metal wiring layer 512 integral body are positioned at substrate surface 510b with inferior as shown in figure 20.
Metal wiring layer 512 concerns that with the position of transparency conducting layer 511 there is no particular limitation, for example can enumerate, as shown in figure 17, the structure that transparency conducting layer 511 forms on metal wiring layer 512 and substrate surface 510b; As shown in figure 18, transparency conducting layer 511 forms on substrate surface 510b, and the structure that is connected with metal wiring layer 512; As Figure 19 and shown in Figure 20, transparency conducting layer 511 forms on recess 510a and substrate surface 510b, the structure that metal wiring layer 512 forms on transparency conducting layer 511 etc.
Metal wiring layer 512 can contact with the inner face of recess 510a, also can get involved transparency conducting layer 511 and wait other layer between the inner face and metal wiring layer 512 of recess 510a.
Insulating barrier 514 overlaps to form at least on metal wiring layer 512 formation zones.Also can directly be formed at metal wiring layer 512 on, also can be between insulating barrier 514 and metal wiring layer 512, get involved transparency conducting layer 511 and wait other layer.
In any one mode, metal wiring layer 512 is preferably significantly not concavo-convex as far as possible, as the to become shade smooth state that pierces part or space etc.For the difference in height between the substrate surface 510b of the surface of metal wiring layer 512 and base material 510, the preferred heights difference is little.
As mentioned above, if at least a portion of metal wiring layer 512 arrives substrate surface 510b or its following height, can be under the situation of the surface of enlarged metal wiring layer 512 not and the difference in height between substrate surface 510b, the thickness of raising metal wiring layer 512.Therefore, the aperture opening ratio (not forming the ratio of the part of metal wiring layer 512) of base material 510 can be enlarged, and reduce the resistance of circuit.
Electrode base board 51 shown in Figure 21 has formed transparency conducting layer 511 on base material 510, formed metal wiring layer 512 by required pattern on transparency conducting layer 511.On transparency conducting layer 511, be provided with the shielding layer 513 that constitutes by oxide semiconductor thin-film, and on metal wiring layer 512, be provided with insulating barrier 514.
Electrode base board 51 shown in Figure 22, on base material 510, by the requirement pattern formed metal wiring layer 512, on this metal wiring layer 512,, formed transparency conducting layer 511 than wideer zone, metal wiring layer 512 formed zones.On transparency conducting layer 511, be provided with the shielding layer 513 that constitutes by oxide semiconductor thin-film.Then, insulating barrier 514 is with on shielding layer 513, is formed with the mode of the top and side of the pattern overlapping of metal wiring layer 512 and clad metal wiring layer 512.
Electrode base board 51 shown in Figure 23 has formed transparency conducting layer 511 on base material 510, on transparency conducting layer 511, formed metal wiring layer 512 by required pattern.On this metal wiring layer 512, formed insulating barrier 514.Shielding layer 513 not only is formed on the transparency conducting layer 511, also is formed on metal wiring layer 512 or the insulating barrier 514.
Though to compare problem smaller with metal wiring layer 512, also finding has the reverse electron transfer phenomenon that is taken place by transparency conducting layer 511.By shielding layer 513 being set, can obtain higher screening effect in the mode that covers on the transparency conducting layer 511.
As the material of shielding layer 513, select with the electron transfer speed of electrolyte that contains the redox kind low, and the compound that photopermeability, photoelectron-transfer can be high, for example: titanium oxide (TiO 2), zinc oxide (ZnO), niobium oxide (Nb 2O 5), tin oxide (SnO 2), fluorine doped tin oxide (FTO), tin-doped indium oxide (ITO) etc.
The shielding layer 513 that forms must be thinner, thereby do not hinder the electron transfer to transparency conducting layer 511, and preferred thickness is about 10～3000nm.As the formation method of shielding layer 513, can enumerate as sputtering method, vapour deposition method, spray heating decomposition (SPD method), whirl coating, infusion process, scraper plate finishing etc.But, use these methods, the density of shielding layer 513, and can't say the surface configuration adaptability of base material 510 very abundant, so be difficult to fully metal wiring layer 512 be covered.Therefore, under the situation that has formed shielding layer 513, being necessary on metal wiring layer 512, is intermediary directly or with transparency conducting layer 511 or shielding layer 513 etc., forms insulating barrier 514.Thus, reach enough insulation of metal wiring layer 512 are covered.
Formation method as shielding layer 513 has no particular limits, can list as, with purpose compound oxides semiconductor or its precursor by dry process (vapor phase method) such as sputtering method, vapour deposition method, CVD method the method for film forming.For example, in precursor film forming such as metals, can make its oxidation obtain shielding layer 513 by heat treated or chemical treatment etc.
Under the situation of damp process, after the liquid that contains purpose compound or its precursor can being applied by methods such as whirl coating, infusion process, scraper plate finishings, is the purpose compound by heat treated or chemical treatment etc. with its chemical change, obtains shielding layer 513 therefrom.As precursor, salt, complex of the formation metallic element that contains the purpose compound etc. are for example arranged.In order to obtain fine and close film, than comparing preferred solution with dispersion liquid.
As the additive method that forms shielding layer 513, for example, also can use and pass through spray heating decomposition, under base material 510 heated state that will have transparency conducting layer 511, spray with the material of the precursor of formation shielding layer 513 to this base material 510, make its thermal decomposition, and be changed to the purpose oxide semiconductor, thus the method for formation shielding layer 513.
According to above-mentioned way, by the shielding layer 513 in order to cover transparency conducting layer 511 is set, reverse electron transfer can be suppressed, therefore, the high components of photo-electric conversion of light-to-current inversion efficient can be prepared by the electrode base board that uses this execution mode from transparency conducting layer 511.
Shielding layer 513 according to the characteristic needs, can make it have the effect that purpose for example is different from the protective layer of insulating barrier 514.
For example, electrode base board 51 as shown in figure 23 also can use the protective layer of shielding layer 513 as metal wiring layer 512 or insulating barrier 514.
Following table illustrates the other execution mode of electrode base board of the present invention.Electrode base board 51 shown in Figure 24 on the 1st transparency conducting layer 511a, has formed metal wiring layer 512 with the cloth wire pattern of clathrate, striated, pectination etc., on metal wiring layer 512, is provided with the insulating barrier 514 that is used to cover metal wiring layer 512.In addition, cross on metal wiring layer 512 or the insulating barrier 514, formed the 2nd layer of transparency conducting layer 511b.That is, metal wiring layer 512 or insulating barrier 514 are clipped between the 1st transparency conducting layer 511a and the 2nd transparency conducting layer 511b.The the 1st and the 2nd transparency conducting layer 511a, 511b are identical with above-mentioned transparency conducting layer 511, are the films that contains conductive metal oxides such as ITO, FTO.
By such electrode base board 51, can be insulated when covering by 514 pairs of metal wiring layers 512 of insulating barrier, can be by the 2nd transparency conducting layer 511b, protection metal wiring layer 512 or insulating barrier 514.By having the 1st transparency conducting layer 511a and the 2nd transparency conducting layer 511b simultaneously, can improve current collecting efficiency.
Then, the components of photo-electric conversion to present embodiment are illustrated.
Figure 25 is the example that expression constitutes the components of photo-electric conversion of dye-sensitized solar cells.These components of photo-electric conversion 56, on electrode base board 51, be provided with work electrode 53 and with this work electrode 53 be oppositely arranged to electrode 54, the oxide semiconductor perforated membrane 52 that this work electrode 53 has oxide semiconductor particulates such as containing titanium oxide and supported sensitizing dyestuff.At work electrode 52 and between, be provided with the charge transport layer 55 of the electrolyte that contains electrolyte etc. or p N-type semiconductor N etc. to electrode 54.In these routine components of photo-electric conversion 56, on the surface of electrode base board 51, form the oxide semiconductor perforated membrane 52 that supports sensitizing dyestuff, constituted the work electrode 53 of the components of photo-electric conversion 56 by electrode base board 51 and oxide semiconductor perforated membrane 52.
Electrode base board 51 shown in Figure 25 is electrode base boards 51 of structure shown in Figure 14, but not merely is defined in this, also can use the electrode base board of any one execution mode.
Oxide semiconductor perforated membrane 52 is to contain titanium oxide (TiO 2), tin oxide (SnO 2), tungsten oxide (WO 3), zinc oxide (ZnO), niobium oxide (Nb 2O 5) the film of porous matter of a kind of or compound multiple oxide semiconductor particulate in waiting.In the preferred 1～1000nm scope of the average grain diameter of oxide semiconductor particulate.The thickness of oxide semiconductor perforated membrane 52, about preferred 0.5～50 μ m.
Form the method for oxide semiconductor perforated membrane 52, have no particular limits, for example can list, dispersion liquid that the oxide semiconductor microparticulate of market sale is formed in desired dispersant or the colloidal solution that can adjust by sol-gel process etc., added after the desired additives method that applies by well-known coating methods such as silk screen print method, ink jet printing method, roller coating process, scraper plate finishing, whirl coating, spraying processes as required.In addition, can also use electrode base board 51 is immersed in the colloidal solution, by electrophoresis with the oxide semiconductor particulate attached to the electrophoretic deposition on the electrode base board 51; In colloidal solution or dispersion liquid, add blowing agent, apply after the mixing, carry out the method for porous by sintering; After mixing coating with polymer microballoon etc., remove the interstitial porous method of this polymer microballoon by heat treated or chemical treatment.
The sensitizing dyestuff that supports in oxide semiconductor perforated membrane 2 has no particular limits.Can be from organic dyestuff such as the containing metal complex of the ruthenium complex that for example has the ligand that contains bipyridine structure, three pyridine structures etc., iron complex compound, porphyrin system or the blue or green system of phthalein, eosin, base rhodamine, part cyanines etc., suitably select and used and have the material that excites behavior that is suitable for purposes and oxide semiconductor.
Constituting by electrolyte under the situation of charge transport layer 55, for example can use the electrolyte that contains redox couple.Also can use gel-like electrolyte, it is the gel-like electrolyte that described electrolyte is formed the class solid by suitable gelating agent.Solvent as electrolyte, can select to use as, the organic solvent of acetonitrile, methoxyacetonitrile, propionitrile, propene carbonate, diethyl carbonate, gamma-butyrolacton etc. contains season imidazoles cation and the room temperature fuse salt of iodide ion or two fluoroform sulphonyl imido anion etc. etc.
Redox couple as being contained in the electrolyte has no particular limits, can by add to use iodine/iodide ion, bromine/bromide ion etc. to obtaining.As the source that iodide ion or bromide ion are provided, can independent or compound use lithium salts, season imidazole salts, 4-butyl ammonium etc.In electrolyte, also can add the additive of tert .-butylpyridine etc. as required.
Charge transport layer 55 replaces electrolyte also can use the p N-type semiconductor N.As the p N-type semiconductor N, for example, can suitably use monovalence copper compounds such as cupric iodide, copper rhodanide.The method that is formed charge transport layer 55 by the p N-type semiconductor N has no particular limits, and can enumerate for example casting method, sputtering method, vapour deposition method etc.For this p N-type semiconductor N,, can contain proper additive according to the needs on the film forming.
As to electrode 54, for example, can use that the semi-conductive electrode of electroconductive oxide that forms metal material, ITO or the FTO etc. that contain various carbon-based materials or gold, platinum etc. on the substrate that contains non-conductive material such as glass forms to electrode.
Electrode for example, is under the situation of platinum film, for example can obtain through methods such as heat treatments by the coating chloroplatinic acid.Also can adopt methods such as vapour deposition method or sputtering method to form electrode.
Charge transport layer 55 uses under the situation of solid p N-type semiconductor N, also can use on charge transport layer 55 by method cambium layer such as direct, sputter, coatings.
The components of photo-electric conversion 56 of present embodiment, because the insulating barrier 514 of electrode base board 51 is a principal component with the heat-stable ceramic, therefore, thermal endurance and acid resistance etc. are superior, thermal history that can be owing to not making and by deterioration.Therefore, metal wiring layer 512 is positively covered electrolyte to avoid charge transport layer 55 etc., has suppressed the corrosion and the leakage current of metal wiring layer 512 effectively.Prevented contacting of metal wiring layer 512 and dielectric substrate 55, the output that has suppressed to be caused by the burn into leakage current reduces, thereby can increase substantially the characteristic of battery unit.
Embodiment E 1
The preparation of electrode base board
According to following step, prepared electrode base board 51 as shown in figure 15.
As transparency conducting layer 511 and base material 510, used the glass substrate of the subsidiary FTO film of 100mm * 100mm.On the surface of glass substrate, (specific insulation behind the sintering is 3 * 10 with silver-colored paste to printing -6Ω) silk screen printing.After 10 minutes leveling, 135 ℃ were descended dry 20 minutes in hot-air drying stove, burnt till 15 minutes at 550 ℃, had just formed the metal wiring layer 512 of argentiferous circuit.The circuit width of metal wiring layer 512 is 500 μ m, and thickness is 5 μ m, has formed from current-collecting terminals and has extended into rectangular shape.Pass through CCD camera adjusting position on one side, on one side overlapping with metal wiring layer 512, by silk screen printing, 5 kinds of diaphragm materials shown in the table 1 are printed respectively, thereby form insulating barrier 514.The formation width of insulating barrier 514 is, at the every one-sided 100 μ m that remain out in the Width both sides of metal wiring layer 512, the height that begins with the surface from glass substrate is that 10 μ m are benchmark, thereby the insulating barrier 514 of gained is approximately 5 μ m from the thickness of metal wiring layer 512 beginnings.
Among the embodiment E 1-2 in the table 1, described [aluminium oxide+metal alkoxide/low-melting glass paste] expression will be that the 1st insulating barrier of principal component carries out lamination with the 2nd insulating barrier that is principal component with [low-melting glass paste] with [aluminium oxide+metal alkoxide].The 2nd insulating barrier is to use PbO-B 2O 3The low-melting glass paste of the market sale of system by silk screen printing, forms at the 1st insulating barrier superimposed layer.In this case, the thickness of the 1st insulating barrier is about 5 μ m, and the thickness of the 2nd insulating barrier is about 5 μ m.
The preparation of the components of photo-electric conversion
On the electrode base board 51 of gained, the coating average grain diameter is the dispersion liquid of the titanium oxide of 20～25nm, and dry after heating in 450 ℃, 1 hour, sintering have formed oxide semiconductor perforated membrane 52.Then, it is flooded in the ethanolic solution of ruthenium bipyridine complex (N3 dyestuff) carry out dyestuff a night and support, prepared work electrode 53.
As to electrode 54, use the FTO glass electrode substrate of platinum sputter, this to electrode 54 and work electrode 53, is oppositely arranged under the state that with the thick thermoplastic resin board of 50 μ m is the dividing plate intervention, by the heat fusing of resin plate, fixed two electrodes 53 and 54.At this moment, owing to, will vacate to the part of electrode 54 sides as electrolytical inlet.Injecting with 0.5M iodide salt and 0.05M iodine by this inlet is after the methoxyacetonitrile solution of principal component has formed charge transport layer 55, is that potting resin encapsulates with periphery and inlet with thermoplastic resin plate or epoxy, form current-collecting terminals portion by glass solder, thereby made the components of photo-electric conversion that become the Experimental cell unit.
The light-to-signal transfer characteristic of this Experimental cell unit is by air mass (AM) 1.5,100mW/cm 2Simulated solar irradiation detect, obtain the result of the light-to-current inversion efficient shown in the table 1.
Table 1
The principal component of diaphragm material Light-to-current inversion efficient (%)
Embodiment E 1-1 Aluminium oxide+metal alkoxide 3.9
Embodiment E 1-2 Aluminium oxide+metal alkoxide/low-melting glass paste 3.7
Embodiment E 1-3 Zirconia 3.5
Embodiment E 1-4 Silica 3.3
Embodiment E 1-5 Aluminium oxide+alkyl silicate+metal alkoxide 3.5
Embodiment E 2
The preparation of electrode base board
According to following step, prepared electrode base board 51 as shown in figure 16.
As base material 510, use the glass substrate of 100mm * 100mm, on its surface, formed golden circuit (metal wiring layer 512) by coating process.Circuitry shapes is identical with embodiment E 1, and circuit thickness is 2 μ m.On glass substrate and golden circuit, by spray heating decomposition, having formed thickness is the FTO/ITO composite membrane of 1000nm.Then, use the test portion in the table 1, same with embodiment E 1, formed insulating barrier 514 pattern of complexed metal wiring layer 512.
The preparation of the components of photo-electric conversion
Use the electrode base board 51 of gained, the step according to identical with embodiment E 1 has made the components of photo-electric conversion that become the Experimental cell unit, estimates the light-to-signal transfer characteristic result and shows that its light-to-current inversion efficient is 3.0%.
Embodiment E 3
According to following step, prepared the electrode base board 51 that shows as Figure 19.
As base material 510, use the glass substrate of 100mm * 100mm, on its surface, along the ditch 10a of rectangular wiring pattern corrosion formation dark 10 μ m, wide 500 μ m.Thereon, by spray heating decomposition, having formed thickness is the FTO/ITO composite membrane of 1000nm.Then, the method according to identical with embodiment E 1 has formed silver-colored printed wiring layer.By multiple printing, formed until the silver wiring that exceeds substrate surface 510b 2 μ m, the width of metal wiring layer 512 is also wideer than the width of ditch 510a, promptly every one-sided wide respectively 200 μ m that go out.Then,, use the test portion 1 of table 1 to cover the mode on the metal wiring layer 512, with embodiment E 1 similarly complexed metal wiring layer 512 pattern formed insulating barrier 514.
The preparation of the components of photo-electric conversion
Use the electrode base board 51 of gained, the step according to identical with embodiment E 1 has made the components of photo-electric conversion that become the Experimental cell unit, estimates the light-to-signal transfer characteristic result and shows that its light-to-current inversion efficient is 4.2%.
Comparative Example E 1
The preparation of electrode base board
Heat resistant glass substrate (base material) surface at 100mm * 100mm, according to the step same with embodiment E 1, after using printing to form metal wiring layer 512 with silver-colored paste, then on this metal wiring layer 512, according to the step same with embodiment E 2, the thickness that formation has transparency conducting layer and shielding layer concurrently is the FTO/ITO composite membrane of 1000nm, has prepared electrode base board 51.
The preparation of the components of photo-electric conversion
Use the electrode base board 51 of gained, the step according to identical with embodiment E 1 has made the components of photo-electric conversion that become the Experimental cell unit.Observe the electrolyte that injects this Experimental cell unit and find, when this liquid just has been injected into, be dark brown,, become almost transparent through after a few minutes.This can think because covering of silver-colored circuit is not very abundant, the I in the electrolyte 3 -Ion is given birth to reaction with the silver hair that exposes and is reduced to I -Cause.The light-to-signal transfer characteristic of this Experimental cell unit is that the result that 1.5 simulated solar irradiation detects shows that its light-to-current inversion efficient is 0.2% by air mass (AM).
Can learn that thus under the situation that insulating barrier is not set, covering of silver-colored circuit is abundant inadequately, can not well give play to the characteristic of the substrate that has metal line.
Comparative Example E 2
The preparation of electrode base board
At the glass baseplate surface of the subsidiary FTO film of 100mm * 100mm, same by coating process with embodiment E 2, formed golden circuit (metal wiring layer).On this metal wiring layer, according to the step same with embodiment E 2, forming the thickness that has transparency conducting layer and shielding layer concurrently is the FTO film of 300nm, has prepared electrode base board 51.
Observed the surface of the electrode base board 51 that so forms by SEM, EDX and find, the part that pierces that the hauling-out bottom that is considered to by anti-coating causes is arranged in the bottom of metal wiring layer 512, this pierces the coating that dash area does not partly form FTO.
The preparation of the components of photo-electric conversion
Use this electrode base board 51, according to the step identical with embodiment E 1, having made the components of photo-electric conversion that become the Experimental cell unit, is that the result that 1.5 simulated solar irradiation detects the light-to-signal transfer characteristic of the components of photo-electric conversion shows that its conversion efficiency is 0.41% by AM.In this case, covering of metal wiring layer 512 is abundant inadequately, can not well give play to the characteristic of the substrate that has metal line.
Comparative Example E 3
The preparation of electrode base board
Glass baseplate surface at the subsidiary FTO film of 100mm * 100mm, metal wiring layer is not set, as electrode base board 51 uses, the step according to identical with embodiment E 1 has made the components of photo-electric conversion that become the Experimental cell unit with the glass substrate of subsidiary FTO film itself.The light-to-signal transfer characteristic of this Experimental cell unit is that the result that 1.5 simulated solar irradiation detects shows that its conversion efficiency is 0.23% by AM.Can learn that thus under the situation that metal wiring layer is not set, the resistance of electrode base board 51 is very big, therefore, cause the reduction of the light-to-current inversion efficient of the components of photo-electric conversion.
Industrial applicibility
Electrode base board of the present invention, the transparency conducting layer that has metal wiring layer and be electrically connected with this metal wiring layer at base material, and metal wiring layer is insulated a layer insulating wrapped. So metal wiring layer is positively covered to avoid electrolyte solution etc., can effectively suppress its corrosion or leakage current. Compare when only transparency conducting layer being used as the electric conductor of electrode, electric conductivity is more superior.

Claims (5)

1. electrode base board, it has transparency carrier, the metal wiring layer that is provided with and transparency conducting layer on described transparency carrier; Described metal wiring layer forms along the ditch of the formation wiring pattern that forms on described transparency carrier, at least a portion of described metal wiring layer is housed in the described ditch, and the upper end of described metal wiring layer bloats from described transparency conducting layer.
2. according to the electrode base board described in the claim 1, wherein, the surperficial crested layer of described at least metal wiring layer coats.
3. according to the electrode base board described in the claim 2, wherein, described shielding layer contains and is selected from least a in glass ingredient, metal oxide composition and the electrochemistry inert plastic composition.
4. the components of photo-electric conversion, it possesses: the electrode base board described in the claim 1, relative with the described transparency conducting layer side of described electrode base board and be provided with to electrode and at described dielectric substrate or the charge transport layer that is provided with between to electrode and described electrode base board.
5. according to the electrode base board described in the claim 1, wherein, described metal wiring layer covers the edge of adjacent described transparency conducting layer.
CN 200810126942 2002-10-03 2003-10-03 Electrode substrate and photoelectric conversion element Expired - Fee Related CN101312096B (en)

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