CN101667493B - Oxide semiconductor electrode, dye-sensitized solar cell, and, method of producing the same - Google Patents

Oxide semiconductor electrode, dye-sensitized solar cell, and, method of producing the same Download PDF

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Publication number
CN101667493B
CN101667493B CN2009101673493A CN200910167349A CN101667493B CN 101667493 B CN101667493 B CN 101667493B CN 2009101673493 A CN2009101673493 A CN 2009101673493A CN 200910167349 A CN200910167349 A CN 200910167349A CN 101667493 B CN101667493 B CN 101667493B
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oxide semiconductor
electrode
layer
dye
base material
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CN101667493A (en
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薮内庸介
中川博喜
小堀裕之
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority claimed from JP2005285323A external-priority patent/JP4915076B2/en
Priority claimed from JP2005285339A external-priority patent/JP5114837B2/en
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

An oxide semiconductor electrode is provided with a base material; a bonding layer formed on the base material made of a thermoplastic resin; a first electrode layer formed on the bonding layer made of a metal oxide; and a porous layer formed on the first electrode and made of the fine particle of a metal oxide semiconductor, wherein the thermoplastic resin includes a silane-modified resin. The present invention further provides a method of producing an oxide semiconductor electrode. The method is characterized by comprising a step of forming a laminate for oxide semiconductor electrode, a step of forming an oxide semiconductor electrode having a heat-resistive substrate by carrying out the substrate forming step on the first electrode layer on the laminate for oxide semiconductor electrode, a step of peeling off the heat-resistive substrate on the oxide semiconductor electrode having heat-resistive substrate, wherein the step comprises: a step of forming pattern for sandwich layer, a step of forming a layer for oxide semiconductor layer, a step of forming a sandwic.

Description

Oxide semiconductor electrode, dye-sensitized solar cell and their manufacturing approach
The application divides an application, the application number of its female case application: 200610068365.3, and the applying date: 2006.3.30, denomination of invention: oxide semiconductor electrode, dye-sensitized solar cell and their manufacturing approach
Technical field
The present invention relates to oxide semiconductor electrode and used its dye-sensitized solar cell and their manufacturing approach.
Background technology
In recent years, the environmental problems such as global warming that caused by the increase of carbon dioxide become seriously, and the whole world is all in its countermeasure of research.Wherein, the energy of, cleaning little as the burden to environment is among the relevant research and development that utilized the solar cell of solar energy are being carried out energetically.As this kind solar cell, though monocrystaline silicon solar cell, polysilicon solar cell, amorphous si solar cells and compound semiconductor solar cell etc. by practicability, these solar cells have problems such as manufacturing cost height.So little and can cut down the solar cell of manufacturing cost as environmental pressure, dye-sensitized solar cell receives publicity, its research and development are in progress.
In this kind dye-sensitized solar cell, used oxide semiconductor electrode with the porous layer that comprises the metal-oxide semiconductor (MOS) particulate.
The general formation of dye-sensitized solar cell is shown among Fig. 1.As shown in Figure 1; General dye-sensitized solar cell 11 has following formation; Promptly; With the 1st electrode layer 2 and the porous layer 3 that contains the metal-oxide semiconductor (MOS) particulate that has supported dye-sensitized dose with the porous layer 3 of this sequential cascade at the oxide semiconductor electrode on the base material 1 13 on, dielectric substrate the 4, the 2nd electrode layer 5, opposed base material 6 with redox couple is by with this sequential cascade, the sensitizing coloring matter that is adsorbed in the oxide semiconductor microparticle surfaces is excited because of receiving sunlight from base material 1 side; The electronics that has been excited conducts to the 1st electrode layer, passes external circuit and is conducted to the 2nd electrode layer.By redox couple electronics get back to the substrate energy level of sensitizing coloring matter and generate electricity thereafter.As this kind dye-sensitized solar cell; Representational have by poriferous titanium dioxide constitute said porous layer; Increase the Grazel cell of dye-sensitized dose content, become the object of broad research as the high dye-sensitized solar cell of generating efficiency.
When the porous layer that forms as the porous of the characteristic of said Grazel cell, generally need form and carry out 300 ℃～700 ℃ the processing of burning till with composition to porous layer.So, as said base material, can tolerate the stable on heating material of burning till processing if not having, then can't use, thereby the problem that can't use general macromolecule membrane is arranged.
Open in the 2002-184475 communique the spy; Announcement has the manufacturing approach of the semi-conducting electrode with following characteristic; That is, on heat resistant substrate, form oxide semiconductor and/or contain the layer of its presoma, will to its heating burn till and oxide semiconductor film be transferred to and be transferred on the base material.According to this kind transfer printing mode,, just can form porous layer through being transferred transfer printing on the base material to arbitrarily at the oxide semiconductor film that has burnt till on the heat resistant substrate.So regardless of the material that is transferred base material how this kind transfer printing mode can be, and according to the selections such as purposes of oxide semiconductor electrode suitable to be transferred the base material aspect very useful.
In said transfer printing mode, though be transferred to be transferred and form porous layer on the base material through being formed at oxide semiconductor film on the heat resistant substrate, when implementing this kind transfer printing, need form adhesive linkage on the base material being transferred.So, for example in the time will being used for dye-sensitized solar cell, in the general formation of dye-sensitized solar cell shown in Figure 1, will append adhesive linkage with the oxide semiconductor electrode that the transfer printing mode has formed porous layer.Represented to have used the formation of the dye-sensitized solar cell of the oxide semiconductor electrode that utilizes the transfer printing mode to form porous layer among Fig. 2.As shown in Figure 2, when having used the oxide semiconductor electrode that utilizes the transfer printing mode to form porous layer, in dye-sensitized solar cell 12, between base material 1 and the 1st electrode layer 2, will form adhesive linkage Z.In the past, as employed binding agent in this kind adhesive linkage, though not special the qualification, general various synthetic resin or the inorganic binder of many uses.
Here, when using said transfer printing mode to make the oxide semiconductor electrode of exhibiting excellent stability with time, said adhesive linkage need have good bonding force, and is kept stable for a long time.But, in the employed in the past binding agent, have bonding force not enough, along with the problem that produces splitting time lapse.In addition, for example when oxide semiconductor electrode was used for said dye-sensitized solar cell, because porous layer is a porous character, therefore confirming had solvent and redox couple in the dielectric substrate can see through porous layer, sees through the phenomenon of electrode layer then again.Thus, in the dye-sensitized solar cell with adhesive linkage as shown in Figure 2, the effect because of redox couple in the said dielectric substrate and solvent etc. reduces with regard to the bonding force that has adhesive linkage, produces the problem of splitting.Because this kind problem is difficult to use the transfer printing mode to make the dye-sensitized solar cell of exhibiting excellent stability with time.In addition; Though said transfer printing mode has advantage aspect the material that need not consider to be transferred base material; But with porous layer on being transferred base material during transfer printing, still leave the problem of the essence that the porous layer breakage falls, thereby problem not good on practicality arranged.
In addition; In general; Because dye-sensitized solar cell and silicon solar cell etc. are compared, energy conversion efficiency is lower, therefore needs the oxide semiconductor electrode of the further raising of the energy conversion efficiency that can realize dye-sensitized solar cell.
Summary of the invention
The present invention accomplishes in view of said problem; Its main purpose is, provides to possess at adhesive linkage good aspect the ageing stability of bonding force and at oxide semiconductor electrode good aspect the productivity of utilizing the transfer printing mode, used its dye-sensitized solar cell and the manufacturing approach that can make the oxide semiconductor electrode of the good oxide semiconductor electrode of energy conversion efficiency with high productivity.
In order to solve said problem; The present invention provides a kind of oxide semiconductor electrode; The 1st electrode layer that is the adhesive linkage that has base material, be formed on the said base material and process by thermoplastic resin, is formed on the said adhesive linkage and processes by metal oxide, be formed on said the 1st electrode layer and contain the oxide semiconductor electrode of the porous layer of metal-oxide semiconductor (MOS) particulate; Wherein
Said thermoplastic resin contains silane-modified resin.
According to the present invention; Because through using silane-modified resin as said thermoplastic resin; Just can make adhesive linkage more firm to the bonding force of base material 1 and the 1st electrode layer; Therefore oxide semiconductor electrode of the present invention is being used under the situation of dye-sensitized solar cell,, also can obtaining can not damage the bonding stability of bonding force even redox couple penetrates into adhesive linkage from dielectric substrate.So according to the present invention, can obtain can be because of the oxide semiconductor electrode along with the exhibiting excellent stability with time that produces time lapse such as splitting etc.
In addition; The present invention provides a kind of oxide semiconductor electrode; The 1st electrode layer that is the adhesive linkage that has base material, be formed on the said base material and process by thermoplastic resin, is formed on the said adhesive linkage and processes by metal oxide, be formed on said the 1st electrode layer and contain the oxide semiconductor electrode of the porous layer of metal-oxide semiconductor (MOS) particulate; Wherein
Said porous layer by the oxide semiconductor layer that contacts with said the 1st electrode layer, be formed on the said oxide semiconductor layer and compare the higher folder interlayer of void content and constitute with said oxide semiconductor layer.
According to the present invention; Because of said porous layer by the oxide semiconductor layer that contacts with said the 1st electrode layer, be formed on the said oxide semiconductor layer and compare the higher folder interlayer of void content and constitute with said oxide semiconductor layer; Thereby when utilizing the transfer printing mode to form porous layer, can reduce the power of connecting airtight of said heat resistant substrate and porous layer.So,, can obtain good oxide semiconductor electrode aspect the productivity of utilizing the transfer printing mode according to the present invention.
In addition; According to the present invention; Because said adhesive linkage processed by thermoplastic resin, can make adhesive linkage good aspect flexible, therefore just can obtain in adhesive linkage self, to be difficult to produce " crackle " etc., possess the oxide semiconductor electrode of resisting the tolerance of external impact.
Among the present invention, said thermoplastic resin preferably contains adhesive resin.This be because; Because through making said thermoplastic resin contain adhesive resin; Just can be so that the bonding force of the base material of said adhesive linkage and the 1st electrode layer is firm; Therefore can obtain not only possess the high productivity that utilizes the transfer printing mode, and can be because of the oxide semiconductor electrode of the exhibiting excellent stability with time that produces splitting as time goes by.
In addition, among the present invention, said base material preferred resin made membrane base material.This is because because of said base material is the resin-made membrane base material, just can make oxide semiconductor electrode of the present invention good aspect flexible.
In addition, among the present invention, said porous layer preferably contains and the identical metallic element of the metallic element that metal oxide had that constitutes said the 1st electrode layer.This be because, through said porous layer contain with the formation said the 1st electrode layer the identical metallic element of the metallic element that metal oxide had, just can make oxide semiconductor electrode of the present invention good aspect conductivity.
In addition, among the present invention, said porous layer is preferably carried out pattern to be handled.This be because, handle through said porous layer being carried out pattern, for example oxide semiconductor electrode of the present invention is being used under the situation of dye-sensitized solar cell, just can the high dye-sensitized solar cell of manufacturing module electromotive force.
In addition, among the present invention, the surface adsorption that is preferably in metal-oxide semiconductor (MOS) particulate contained in the said porous layer has the pigment sensitizer.This be because, contain dye-sensitized dose through said porous layer, be used at oxide semiconductor electrode under the situation of dye-sensitized solar cell this mode, just can make the manufacturing process simplification of dye-sensitized solar cell.
In addition, the present invention provides a kind of oxide semiconductor electrode that has heat resistant substrate, it is characterized in that, on the porous layer that said oxide semiconductor electrode had, has heat resistant substrate.
According to the present invention; On the porous layer that said oxide semiconductor electrode had, have heat resistant substrate, thereby can obtain easily to process through heat-resistant material is peeled off the oxide semiconductor electrode that has heat resistant substrate of the good oxide semiconductor electrode of the connecting airtight property of each layer.
In addition; The present invention provides a kind of dye-sensitized solar cell; It is characterized in that, in said porous layer the surface adsorption of contained metal-oxide semiconductor (MOS) particulate dye-sensitized dose said oxide semiconductor electrode porous layer, by what the 2nd electrode layer and opposed base material constituted the 2nd electrode layer of electrode base material is pressed from both sides at a distance from the dielectric substrate that contains redox couple and opposed.
According to the present invention,, thereby just can obtain in adhesive linkage self, to be difficult to produce " crackle " and wait, possessed the dye-sensitized solar cell of resisting the tolerance of external impact because of said welding layer is made up of thermoplastic resin.In addition; According to the present invention; Owing to, can therefore can obtain can not produce dye-sensitized solar cell splitting, exhibiting excellent stability with time so that the bonding force of said adhesive linkage is firm because of the passage of time through said adhesive linkage is made up of silane-modified resin.
In addition; The present invention provides the manufacturing approach of a kind of oxide semiconductor electrode with laminated body; It is characterized in that; Comprise: the folder interlayer that on heat resistant substrate, contains organic substance and metal-oxide semiconductor (MOS) particulate with pattern-like coating forms with applying liquid, makes it to be solidified to form the folder interlayer formation that the folder interlayer forms with pattern and forms operation with pattern; On the said heat resistant substrate and on said folder interlayer forms with pattern; Coating forms with applying liquid than the higher oxide semiconductor layer of concentration of metal-oxide semiconductor (MOS) particulate in solid formation branch with applying liquid phase with said folder interlayer formation, makes it to be solidified to form oxide semiconductor formation and uses the oxide semiconductor layer of layer to form with a layer formation operation; Process porous body through said folder interlayer formation is burnt till with layer with pattern and oxide semiconductor layer formation, form the firing process of folder interlayer and oxide semiconductor layer; The 1st electrode layer that on said oxide semiconductor layer, forms the 1st electrode layer forms operation.
According to the present invention; The oxide semiconductor electrode that can obtain to have the folder interlayer that has been made into pattern-like is used laminated body; Through using this oxide semiconductor electrode to use laminated body, the oxide semiconductor electrode that just can obtain on the 1st electrode layer, to press from both sides interlayer and oxide semiconductor layer patterning.
In addition; In said invention; Best said heat resistant substrate possesses the wettability change layer that wettability is changed because of the light-catalysed effect that is accompanied by energy exposure on the surface; Carry out said folder interlayer form form operation with pattern before, through said wettability change layer is carried out energy exposure, form the wettability change pattern.This is because along said wettability change pattern, can precision form the folder interlayer and form and use pattern goodly.
In addition; The present invention provides a kind of manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate; It is characterized in that, carry out on 1st electrode layer of oxide semiconductor electrode that the manufacturing approach of utilizing said oxide semiconductor electrode with laminated body obtains, being provided with the base material formation operation of base material with laminated body.
According to the present invention; For example be used for to obtain the good dye-sensitized solar cell of energy conversion efficiency under the situation of making of dye-sensitized solar cell at the oxide semiconductor electrode that has heat resistant substrate that will utilize said manufacturing approach to obtain.
In addition; The present invention provides a kind of manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate; It is characterized in that; Through carrying out following operation; That is, the folder interlayer that on heat resistant substrate, contains organic substance and metal-oxide semiconductor (MOS) particulate with pattern-like coating forms with applying liquid, make it to be solidified to form the folder interlayer form folder interlayer with pattern form with pattern form operation, on the said heat resistant substrate and the formation of said folder interlayer with pattern on; Coating forms with applying liquid phase with said folder interlayer and forms with applying liquid at the solid higher oxide semiconductor layer of concentration that forms in dividing than metal-oxide semiconductor (MOS) particulate; Make it to be solidified to form oxide semiconductor and form oxide semiconductor layer with layer and form with layer and form an operation, process porous body through said folder interlayer being formed form to burn till with layer with pattern and oxide semiconductor layer, the firing process of interlayer and oxide semiconductor layer is pressed from both sides in formation, forms the oxide semiconductor substrate; Use said oxide semiconductor substrate, possessed the electrode base material of base material and the 1st electrode layer, said oxide semiconductor layer is overlapped with said the 1st electrode layer.
According to the present invention; For example be used for to obtain the good dye-sensitized solar cell of energy conversion efficiency under the situation of making of dye-sensitized solar cell at the oxide semiconductor electrode that has heat resistant substrate that will utilize said manufacturing approach to obtain.
In addition; The present invention provides a kind of manufacturing approach of oxide semiconductor electrode; It is characterized in that, carry out from utilize the oxide semiconductor electrode that has heat resistant substrate that the said manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate obtains, the stripping process that heat resistant substrate is peeled off.
According to the present invention, for example be used under the situation of dye-sensitized solar cell at the oxide semiconductor electrode that will utilize said manufacturing approach to obtain, can obtain the good dye-sensitized solar cell of energy conversion efficiency.
In addition; The present invention provides a kind of manufacturing approach of dye-sensitized solar cell, it is characterized in that, comprises electrode base material is formed operation; Use oxide semiconductor electrode that the manufacturing approach utilize said oxide semiconductor electrode obtains in this operation, possessed the 2nd electrode pattern and opposed base material to electrode base material; Said folder interlayer is faced with said the 2nd electrode pattern mutually, and it is right with base material to form dye-sensitized solar cell
In the manufacturing approach of said dye-sensitized solar cell; To said oxide semiconductor electrode with laminated body, it is said that to have the oxide semiconductor electrode of heat resistant substrate, said oxide semiconductor electrode or said dye-sensitized solar cell right with base material; Fill processing, this filling is handled and comprised: support dye-sensitized dose on the pore surface of said folder interlayer and said oxide semiconductor layer dye-sensitized dose supports operation; And after said dye-sensitized dose supported operation, between said the 2nd electrode pattern and said folder interlayer, and the porous body pore of said oxide semiconductor layer and said folder interlayer was inner, and the dielectric substrate that forms dielectric substrate forms operation.
According to the present invention, for example, can obtain the good dye-sensitized solar cell of energy conversion efficiency in that said oxide semiconductor electrode etc. is used under the situation of dye-sensitized solar cell.
In addition, in said invention, preferably to said oxide semiconductor electrode with laminated body or said oxide semiconductor electrode, carry out said the 1st electrode layer is processed pattern-like and the 1st electrode pattern that forms the 1st electrode pattern form to be handled.This is because through using said the 1st electrode pattern, can obtain the good dye-sensitized solar cell of energy conversion efficiency.
The present invention plays following effect, that is, can obtain the bonding excellent in stability of each layer and possess the oxide semiconductor electrode and the dye-sensitized solar cell of high productivity.In addition, the present invention also plays following effect,, can make the good oxide semiconductor electrode of energy conversion efficiency with high productivity that is.
Description of drawings
Fig. 1 is the summary section of an example of the general formation of expression dye-sensitized solar cell.
Fig. 2 is the summary section of an example that expression has the dye-sensitized solar cell of adhesive linkage.
Fig. 3 is the summary section of an example of the oxide semiconductor electrode of expression invention.
Fig. 4 is the summary section of other examples of the oxide semiconductor electrode of expression invention.
Fig. 5 is the summary section of other examples of expression oxide semiconductor electrode of the present invention.
Fig. 6 is the process chart of an example of the manufacturing approach of the expression base material that has a heat resistant substrate of the present invention.
Fig. 7 is the process chart of an example of expression heat resistant substrate stripping process of the present invention.
Fig. 8 is the process chart of an example of the pattern treatment process of expression porous layer of the present invention.
Fig. 9 is the summary section of an example of the expression oxide semiconductor electrode that has a heat resistant substrate of the present invention.
Figure 10 is the summary section of an example of expression dye-sensitized solar cell of the present invention.
Figure 11 is that explanation utilizes oxide semiconductor electrode that the present invention the obtains key diagram with the shape of laminated body.
Figure 12 is the process chart of expression oxide semiconductor electrode of the present invention with an example of the manufacturing approach of laminated body.
Figure 13 is the key diagram of an example of the formation method of employed the 1st electrode layer among expression the present invention.
Figure 14 is the key diagram of other examples of the formation method of employed the 1st electrode layer among expression the present invention.
Figure 15 is the key diagram of other examples of the formation method of employed the 1st electrode layer among expression the present invention.
Figure 16 is the process chart of an example of the manufacturing approach of the expression oxide semiconductor electrode that has a heat resistant substrate of the present invention.
Figure 17 is the process chart of other examples of the manufacturing approach of the expression oxide semiconductor electrode that has a heat resistant substrate of the present invention.
Figure 18 is the process chart of an example of the manufacturing approach of expression oxide semiconductor electrode of the present invention.
Figure 19 is the process chart of an example of the manufacturing approach of expression dye-sensitized solar cell of the present invention.
Figure 20 is the key diagram that expression utilizes an example of the dye-sensitized solar cell that the present invention obtains.
Embodiment
To describe with the manufacturing approach of the manufacturing approach of laminated body, the manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate, oxide semiconductor electrode and the manufacturing approach of dye-sensitized solar cell oxide semiconductor electrode of the present invention, the oxide semiconductor electrode that has heat resistant substrate, dye-sensitized solar cell, oxide semiconductor electrode below.
A. oxide semiconductor electrode
At first, oxide semiconductor electrode of the present invention is described.The adhesive linkage that oxide semiconductor electrode of the present invention has base material, be formed on the said base material and processed by thermoplastic resin, the 1st electrode layer that is formed on the said adhesive linkage and processes by metal oxide, be formed on said the 1st electrode layer and contain the porous layer of metal-oxide semiconductor (MOS) particulate.
Below, in reference to accompanying drawing, oxide semiconductor electrode of the present invention is described.The summary section that has shown an example representing oxide semiconductor electrode of the present invention among Fig. 3.The adhesive linkage 22 that as shown in Figure 3, oxide semiconductor electrode 20a of the present invention has base material 21, be formed on the said base material and processed by thermoplastic resin, the 1st electrode layer 23 that is formed on the said adhesive linkage 22 and processes by metal oxide, be formed on said the 1st electrode layer and contain the porous layer 24 of metal-oxide semiconductor (MOS) particulate.
Oxide semiconductor electrode of the present invention can be divided into: with said thermoplastic resin contain " oxide semiconductor electrode of mode one " that silane-modified resin is a characteristic, with said porous layer by the oxide semiconductor layer that contacts with said the 1st electrode layer, be formed on the said oxide semiconductor layer and compare " oxide semiconductor electrode of mode two " that the higher folder interlayer of void content constitutes characteristic with said oxide semiconductor layer.Below, for oxide semiconductor electrode of the present invention, will be divided into the oxide semiconductor electrode of mode one and the oxide semiconductor electrode of mode two, at length describe.
A-1: the oxide semiconductor electrode of mode one
At first, the oxide semiconductor electrode for mode one describes.The 1st electrode layer that the oxide semiconductor electrode of mode one is the adhesive linkage that has base material, be formed on the said base material and processed by thermoplastic resin, be formed on the said adhesive linkage and processed by metal oxide, be formed on said the 1st electrode layer and contain the oxide semiconductor electrode of the porous layer of metal-oxide semiconductor (MOS) particulate; Wherein, said thermoplastic resin contains silane-modified resin.
According to the oxide semiconductor electrode of mode one,, just can make the bonding force of base material and the 1st electrode layer of said adhesive linkage firm through using silane-modified resin as said thermoplastic resin.Though through using silane-modified resin like this as said thermoplastic resin; The mechanism that makes the bonding force of base material and the 1st electrode layer of said adhesive linkage improve is not clear; But can think because; The reactive functional group that silane-modified resin had produces condensation reaction etc. with the compound that constitutes base material and the 1st electrode layer, thereby forms chemical bond.
In addition; Because through using silane-modified resin as said thermoplastic resin; Just can as said, make the bonding force of adhesive linkage firm,, also can obtain can not damage the bonding stability of bonding force even therefore redox couple penetrates into adhesive linkage from dielectric substrate.So according to the oxide semiconductor electrode of mode one, can obtain not can be because of the oxide semiconductor electrode of the exhibiting excellent stability with time that produces splitting etc. with the passing of time.
Utilize the manufacture method of oxide semiconductor electrode of transfer printing mode very useful aspect the material of the base material that need not consider to be used for oxide semiconductor electrode; Yet when making the oxide semiconductor electrode of exhibiting excellent stability with time; Adhesive linkage need have good bonding force, and bonding force need be kept long-term and stably.But, in the making of the oxide semiconductor electrode that in the past utilizes the transfer printing mode, in the employed binding agent, have bonding force not enough, along with the problem that produces splitting time lapse.
In addition; For example said oxide semiconductor electrode is being used under the situation of dye-sensitized solar cell; Because porous layer is a porous character, therefore confirming has redox couple contained in the dielectric substrate to see through porous layer, and then sees through the phenomenon of electrode layer again.Thus, in the dye-sensitized solar cell that has used oxide semiconductor electrode,, there is the bonding force of adhesive linkage to reduce, produces the problem of splitting because of the effect of redox couple in the said dielectric substrate and solvent etc. with adhesive linkage.Because the oxide semiconductor electrode that this kind problem, very difficult use utilize the transfer printing mode to form is made the dye-sensitized solar cell of exhibiting excellent stability with time.
Oxide semiconductor electrode according to mode one of the present invention; Owing to be made as silane-modified resin through the thermoplastic resin that will constitute said adhesive linkage; Can make the bonding force of base material, the 1st electrode layer of adhesive linkage firm, therefore can obtain the oxide semiconductor electrode of exhibiting excellent stability with time.Below, will respectively the constituting of oxide semiconductor electrode of this mode be described.
1. adhesive linkage
At first, the adhesive linkage to the oxide semiconductor electrode of mode one describes.The adhesive linkage of this mode is the layer with effect that said base material, said the 1st electrode layer is bonding, it is characterized in that, is made up of silane-modified resin.
(1) silane-modified resin
Employed silane-modified resin is so long as demonstrate thermoplasticity in this mode; Demonstrate with after the material of cementability of the base material stated and the 1st electrode layer, just not special the qualification, however wherein; In this mode; In preferred 50 ℃～200 ℃ scope of fusing point, in preferred especially 60 ℃～180 ℃ scope, in wherein preferred again 65 ℃～150 ℃ scope.This be because; When fusing point is lower than said scope, for example under the situation that the dye-sensitized solar cell that the oxide semiconductor electrode that will use this mode is made uses without, just might keep the connecting airtight property between base material and the 1st electrode layer fully; In addition; When fusing point is higher than said scope, then for example when utilizing transfer printing to make dye-sensitized solar cell, owing in transfer printing process, need the heating process more than the fusing point by the oxide semiconductor electrode of this mode; Therefore different according to employed kind in this mode, have the situation that base material self receives the damage that is caused by heat.
Employed silane-modified resin in this mode is so long as have the material of said fusing point, just not special the qualification.Wherein, as employed silane-modified resin in this mode, preferably use the copolymer of polyolefin compound and ethene property unsaturated silane compound.This be because, through using this kind copolymer, for example just can be according to the manufacturing approach of the oxide semiconductor electrode of this mode etc., the many rerum naturas with silane-modified resin are adjusted into suitable scope at an easy rate.In this mode, no matter said copolymer utilizes the crosslinked of silane alcohol catalyst can or do not carry out.
As employed said polyolefin compound in this mode; The carbon number such as homopolymers, these alpha-olefins and ethene, propylene, 1-butylene, 3-methyl-1-butene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene that can enumerate carbon numbers such as ethene, propylene, 1-butylene and be about 2～8 alpha-olefin is about 2～20 other the copolymer of alpha-olefin, vinyl acetate, (methyl) acrylic acid, (methyl) acrylic acid ester etc.; Specifically, for example can enumerate the 1-butylene resinoids such as propylene resin such as Alathon, ethylene-propylene copolymer, ethene-1-propylene copolymer, ethene-4 methyl 1 pentene copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethene-(methyl) acrylic copolymer, ethene-vinyl resins, Noblen, propylene-ethylene copolymers, propylene-ethylene-butene-1 copolymers such as (methyl) ethyl acrylate copolymer and 1-chevron, 1-butylene-ethylene copolymer, 1-butylene-propylene copolymer etc. of low middle-high density polyethylene etc. (branched or straight chain shape).Wherein, in this mode, the preferably polyethylene resinoid.
No matter employed said copolymer is that any of random copolymer, alternate copolymer, block copolymer and graft copolymer can in this mode.In this mode, preferred graft copolymer, more preferably with polymerization with polyethylene as main chain, with ethene property unsaturated silane compound as side chain and polymerization graft copolymer.This is because owing to help the degree of freedom of the silanol group of bonding force to uprise, therefore can make the bonding force of adhesive linkage more firm in this kind graft copolymer.
As employed said polythylene resin in this mode (below be called polymerization use polyethylene), so long as the polymer of polyethylene kind, just not special the qualification.As the polymer of this kind polyethylene kind, can enumerate low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), ultra-low density polyethylene, utmost point ultra-low density polyethylene or straight chain shape low density polyethylene (LDPE).In addition, in this mode, both can a kind of of these polyethylene based polymers be used as monomer, also can use in addition mixing more than 2 kinds.
In addition, in this mode employed polymerization with the preferred lower material of density among said polyethylene based polymers of polyethylene, specifically, the preferred 0.850g/cm of density 3～0.960g/cm 3Scope in, preferred especially 0.865g/cm 3～0.930g/cm 3Scope in.Therefore low density polyethylene based polymers can perform well in the glycerol polymerization owing in general contain a lot of side chains.So when density was higher than said scope, it is insufficient that glycerol polymerization just becomes, have the situation that can't give required bonding force to adhesive linkage, in addition, when density is lower than said scope, then might damage the mechanical strength of adhesive linkage.
As employed said ethene property unsaturated silane compound in this mode, so long as can use polyethylene polymerization, form the material of thermoplastic resin, just not special the qualification with said polymerization.As this kind ethene property unsaturated silane compound, that preferably from be made up of vinyltrimethoxy silane, VTES, vinyl tripropoxy silane, vinyl three butoxy silanes, vinyl three amoxy silane, vinyl triple phenoxyl silane, vinyl three benzyloxy silane, vinyl propylidene dihydroxy base silane, vinyl triethylene dihydroxy silane, vinyl propionyloxy silane, vinyltriacetoxy silane and vinyl tricarboxylic base silane one group, selects is at least a.
Below, the manufacturing approach of the graft copolymer of said polyolefin compound and said ethene property unsaturated silane compound is described.The manufacturing approach of this kind graft copolymer is so long as can obtain the method for required yield, and just not special the qualification can utilize known polymerization to make.Wherein, in this mode, preferably through mixing the method that obtains graft copolymer by the silane-modified resin combination heating and melting that said polyolefin compound, said ethene property unsaturated silane compound, free radical initiator constitute.This is because according to this kind method, can obtain said graft copolymer with high yield at an easy rate.
Heating-up temperature when said heating and melting mixes be so long as can finish in the required time in the scope of polymerization reaction, and just not special the qualification is common preferred below 300 ℃, preferred especially below 270 ℃, wherein, and in preferred 160 ℃～250 ℃ scope.When heating-up temperature is lower than said scope, then have the situation that polymerization reaction is not carried out fully, in addition when heating-up temperature is higher than said scope, then can silanol group partial cross-linked and gelation.
As free radical initiator, so long as can help the compound of the promotion of said polymerization reaction, just not special the qualification.As the free radical initiator of this kind, for example can enumerate hydrogen peroxide diisopropyl benzene, 2,5-dimethyl-2, hydroperoxide kinds such as 5-two (peroxy) hexane; Peroxidating two-tert-butyl group, tert-butyl peroxide cumyl, dicumyl peroxide, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,5-dimethyl-2, class such as dialkyl peroxide such as 5-two (t-peroxy) hexane-3 grade; Two-3,5,5-trimethyl acetyl base peroxide, sim peroxides, benzoyl peroxide, o-methyl benzoyl peroxide, 2, diaryl peroxides such as 4-dichloro benzoyl peroxide; The tert-butyl group-peroxide isobutyrate, t-butyl peroxy acetic acid esters, t-butylperoxy-2 ethyl hexanoic acid ester, t-butyl peroxy trimethylace tonitric ester, t-butyl peroxy caprylate, t-butyl peroxy isobutyl carbonate propyl ester, t-butyl peroxy benzoate, di-t-butyl peroxide phthalic acid ester, 2; 5-dimethyl-2; 5-two (benzoyl peroxy) hexane, 2; 5-dimethyl-2, peroxyesters such as 5-two (benzoyl peroxy) hexene-3 grade; Organic peroxides such as ketone peroxide class such as methyl-ethyl-ketone peroxide, cyclohexanone peroxide; Or azodiisobutyronitrile, azo azo-compounds such as (2, the 4-methyl pentane nitrile) etc.These free radical initiators both can only use as monomer a kind of, also can two or more mixing be used in addition.
Though the content of the free radical initiator in the said silane-modified resin combination can be according to the kind of free radical initiator with polymeric reaction condition and decision at random, utilize the remaining quantity in the silane-modified resin that polymerization reaction obtains preferably to be in the following scope of 0.001 quality %.In this mode, as a rule, polyolefin compound 100 weight portions with respect in the said silane-modified resin combination preferably contain more than 0.001 weight portion, especially preferably contain 0.01 weight portion～5 weight portions.
The content of the ethene property unsaturated silane compound in the said silane-modified resin combination with respect to polymerization with polyethylene 100 weight portions, in the scope of preferred 0.001 weight portion～4 weight portions, in the scope of preferred especially 0.01 weight portion～3 weight portions.This be because; When the content of ethene property unsaturated silane compound than said scope more for a long time; Then might remainingly have not by polymerization and free ethene property unsaturated silane compound, in addition, when still less than said scope; Then the power of connecting airtight of adhesive linkage becomes insufficient, thereby the situation of the stability of the oxide semiconductor electrode that damages our formula is arranged.
(2) other compound
In the adhesive linkage of this mode, can contain other the compound beyond the silane-modified resin as required.In this mode, preferably use thermoplastic resin, wherein, preferably use polyolefin compound (below be called to add use polyolefin compound) as other compound of this kind.In addition; As said silane-modified resin contained in the adhesive linkage; Under the situation of the copolymer that uses polyolefin compound and ethene property unsaturated silane compound; Polyolefin compound is used in interpolation as this kind, preferred use with said copolymer in the identical compound of employed polyolefin compound.
In this mode, the said interpolation in the adhesive linkage with the content of polyolefin compound with respect to said silane-modified resin 100 weight portions, in the scope of preferred 0.01 weight portion～9900 weight portions, in the scope of special more preferably 0.1 weight portion～2000 weight portions.This be because, when adding with the content of polyolefin compound than said scope still less, it is unfavorable then aspect cost, can to become sometimes, in addition, when than said scope more for a long time, bonding force that then might adhesive linkage becomes insufficient.
In this mode, as said polyolefin compound, preferably use polythylene resin (below be called to add and use polyethylene.)。This is because in this mode, as said silane-modified resin, preferably use the copolymer of polythylene resin and ethene property unsaturated silane compound.
Use polyethylene as said interpolation, that preferably from be made up of low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), ultra-low density polyethylene and straight chain shape low density polyethylene (LDPE) one group, selects is at least a.
In addition, employed adhesive linkage preferably contains at least a additive of from be made up of Photostabilised dose, ultra-violet absorber, heat stabilizer and oxidation inhibitor a group, selecting in this mode.This is because through adding these additives, just can obtain mechanical strength steady in a long-term, anti-xanthochromia, prevent blind crack, good flexibility (adaptability) of operation.
Photostabilised dose is the spike of the initiation light deterioration in the employed thermoplastic resin in replenishing adhesive linkage, prevents the material of photooxidation.Specifically, can enumerate Photostabilised dose of hindered amine compound, hindered piperidine compounds etc.
Ultra-violet absorber is the harmful ultraviolet ray that absorbs in the sunlight, converts heat energy harmless in molecule into, prevents the material that the spike of the initiation light deterioration in the employed thermoplastic resin in adhesive linkage is excited.0.01 μ m～0.06 μ m) or ultra-fine particles of zinc oxide (particle diameter: ultra-violet absorbers such as mineral-type such as 0.01 μ m～0.04 μ m) specifically, can enumerate Benzophenone class, benzotriazole, salicylate class, vinyl cyanide, metal complex salt, hindered amines and ultrafine particulate titanium oxide (particle diameter:.
As heat stabilizer, can enumerate three (2,4-two-tert-butyl-phenyl) phosphide, two [2; 4-two (1; The 1-dimethyl ethyl)-and the 6-aminomethyl phenyl] ethyl ester phosphorous acid, four (2,4-two-tert-butyl-phenyl) [1, the 1-diphenyl]-4; Phosphorus heat stabilizers such as 4 '-two basic biphosphinates and two (2,4-two-tert-butyl-phenyl) pentaerythrite diphosphides; 8-hydroxyl-5, lactone heat stabilizers such as the reaction product of 7-two-tert-butyl group-furans-2-ketone and ortho-xylene etc.Preferably Phosphorus heat stabilizer and lactone heat stabilizer are used simultaneously.
Oxidation inhibitor is the material that prevents the oxidative degradation of employed thermoplastic resin in the adhesive linkage.Specifically, can enumerate oxidation inhibitors such as phenol, amine, sulphur class, Phosphorus and lactone.
Even these Photostabilised dose, ultra-violet absorber, heat stabilizer and oxidation inhibitor separately with a kind of use, also can use combination more than 2 kinds.
Though the content of Photostabilised dose, ultra-violet absorber, heat stabilizer and oxidation inhibitor preferably is in the material of each comfortable adhesive linkage in the scope of 0.001 quality %～5 quality % because of its shape of particle, density etc. are different.
In addition, as employed other compound in this mode, except said, can also enumerate crosslinking agent, dispersant, levelling agent, plasticizer, antifoaming agent etc.
(3) adhesive linkage
The thickness of employed adhesive linkage in this mode is so long as in the scope that can embody necessary bonding force with the kind of the said silane-modified resin that constitutes adhesive linkage accordingly; Just not special the qualification; Yet as a rule; In the scope of preferred 5 μ m～300 μ m, in the scope of preferred especially 10 μ m～200 μ m.This be because; When the thickness of adhesive linkage is thinner than said scope; Then have the situation that can't obtain required bonding force, in addition when thickness is thicker than said scope, then in order to utilize adhesive linkage adhesive strength between embodied layers fully; Just need too much heating, thereby have the situation that the fire damage to base material etc. increases.
2. the 1st electrode layer
Below, employed the 1st electrode layer in this mode is described.The characteristic of employed the 1st electrode layer is to be made up of metal oxide in this mode.
(1) metal oxide
As employed metal oxide in this mode, so long as excellent conductivity and for after the redox couple stated demonstrate the material of tolerance, just not special the qualification.Wherein, in this mode, preferably use the permeability excellent material of sunlight.For example; When the oxide semiconductor electrode of this mode of use is processed dye-sensitized solar cell; As a rule; Owing to utilize the mode of receiving sunlight from the base material side joint to use, therefore when said metal oxide is not good aspect the permeability of sunlight, then used the generating efficiency of dye-sensitized solar cell of the oxide semiconductor electrode of this mode will be impaired.
As the good said metal oxide of the permeability of this kind sunlight, for example can enumerate SnO 2, ITO, IZO, ZnO.Among the present invention, in the middle of these metal oxides, the preferred use carried out the SnO that fluorine mixes 2(below be called FTO.)、ITO。This is because FTO and ITO are very good aspect the permeability two of conductivity and sunlight.
(2) the 1st electrode layers
The 1st electrode layer of the present invention both can be to be made up of individual layer, the formation of multilayer that can be range upon range of also in addition.As the range upon range of formation of multilayer, for example can enumerate the mode of the different each other layer of range upon range of work function, the mode of the range upon range of layer that constitutes by mutual different metallic oxide.
The thickness of the 1st electrode layer of this mode is so long as can realize in the scope of required conductivity just not special the qualification with the purposes of the dye-sensitized solar cell of the oxide semiconductor electrode that has used this mode etc. accordingly.As the thickness of the 1st electrode layer of this mode, as a rule, in the scope of preferred 5nm～2000nm, in the scope of preferred especially 10nm～1000nm.This is because when thickness is bigger than said scope, then have the situation that is difficult to form uniform the 1st electrode layer; In addition; When thickness than said scope more hour, then according to the purposes of the oxide semiconductor electrode of this mode, conductivity that might the 1st electrode layer is not enough.
And the thickness of said transparency electrode is meant the gross thickness after the thickness total of all layers under the situation that transparency electrode is made up of multilayer.
In addition, as the 1st electrode layer of the present invention, also can use have on base material opening enough big and have a form of the integrated or range upon range of formation of having changed of wire netting and the said metal oxide of light transmission.
3. porous layer
Below, the porous layer of this mode is described.The characteristic of employed porous layer is among the present invention, contains the metal-oxide semiconductor (MOS) particulate.
(1) metal-oxide semiconductor (MOS) particulate
As employed metal-oxide semiconductor (MOS) particulate in this mode, can enumerate TiO 2, ZnO, SnO 2, ITO, ZrO 2, MgO, Al 2O 3, CeO 2, Bi 2O 3, Mn 3O 4, Y 2O 3, WO 3, Ta 2O 5, Nb 2O 5, La 2O 3Deng.These metal-oxide semiconductor (MOS) particulates can be realized the raising of energy conversion efficiency, the reduction of cost owing to be suitable for forming porous porous layer, therefore are applicable in the oxide semiconductor electrode of this mode.In addition, in this mode, both can use in the middle of the said metal-oxide semiconductor (MOS) particulate any one, also can use in addition mixing more than 2 kinds.In addition, also can adopt following core shell structure, that is, a kind of with in the middle of the described metal-oxide semiconductor (MOS) particulate as the core particulate, the metal-oxide semiconductor (MOS) particulate that utilizes other comprises the core particulate and forms shell.In this mode,, most preferably use TiO as said conductor oxidate particulate 2
Particle diameter as employed metal-oxide semiconductor (MOS) particulate in this mode; So long as in the scope that can in porous layer, obtain required surface area, just not special the qualification, as a rule; In the scope of preferred 1nm～10 μ m, in the scope of preferred especially 10nm～1000nm.This be because; When the said scope of size ratio more hour, then have each metal-oxide semiconductor (MOS) particle coagulation and form the situation of offspring, in addition; When the said scope of size ratio is bigger; Then porous layer generation thick filmization not only, and the vesicularity of porous layer, promptly specific area reduces; For example be used under the situation of dye-sensitized solar cell, have and in porous layer, can't support dye-sensitized dose situation enough for opto-electronic conversion at oxide semiconductor electrode with this mode.
In addition, in this mode,, also can use the mixture of the different a plurality of metal-oxide semiconductor (MOS) particulates of particle diameter as said metal-oxide semiconductor (MOS) particulate.Because through using the mixture of particle diameter different metallic oxide semiconductor particulate; Can improve the light scattering effect of porous layer; Therefore for example be used under the situation of dye-sensitized solar cell, just can utilize dye-sensitized dose light absorption effectively at oxide semiconductor electrode with this mode.So, in this mode, especially preferably use the mixture of particle diameter different metallic oxide semiconductor particulate.
As the mixture of the different a plurality of metal-oxide semiconductor (MOS) particulates of this kind particle diameter, both can be the mixture of the metal-oxide semiconductor (MOS) particulate of identical type, also can be the mixture of different kinds of metals oxide semiconductor particulate in addition.As the combination of different-grain diameter, for example can enumerate the metal-oxide semiconductor (MOS) particulate in the scope that is in 10～50nm, the metal-oxide semiconductor (MOS) particulate that is in the scope of 50～800nm are mixed the mode of using.
(2) other compound
In the porous layer in this mode, preferably contain and identical metallic element (the following electrode metal element that is called sometimes of the metallic element that metal oxide had that constitutes said the 1st electrode layer.)。This be because, contain the electrode metal element through said porous layer, just can the oxide semiconductor electrode of this mode be processed high conductive electrode.
Though the existence of the electrode metal element in the said porous layer distributes can be according to the purposes of the oxide semiconductor electrode of this mode etc. and decision at random preferably has the existence distribution that has the concentration gradient that reduces tendency from the surface of the 1st electrode layer side towards the surface of an opposite side.This is because the electrode metal element distributes like this in porous layer, just can further improve the current collecting efficiency of porous layer.
In this mode, about in porous layer, containing the electrode metal element and have the situation that described existence distributes, can through with electron ray as probe and the characteristic X-ray intensity of metallic element that will be specific is mapped and judged two-dimentionally.Specifically, can utilize the EPMA (Electron Probe Micro Analyzer) of company of NEC (JEOL) system to judge.In addition, for the concentration gradient of said metallic element, can utilize the detected intensity of vertical (the vertical section direction) of the section element schema mapping that obtains by said EPMA to analyze and judge.
In addition, the porous layer of this mode preferably contains dye-sensitized dose.That is the surface adsorption that, is preferably in metal-oxide semiconductor (MOS) particulate contained in the said porous layer has the pigment sensitizer.This be because, contain dye-sensitized dose through said porous layer, be used at oxide semiconductor electrode under the situation of dye-sensitized solar cell this mode, just can make the manufacturing process simplification of dye-sensitized solar cell.As in this mode employed dye-sensitized dose, so long as can absorbing light and produce the material of electromotive force, just not special the qualification.As dye-sensitized dose of this kind and since with after the content put down in writing in the part of " manufacturing approach of G. dye-sensitized solar cell " stated identical, therefore the explanation is here omitted.
And the what is called described in this mode contains " dye-sensitized dose " and is meant, is adsorbed on the surface of metal-oxide semiconductor (MOS) particulate contained in the porous layer (folder interlayer and oxide semiconductor layer).
(3) porous layer
The thickness of the porous layer of this mode is so long as can give in the scope of required mechanical strength just not special the qualification according to the purposes of oxide semiconductor electrode of the present invention to porousness.The thickness of porous layer of the present invention as a rule, in the scope of preferred 1 μ m～100 μ m, in the scope of preferred especially 5 μ m～30 μ m.This be because; When porous layer thickness is bigger than said scope, then have the cohesion that causes easily with the peeling off of adhesive linkage, porous layer self and destroy, form the situation of film resistance easily; In addition; When more hour than said scope, then be difficult to form the uniform porous layer of thickness, for example be used under the situation of dye-sensitized solar cell at oxide semiconductor electrode with this mode; Because the porous layer that contains dye-sensitized dose can't absorb sunlight etc. fully, therefore just might cause performance bad.
The porous layer of this mode both can be to be made up of single layer, a plurality of layers the formation that can be range upon range of also, but in this mode, preferably have range upon range of a plurality of layers formation.As range upon range of a plurality of layers formation, can suitably select to adopt arbitrarily to constitute according to the manufacturing approach of the oxide semiconductor electrode of this mode etc.Wherein, In this mode, more preferably porous layer is made as by the oxide semiconductor layer that contacts with said the 1st electrode layer, is formed on the said oxide semiconductor layer and compares 2 layers of structure that the higher folder interlayer of void content constitutes with said oxide semiconductor layer.This be because; Through porous layer being made as 2 layers of structure of planting oxide semiconductor layer and folder interlayer formation thus; When utilizing the transfer printing mode to form porous layer; Just can reduce the power of connecting airtight of said heat resistant substrate and porous layer, thereby can obtain to utilize the oxide semiconductor electrode of the highly productive of transfer printing mode.
In this mode; Porous layer is being made as by the oxide semiconductor layer that contacts with said the 1st electrode layer, is being formed on the said oxide semiconductor layer and compares with said oxide semiconductor layer under the situation of 2 layers of structure that the higher folder interlayer of void content constitutes; Said folder interlayer does not need adequate relief to be formed on the said oxide semiconductor layer; Both can have thickness distribution, and also can on oxide semiconductor layer, have in addition not have the part of pressing from both sides interlayer.This is because even the folder interlayer exists with this kind mode, also can obtain to utilize the oxide semiconductor electrode of the highly productive of transfer printing mode.
As long as oxide semiconductor layer when porous layer is made as 2 layers of structure of said oxide semiconductor layer and said folder interlayer and the thickness ratio of folder interlayer are according to the decisions at random such as manufacturing approach of the oxide semiconductor electrode of this mode.Wherein, in this mode, the thickness of said oxide semiconductor layer and said folder interlayer is than in preferred 10: 0.1～10: 5 scope, wherein more preferably in 10: 0.1～10: 3 the scope.This be because; When the thickness that presss from both sides interlayer is bigger than said scope; Then destroy because of the cohesion that causes the folder interlayer easily; Thereby when producing oxide semiconductor electrode of the present invention the rate of finished products variation, for example when the oxide semiconductor electrode with this mode is used for dye-sensitized solar cell, might be in porous layer the surface of contained metal-oxide semiconductor (MOS) particulate can't adsorb dye-sensitized dose of aequum.In addition, when thickness than said scope more hour, then have the situation that the productivity of the oxide semiconductor electrode that can't help this mode improves.
In the scope as the void content of said oxide semiconductor layer preferred 10%～60%, wherein, more preferably in 20%～50% the scope.This is because for example, be used at the oxide semiconductor electrode with this mode under the situation of dye-sensitized solar cell; When the void content of oxide semiconductor than said scope more hour; Then because specific area diminishes, the porous layer that therefore contains dye-sensitized dose just might absorb sunlight etc. effectively, in addition; When bigger, then might in oxide semiconductor layer, contain dye-sensitized dose of aequum than said scope.
As the void content of said folder interlayer, as long as bigger than the void content of said oxide semiconductor layer, just not special the qualification, yet as a rule, in preferred 25%～65% the scope, wherein more preferably in 30%～60% the scope.This be because, when the void content of folder interlayer than said scope more hour, then owing to improve with the power of connecting airtight of heat resistant substrate, therefore just might be not good on productivity, in addition, when bigger, then have the situation that is difficult to form uniform folder interlayer than said scope.
And so-called void content of the present invention is meant the non-occupation rate of the metal semiconductor particulate of per unit volume.As the assay method of said void content, be to utilize gas absorption amount determining device (Autosorb-1MP; The Quantachrome system) measures pore volume, according to calculating with the ratio of the volume of per unit area.For the void content of folder interlayer, be to be used as with the range upon range of porous layer of oxide semiconductor layer to try to achieve, calculate according to the value of utilizing the oxide semiconductor layer monomer to try to achieve.
4. base material
Below, employed base material in this mode is described.The base material that can be used for this mode is so long as according to purposes of the oxide semiconductor electrode of this mode etc.; Have the required transparency, just do not have special qualification, but as a rule; Transmitance with respect to the light of wavelength 400nm～1000nm is preferred more than 78%, more preferably more than 80%.This be because, when the transmitance of base material is lower than said scope, then for example process under the situation of dye-sensitized solar cell at the oxide semiconductor electrode of this mode of use, generating efficiency just might be impaired.
In addition, employed base material has in the middle of the material of the said transparency in this mode, more preferably in thermal endurance, weatherability, to excellent material aspect the shielding of steam and other gases.This is because because of base material has gas-barrier property, for example be used for just can improving ageing stability under the situation of dye-sensitized solar cell at the oxide semiconductor electrode with this mode.Wherein, in this mode, more preferably use the base material with following gas-barrier property, that is, oxygen permeability is 1cc/m under the condition of 23 ℃ of temperature, humidity 90% 2Below/the dayatm, moisture-vapor transmission is 1g/m under the condition of 37.8 ℃ of temperature, humidity 100% 2Below/the day.In this mode,, also can use the material that on base material arbitrarily, is provided with gas shielding layer in order to reach this kind gas-barrier property.
As the base material that possesses said gas-barrier property, can enumerate quartz glass, パ イ レ Star Network ス (registered trade mark), synthetic quartz plate etc. does not have flexible transparent rigid material, ethylene tetrafluoroethylene copolymer film, biaxial tension pet film, polyether sulfone (PES) film, polyether-ether-ketone (PEEK) film, PEI (PEI) film, polyimides (PI) film, polyester naphthalene ester film (PEN), Merlon resin-made membrane base materials such as (PC).
In this mode, in the middle of said base material, more preferably use the resin-made membrane base material.This be because, the resin-made membrane base material is because good aspect processability, therefore the combination of equipment with other is more easy, can widen the scope of purposes.In addition, also because, can help the reduction of manufacturing cost through using resin-made membrane.In addition, the base material of this mode both can use a kind of separately, in addition also can be with two or more range upon range of uses.In this mode, especially preferably use biaxial tension pet film (PET), polyester naphthalene ester (PEN), Merlon (PC) as base material.
The thickness of employed base material in this mode is so long as have in the scope of required self-supporting property just not special the qualification according to the purposes of the oxide semiconductor electrode of this mode etc.In this mode, as a rule, in the scope of preferred 50 μ m～2000 μ m, in the scope of preferred especially 75 μ m～1800 μ m, wherein more preferably in the scope of 100 μ m～1500 μ m.This be because, when the thickness of base material than said scope more hour, then have the situation that can't guarantee necessary self-supporting property, in addition, when thickness is bigger than said scope, then might damage flexibility (adaptability) of operation.
5. oxide semiconductor electrode
Porous layer in the oxide semiconductor electrode of this mode is preferably carried out pattern to be handled.This is because through porous layer being carried out the pattern processing, just can make the oxide semiconductor electrode of our formula be suitable for the high dye-sensitized solar cell of manufacturing module electromotive force.In with reference to accompanying drawing, the pattern of the porous layer of this mode handled describing.Fig. 5 is the summary section of an example of pattern processing mode of the porous layer of this mode of expression.The pattern of the porous layer of this mode is handled as Fig. 5 (a) shown in, and porous layer 24 is carried out the pattern processing and gets final product at least.In addition, shown in Fig. 5 (b), under the situation that porous layer 24 is made up of oxide semiconductor layer 24a, folder interlayer 24b, best two-layer quilt is handled with the identical shaped pattern that carries out.
In addition, as the pattern processing mode of the porous layer of this mode, preferably porous layer 24 is carried out the pattern processing with the 1st electrode layer 23.Carried out under the situation of pattern processing at porous layer 24 and the 1st electrode layer 23; The pattern of porous layer 24 and the 1st electrode layer 23 is handled shape and is for example preferably utilized the pattern processing shape of porous layer 24 to handle modes such as shape is littler than the pattern of the 1st electrode layer 23, and it is different each other to make pattern handle shape.
Though in this mode porous layer carried out the pattern of pattern when handling can be according to the purposes of the oxide semiconductor electrode of this mode etc. and decision at random wherein, most preferably is made as the pattern processing of shape of stripes.
As said porous layer being carried out the method that pattern is handled, so long as can precision the porous layer pattern be treated to required method of patterning, just not special the qualification goodly.As employed pattern processing method in this mode, for example can enumerate laser scribing method, wet etching, peel off (lift off) method, dry-etching method, mechanical marking method etc., wherein more preferably laser scribing method and mechanical marking method.
As the pattern processing method beyond said; As shown in Figure 8; Can enumerate oxide semiconductor electrode that the pattern that on substrate 31 arbitrarily, will have the hot melt resin bed of having been handled by pattern 32 handles base material 30, this mode according to after making hot melt resin bed 32 and mode thermal welding that porous layer 24 contacts; Peel off through pattern being handled base material 30, and porous layer is carried out the example that pattern is handled.On said base material 31, form method not special qualification of the hot melt resin bed of having been handled by pattern, for example can use known method such as print process.
When the oxide semiconductor electrode of this mode of use is made dye-sensitized solar cell; Said pattern treatment process both can not contain at porous layer to be implemented pattern and handles under dye-sensitized dose the state; In addition also can after state dye-sensitized dose support operation after, contain at porous layer and to implement pattern under dye-sensitized dose the state and handle.
The oxide semiconductor electrode of this mode can be used as employed coloring matter sensitization type light charging capacitor in the coloring matter sensitization type light charging capacitor and decomposes in substrate and the dye-sensitized solar cell employed dye-sensitized solar cell with uses such as base materials with employed electroluminescent display in base material, the electroluminescent display with base material, the pollutant that can use light-catalyzed reaction to decompose the pollutant in the atmosphere; Yet wherein, be more suitable for being used for the employed dye-sensitized solar cell of dye-sensitized solar cell and use base material.
6. the manufacturing approach of oxide semiconductor electrode
As the manufacturing approach of the oxide semiconductor electrode of this mode, so long as can make the method for oxide semiconductor electrode, just not special the qualification with said formation.As this kind method, as a rule, use to press from both sides at a distance from adhesive linkage, on said base material, the method that the mode of the laminated body of transfer printing porous layer and the 1st electrode layer is made.For the manufacture method of this kind oxide semiconductor electrode, will in reference to accompanying drawing, describe.Fig. 6 is the skeleton diagram of an example of manufacture method of the oxide semiconductor electrode of this mode of expression.As shown in Figure 6; The oxide semiconductor electrode of this mode can utilize following method to make; Promptly; Form operation utilizing by the base material that has heat resistant substrate that forms operation (Fig. 6 (a)) at the porous layer that forms porous layer 24 on the heat resistant substrate 25, forms operation (Fig. 6 (b)), the base material of on said the 1st electrode layer 23, giving adhesive linkage 22 and base material 21 forms operation (Fig. 6 (c)) formation at the 1st electrode layer that forms the 1st electrode layer 23 on the said porous layer 24; Made after the oxide semiconductor electrode 40 that has heat resistant substrate; In heat resistant substrate stripping process shown in Figure 7, the heat resistant substrate 25 that the said oxide semiconductor electrode 40 that has heat resistant substrate is had is peeled off from said porous layer 24.In this mode, as this kind method, the method that is described in detail in the part of " manufacturing approach of F. oxide semiconductor electrode " stated after for example can being suitable for.
A-2: the oxide semiconductor electrode of mode two
Below, the oxide semiconductor electrode of mode two of the present invention is described.The 1st electrode layer that the oxide semiconductor electrode of mode two of the present invention is adhesive linkages of having base material, be formed on the said base material and processed by thermoplastic resin, be formed on the said adhesive linkage and processed by metal oxide, be formed on said the 1st electrode layer and contain the oxide semiconductor electrode of the porous layer of metal-oxide semiconductor (MOS) particulate; Wherein, said porous layer by the oxide semiconductor layer that contacts with said the 1st electrode layer, be formed on the said oxide semiconductor layer and compare the higher folder interlayer of void content and constitute with said oxide semiconductor layer.
The summary section of an example of the oxide semiconductor electrode of expression mode two is shown among Fig. 4.As shown in Figure 4; The characteristic of the oxide semiconductor electrode 20b of mode two of the present invention is, porous layer 24 by the oxide semiconductor layer 24a that contacts with said the 1st electrode layer, be formed at said oxide semiconductor layer 24a and go up and compare the higher folder interlayer 24b of void content and constitute with said oxide semiconductor layer 24a.
According to the oxide semiconductor electrode of mode two,, thereby just can obtain to utilize the oxide semiconductor electrode of the highly productive of transfer printing mode because of said porous layer is made up of said oxide semiconductor layer, said folder interlayer.That is, when utilizing the transfer printing mode to form porous layer, peel off porous layer from heat resistant substrate, however when heat resistant substrate and porous layer connect airtight power when high, when heat resistant substrate is peeled off porous layer, porous layer will be damaged, can't obtain high-quality porous layer.As shown in Figure 4, because porous layer 24 is made up of oxide semiconductor layer 24a, said folder interlayer 24b, can reduce the power of connecting airtight of porous layer 24 and heat resistant substrate thus, therefore just can obtain to utilize the oxide semiconductor electrode of the highly productive of transfer printing mode.Below, will respectively the constituting of oxide semiconductor electrode of this mode be described.
1. porous layer
At first, porous layer is described.The characteristic of the porous layer of this mode is, by the oxide semiconductor layer that contacts with said the 1st electrode layer, be formed on the said oxide semiconductor layer and compare the higher folder interlayer of void content with said oxide semiconductor layer and constitute.Therefore in this mode,, when utilizing the transfer printing mode to form porous layer, just can reduce the power of connecting airtight of said heat resistant substrate and porous layer, can obtain to utilize the oxide semiconductor electrode of the highly productive of transfer printing mode through porous layer being made as 2 layers of structure of this kind.
(1) formation of porous layer
In this mode, the said folder interlayer that constitutes porous layer does not need adequate relief to be formed on the said oxide semiconductor layer, both can have thickness distribution, can on oxide semiconductor layer, have in addition not have the part of pressing from both sides interlayer yet.This is because even the folder interlayer exists with this kind mode, also can obtain to utilize the oxide semiconductor electrode of the highly productive of transfer printing mode.
As long as the thickness ratio of oxide semiconductor layer of this mode and folder interlayer is according to the decisions at random such as manufacturing approach of the oxide semiconductor electrode of this mode.Wherein, in this mode, the thickness of said oxide semiconductor layer and said folder interlayer is than in preferred 10: 0.1～10: 5 scope, wherein more preferably in 10: 0.1～10: 3 the scope.This be because; When the thickness that presss from both sides interlayer is bigger than said scope; Then, might in porous layer, can't contain dye-sensitized dose of aequum, in addition for example the oxide semiconductor electrode of this mode being used under the situation of dye-sensitized solar cell; When thickness than said scope more hour, then have the situation that the productivity of the oxide semiconductor electrode that can't help this mode improves.
Though the void content as said oxide semiconductor layer needs only the decisions at random such as purposes according to the oxide semiconductor electrode of this mode; But wherein; In this mode; In the scope of the void content of said oxide semiconductor layer preferred 10%～60%, wherein, more preferably in 20%～50% the scope.This be because; For example, be used at oxide semiconductor electrode under the situation of dye-sensitized solar cell this mode, when the void content of oxide semiconductor layer than said scope more hour; Then might damage the function that to conduct to the 1st electrode layer by the electric charge of dye-sensitized dose of generation; In addition, when bigger, then might in oxide semiconductor layer, contain dye-sensitized dose of aequum than said scope.
As the void content of said folder interlayer, as long as bigger than the void content of said oxide semiconductor layer, just not special the qualification, yet as a rule, in preferred 25%～65% the scope, wherein more preferably in 30%～60% the scope.This be because, when the void content of folder interlayer is lower than said scope, then owing to improve with the power of connecting airtight of heat resistant substrate, therefore just might be not good on productivity, in addition, when higher, then have the situation that is difficult to form uniform folder interlayer than said scope.
(2) metal-oxide semiconductor (MOS) particulate
Employed metal-oxide semiconductor (MOS) particulate among the present invention since with the part of 3. porous layers (1) the metal-oxide semiconductor (MOS) particulate of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
(3) other compound
In the porous layer of the present invention, as required, also can contain other the compound beyond the metal-oxide semiconductor (MOS) particulate.As other compound of this kind and since with other the part of compound of 3. porous layers (2) of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
(4) porous layer
Porous layer of the present invention since with the part of 3. porous layers (3) porous layer of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
Porous layer of the present invention is preferably carried out pattern to be handled.This is because through porous layer being carried out the pattern processing, just can make oxide semiconductor electrode of the present invention be suitable for the high dye-sensitized solar cell of manufacturing module electromotive force.The pattern processing mode of the porous layer of this mode since with the part of 3. porous layers (3) porous layer of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
2. adhesive linkage
Below, the adhesive linkage of this mode is described.The characteristic of adhesive linkage of the present invention is to be made up of thermoplastic resin.
(1) thermoplastic resin
Employed thermoplastic resin in the adhesive linkage of this mode is so long as the resin that under required temperature, melts, just not qualification especially.Wherein, in this mode, in preferred 50 ℃～200 ℃ scope of the fusing point of thermoplastic resin, in preferred especially 60 ℃～180 ℃ scope, wherein more preferably in 65 ℃～150 ℃ the scope.This be because, when fusing point is lower than said scope, then for example at the dye-sensitized solar cell of the oxide semiconductor electrode making that will use this mode; Under the situation about using without; Just might keep the connecting airtight property between base material and the 1st electrode layer fully, in addition, when fusing point is higher than said scope; Then for example when utilizing transfer printing to make dye-sensitized solar cell by the oxide semiconductor electrode of this mode; Owing in transfer printing process, need the heating process more than the fusing point, therefore, have the situation that base material self receives the damage that is caused by heat according to the kind of employed base material in this mode.
In addition, the preferred adhesive resin of said thermoplastic resin.As this kind adhesive resin, for example can enumerate cellulose derivatives such as polyolefin, ethylene-vinyl acetate copolymer, ethylene acrylic acid co polymer, ethyl cellulose, Triafol T such as polyethylene, polypropylene, polyisobutene, polystyrene, ethylene-propylene rubber, gather Pioloform, polyvinyl acetal, polyacetals, polyamide, polyimides, nylon, mylar, polyurethane resin, epoxy resin, silicones, the fluorine resins etc. such as copolymer, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral resin of (methyl) acrylic acid and its ester.Wherein, consider preferred polyolefm, ethylene-vinyl acetate copolymer, polyurethane resin, epoxy resin, silane-modified resin and acid modified resin from cementability, the viewpoint of tolerance, light transmission and transfer printing property to electrolyte.
In addition, as other example of said adhesive resin, can enumerate polyolefin compound as follows.As said polyolefin compound, the carbon number such as homopolymers, these alpha-olefins and ethene, propylene, 1-butylene, 3-methyl-1-butene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene that for example can enumerate carbon numbers such as ethene, propylene, 1-butylene and be about 2～8 alpha-olefin is about 2～20 other copolymer, (anhydrous) maleic acid modified resin, silane-modified resin or the olefin type elastomer etc. of alpha-olefin, vinyl acetate, (methyl) acrylic acid, (methyl) acrylic acid ester etc.
As the homopolymers or the copolymer of said alpha-olefin, for example can enumerate the polyolefin such as Alathon, ethylene-propylene copolymer, random polypropylene, Noblen, 1-chevron of low middle-high density polyethylene etc. (branched or straight chain shape); Ethene-butene-1 copolymer; Ethylene-propylene-butene-1 copolymer; Ethene-4 methyl 1 pentene copolymer; Ethene-1-hexene copolymer; Ethene-1-octene copolymer; Propylene-butene-1 copolymer; Propylene-ethylene-butene-1 copolymer; Ethylene-vinyl acetate copolymer; Ethene-(methyl) acrylic copolymer or its ionomer; Ethene such as ethylene-ethyl acrylate copolymer-(methyl) acrylate copolymer; Maleic acid is ethene improved-vinyl acetate copolymerized resin; The maleic acid modified polyolefin resin; Ethylene-ethyl acrylate-maleic anhydride copolymer etc. (anhydrous) maleic acid modified resin; Improved polyalkenes such as silane-modified resin that constitute by the copolymer of ethene unsaturated silane compound and polyolefin compound etc.
As said olefin type elastomer, can enumerate polyethylene or polypropylene as hard fragment, with ethylene-propylene rubber (EPR) or ethylene-propylene-diene rubber (EPDM) as the elastomer of soft segment etc.
These polyolefin compounds can two or more alone or in combination uses.In the middle of these polyolefin compounds; Consider from the viewpoint of cementability; Preferred improved polyalkene, preferred especially ethene improved resinoid (ethylene copolymers such as the silane-modified resin that for example constitutes, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer etc.) by the copolymer of ethene unsaturated silane compound and polyolefin compound.Wherein, most preferably with the situation of silane-modified resin as adhesive linkage.
In this mode, in the middle of described thermoplastic resin, more preferably use silane-modified resin.This is because owing to through using silane-modified resin, can estimate that then adhesive linkage and base material and the 1st electrode layer form chemical bond, the bonding force that therefore adhesive linkage is shown is more firm.For employed silane-modified resin in this mode and since with the part of the silane-modified resin of 1. adhesive linkages (1) of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
(2) other compound
In the adhesive linkage of this mode, can contain other the compound beyond said as required.As employed other compound in this mode and since with other the part of compound of 1. adhesive linkages (2) of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
(3) adhesive linkage
The thickness of the adhesive linkage of this mode since with the part of 1. adhesive linkages (3) adhesive linkage of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
3. the 1st electrode layer
Employed the 1st electrode layer in this mode since with the part of 2. the 1st electrode layers of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
4. base material
Employed base material in this mode since with the part of 4. base materials of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
5. the manufacture method of oxide semiconductor electrode
As the manufacturing approach of the oxide semiconductor electrode of this mode, so long as can make the method for oxide semiconductor electrode, just not special the qualification with said formation.As this kind method, as a rule, use to press from both sides at a distance from adhesive linkage, on said base material, the method that the mode of the laminated body of transfer printing porous layer and the 1st electrode layer is made.In this mode, as this kind mode, the mode that is described in detail in the part of " manufacturing approach of F. oxide semiconductor electrode " stated after can being suitable for.
B. the oxide semiconductor electrode that has heat resistant substrate
Below, the oxide semiconductor electrode that has heat resistant substrate of the present invention is described.The characteristic that has the oxide semiconductor electrode of heat resistant substrate of the present invention is, on the porous layer that oxide semiconductor electrode had of the oxide semiconductor electrode of said mode one or said mode two, has heat resistant substrate.
Below, in reference to accompanying drawing, the oxide semiconductor electrode that has heat resistant substrate of the present invention is described.Fig. 9 is the summary section of an example of the expression oxide semiconductor electrode that has a heat resistant substrate of the present invention.As shown in Figure 9, the oxide semiconductor electrode 30 that has heat resistant substrate of the present invention is on the porous layer 24 that oxide semiconductor electrode 20b is had, and has the electrode of heat resistant substrate 25.
According to the oxide semiconductor electrode that has heat resistant substrate of the present invention; Owing on the porous layer that oxide semiconductor electrode had of the oxide semiconductor electrode of said mode one or said mode two, have heat resistant substrate; Therefore in heat resistant substrate stripping process shown in Figure 7; Through said heat-resistant material is peeled off, just can easily process the good oxide semiconductor electrode of connecting airtight property of each layer.
Below, will describe each formation that has the oxide semiconductor electrode of heat resistant substrate of the present invention.
1. heat resistant substrate
Employed heat resistant substrate among the present invention since with after the content put down in writing in the part of " the D. oxide semiconductor electrode use laminated body " stated identical, the explanation omission therefore will be here.
2. oxide semiconductor electrode
Employed oxide semiconductor electrode among the present invention since with the part of said " A-1: the oxide semiconductor electrode of mode one " and said " A-2: the oxide semiconductor electrode of mode two " in the content put down in writing identical, therefore the explanation is here omitted.
3. the oxide semiconductor electrode that has heat resistant substrate
Though the oxide semiconductor electrode that has heat resistant substrate of the present invention can be used for coloring matter sensitization type light charging capacitor with the making of electrode, electroluminescent display with the making of electrode, making that polluter decomposes substrate and dye-sensitized solar cell with the making of base material etc.; Yet wherein, more be applicable to the making of dye-sensitized solar cell with base material.
4. the manufacture method that has the oxide semiconductor electrode of heat resistant substrate
As the manufacture method that has the oxide semiconductor electrode of heat resistant substrate of the present invention, so long as can make the method for the oxide semiconductor electrode that has heat resistant substrate, just not special the qualification with said formation.As this kind method, the method that is described in detail in the part of " E. has the manufacturing approach of the oxide semiconductor electrode of heat resistant substrate " stated after can being suitable for.
C. dye-sensitized solar cell
Below, dye-sensitized solar cell of the present invention is described.The characteristic of dye-sensitized solar cell of the present invention is, the oxide semiconductor electrode of the oxide semiconductor electrode of said mode one or said mode two and be made up of the 2nd electrode layer and opposed base material electrode base material is pressed from both sides at a distance from the dielectric substrate that contains redox couple and opposed.
For dye-sensitized solar cell of the present invention, in reference to accompanying drawing, describe.Figure 10 is the summary section of an example of expression dye-sensitized solar cell of the present invention.Shown in figure 10; Dye-sensitized solar cell 50 of the present invention is: oxide semiconductor electrode 20b folder is at a distance from the dielectric substrate 41 that contains redox couple; With constitute by the 2nd electrode layer 51 and opposed base material 52 to electrode base material 53 opposed batteries; Wherein, oxide semiconductor electrode 20b has: base material 21, the adhesive linkage 22 that is formed on the said base material 21 and is processed by thermoplastic resin, the 1st electrode layer 23 that is formed on the said adhesive linkage 22 and is processed by metal oxide, be formed on said the 1st electrode layer 23 and contain the porous layer 24 of the metal-oxide semiconductor (MOS) particulate that has supported dye-sensitized dose.
According to the present invention; Owing to use with the said thermoplastic resin that constitutes said adhesive linkage and contain the oxide semiconductor electrode of silane-modified resin as the mode one of characteristic; Can be so that the bonding force of the base material of said adhesive linkage and the 1st electrode layer be firm; Even therefore redox couple penetrates into adhesive linkage from said dielectric substrate, also can obtain can not damage the bonding stability of bonding force.So according to the present invention, can obtain not can be because of the dye-sensitized solar cell of the excellent in stability that produces time lapse such as splitting etc.
In addition; According to the present invention; Through use with said porous layer by the oxide semiconductor layer that contacts with said the 1st electrode layer, be formed on the said oxide semiconductor layer and compare the oxide semiconductor electrode that the higher folder interlayer of void content constitutes the mode two of characteristic with said oxide semiconductor layer, can obtain to utilize the dye-sensitized solar cell of the highly productive of transfer printing mode.
In addition, the oxide semiconductor electrode of mode one of the present invention and mode two since said adhesive linkage constitute by thermoplastic resin, therefore said adhesive linkage have flexible good, in adhesive linkage self, be difficult to produce characteristics such as " crackles ".So,, can obtain to have possessed the dye-sensitized solar cell of resisting the tolerance of external impact according to the present invention.
Below, respectively constituting of dye-sensitized solar cell of the present invention is elaborated.
1. dielectric substrate
At first, dielectric substrate of the present invention is described.The characteristic of dielectric substrate of the present invention is to contain redox couple.
(1) redox couple
As employed redox couple in the dielectric substrate of the present invention, so long as generally employed in dielectric substrate, just not special the qualification.For this kind redox couple and since with after the content put down in writing in the part of " manufacturing approach of G. dye-sensitized solar cell " stated identical, therefore the explanation is here omitted.
(2) other compound
In dielectric substrate of the present invention, other the compound as beyond the said redox couple can also contain additives such as crosslinking agent, Photoepolymerizationinitiater initiater, tackifier, normal temperature fused salt.
(3) dielectric substrate
No matter dielectric substrate is can by gel, solid, shaped or liquid any morphotic dielectric substrate.No matter dielectric substrate is being made as under the gelatinous situation, be that any of physical gel or chemical gel can.Here, physical gel is the material that utilizes near interaction gelation room temperature of physics, and chemical gel is to utilize cross-linking reaction etc. to form the material of gel with chemical bond.
In addition, dielectric substrate is being made as under the liquid situation, for example can be with acetonitrile, methoxyacetonitrile, propene carbonate etc. as solvent, and can be with the liquid that contains redox couple, likewise be that cationic ionic liquid is as solvent with imidazole salts.
In addition, dielectric substrate is being made as under the situation of solid, shaped, so long as do not contain redox couple, and himself agent plays a role as cavity conveying layer gets final product, and for example also can be the cavity conveying agent that contains CuI, polypyrrole, polythiophene etc.
2. to electrode base material
Below, to of the present invention electrode base material is described.Of the present invention electrode base material is made up of the 2nd electrode layer and opposed base material.
(1) the 2nd electrode layer
The 2nd electrode layer of the present invention since with the part of 2. the 1st electrode layers of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
(2) opposed base material
The 2nd electrode layer of the present invention since with the part of 4. base materials of said " A-1: the oxide semiconductor electrode of mode one " in the content put down in writing identical, therefore the explanation is here omitted.
(3) other layer
Of the present invention in the electrode base material, as required, also can contain other the layer beyond said.As among the present invention employed other the layer, can enumerate Catalytic Layer.Among the present invention,, just can dye-sensitized solar cell of the present invention be processed the more good battery of generating efficiency through on said the 2nd electrode layer, forming Catalytic Layer.As the example of this kind Catalytic Layer, though the form of Pt of can having enumerated on said the 2nd electrode layer vapor deposition is not limited thereto.
3. oxide semiconductor electrode
Oxide semiconductor electrode of the present invention since with the part of said " A-1: oxide semiconductor electrode " in the content put down in writing identical, therefore the explanation is here omitted.
4. the manufacture method of dye-sensitized solar cell
As the manufacture method of dye-sensitized solar cell of the present invention, so long as can make the method for dye-sensitized solar cell, just not special the qualification with said formation.As this kind method, the method that is described in detail in the part of " manufacturing approach of G. dye-sensitized solar cell " stated after for example can being suitable for.
D. oxide semiconductor electrode is with the manufacturing approach of laminated body
At first, the manufacturing approach of oxide semiconductor electrode of the present invention with laminated body described.Oxide semiconductor electrode of the present invention with the characteristic of the manufacturing approach of the laminated body of laminated body is; Comprise: the folder interlayer that on heat resistant substrate, contains organic substance and metal-oxide semiconductor (MOS) particulate with pattern-like coating forms with applying liquid, makes it to be solidified to form the folder interlayer formation that the folder interlayer forms with pattern and forms operation with pattern; On the said heat resistant substrate and on said folder interlayer forms with pattern; Coating forms with applying liquid than the higher oxide semiconductor layer of concentration of metal-oxide semiconductor (MOS) particulate in solid formation branch with applying liquid phase with said folder interlayer formation, makes it to be solidified to form oxide semiconductor formation and uses the oxide semiconductor layer of layer to form with a layer formation operation; Process porous body through said folder interlayer formation is burnt till with layer with pattern and oxide semiconductor layer formation, form the firing process of folder interlayer and oxide semiconductor layer; The 1st electrode layer that on said oxide semiconductor layer, forms the 1st electrode layer forms operation.
According to the present invention; The oxide semiconductor electrode that can obtain to have the folder interlayer that has been made into pattern-like is used laminated body; Through using this oxide semiconductor electrode to use laminated body, the oxide semiconductor electrode that just can obtain on the 1st electrode layer, to press from both sides interlayer and oxide semiconductor layer patterning.In the oxide semiconductor electrode that folder interlayer and oxide semiconductor layer are not patterned; For example shown in Figure 11 (a), on all, form oxide semiconductor layer 63 ' on the surface of the 1st electrode layer 64 '; In addition; On this oxide semiconductor layer 63 ', be formed with folder interlayer 62 ', therefore on base material 65, only form 1 battery unit (cell) 70 that constitutes by the 1st electrode layer 64 ', oxide semiconductor layer 63 ' and folder interlayer 62 '; In the equipment that has used this kind oxide semiconductor electrode, have the output current that is difficult to obtain practicality, the situation of output voltage.In contrast; When the oxide semiconductor electrode that use utilizes the present invention to obtain is used laminated body; When making oxide semiconductor electrode, for example shown in Figure 11 (b), be patterned owing to can process oxide semiconductor layer 63 ' and press from both sides interlayer 62 '; Possessed the oxide semiconductor electrode that quilt and the form fit ground of this pattern formed and had the 1st electrode pattern 64 ' of the area bigger than said pattern in addition; On base material 65, form a plurality of battery units 70 that constitute by the 1st electrode pattern 64 ', oxide semiconductor layer 63 ' and folder interlayer 62 ', therefore can these battery units parallel connections be improved output current, perhaps connect and improve output voltage.
In addition, the manufacturing approach as in the past oxide semiconductor electrode has on heat resistant substrate, and folder forms the method for oxide semiconductor layer on heat resistant substrate at a distance from the organic membrane that is made up of the organic substance that does not contain the metal-oxide semiconductor (MOS) particulate.But; In said method; After having carried out burning till processing, because the thermal coefficient of expansion of contained metal-oxide semiconductor (MOS) particulate poor in contained organic substance, the oxide semiconductor in the organic membrane has between organic membrane and oxide semiconductor layer and be easy to generate problem of cracks.On the other hand,,, therefore do not have and be difficult to the problem heat resistant substrate peeled off from the oxide semiconductor layer directly under the situation that has formed oxide semiconductor layer on the heat resistant substrate not pressing from both sides fully because both connecting airtight property obviously improve at a distance from organic membrane.According to the present invention; The folder interlayer that contains the metal-oxide semiconductor (MOS) particulate through use forms with applying liquid, between heat resistant substrate and oxide semiconductor layer, forms the folder interlayer, just can suppress the generation in the crack that the difference because of thermal coefficient of expansion produces; In addition; Through use with after the oxide semiconductor layer stated form with applying the liquid phase folder interlayer lower and form with applying liquid than the concentration of metal-oxide semiconductor (MOS) particulate, form the folder interlayer, just can between heat resistant substrate and folder interlayer, give appropriate connecting airtight property and fissility; Can use laminated body by the oxide semiconductor electrode that utilizes the present invention to obtain, rate of finished products is made oxide semiconductor electrode goodly.In addition; Utilize oxide semiconductor electrode that the present invention obtains connecting airtight property difference with connecting airtight property, oxide semiconductor layer and the heat resistant substrate of the folder interlayer of laminated body and heat resistant substrate; Through utilizing the difference of this connecting airtight property, just can obtain the oxide semiconductor electrode that oxide semiconductor layer and folder interlayer have been patterned.For the manufacturing approach of this kind oxide semiconductor electrode, will after specify in " manufacturing approach of F. oxide semiconductor electrode " stated.
Below, with using accompanying drawing that the manufacturing approach of oxide semiconductor electrode of the present invention with laminated body specified.Figure 12 is the process chart of expression oxide semiconductor electrode of the present invention with an example of the manufacturing approach of laminated body.
At first, shown in Figure 12 (a), on heat resistant substrate 61, be coated with the cloth clamp interlayer with pattern-like and form, make it to be solidified to form the folder interlayer and form with pattern 62 (the folder interlayer forms and forms operation with pattern) with applying liquid.
Then, shown in Figure 12 (b), the coating oxide semiconductor layer forms with applying liquid on heat resistant substrate 61 and folder interlayer form with pattern 62, makes it to be solidified to form oxide semiconductor layer and forms with layer 63 (oxide semiconductor layer forms with layer formation operations).
Then; Burn till through range upon range of folder interlayer being formed form to implement to heat with the heat resistant substrate 61 of layer 63 with pattern 62 and oxide semiconductor layer; Promptly shown in Figure 12 (c), form as folder interlayer 62 ' and oxide semiconductor layer 63 ' (firing process) with porous body of intercommunicating pore.
Then, shown in Figure 12 (d), form the 1st electrode layer 64 (the 1st electrode layer forms operation), obtain oxide semiconductor electrode and use laminated body A through going up at oxide semiconductor layer 63 '.
Below, will be divided into each operation with the manufacturing approach of laminated body to oxide semiconductor electrode of the present invention and describe.
1. the folder interlayer forms and forms operation with pattern
At first, folder interlayer formation of the present invention being formed operation with pattern describes.Folder interlayer of the present invention forms and forms operation with pattern, is on heat resistant substrate, and the folder interlayer that contains organic substance and metal-oxide semiconductor (MOS) particulate with the pattern-like coating forms with applying liquid, makes it to be solidified to form the folder interlayer and forms the operation with pattern.
And said here folder interlayer forms and is meant with pattern, forms with applying the pattern that liquid is coated with and makes it to be solidified to form with pattern-like through pressing from both sides interlayer.In addition, after the folder interlayer stated be meant, burn till with pattern through said folder interlayer is formed, be used as porous body and the pattern that forms.In addition; When the oxide semiconductor electrode that will utilize manufacturing approach of the present invention to obtain was used for dye-sensitized solar cell with laminated body, said folder interlayer was meant that dye-sensitized dose of stating after the utilization supports any one situation that operation has supported dye-sensitized dose layer or do not supported dye-sensitized dose layer.
(1) the folder interlayer forms with applying liquid
At first, employed folder interlayer formation in this operation is described with coating liquid.Employed folder interlayer formation is to contain metal-oxide semiconductor (MOS) particulate and organic liquid at least with coating liquid in this operation.
(a) metal-oxide semiconductor (MOS) particulate
Employed metal-oxide semiconductor (MOS) particulate is in the end to press from both sides interlayer to form with pattern and become in the folder interlayer in this operation, has the particulate of the function of conduct charges.Form with applying in the liquid through said metal-oxide semiconductor (MOS) particulate being added to the folder interlayer, can prevent the generation in crack that the difference by thermal coefficient of expansion causes etc.
Said folder interlayer forms the content with the metal-oxide semiconductor (MOS) particulate in the solid formation branch that applies liquid; So long as than after the oxide semiconductor layer stated form in the content scope still less of the metal-oxide semiconductor (MOS) particulate in dividing with the solid formation that applies liquid just not special the qualification.Wherein, in this mode, the content of metal-oxide semiconductor (MOS) particulate is in said folder interlayer forms with the solid formation branch that applies liquid, in the scope of preferred 20 quality %～80 quality %, in the scope of preferred especially 30 quality %～70 quality %.
In addition; Though said metal-oxide semiconductor (MOS) particulate the folder interlayer form with apply in the liquid concentration if according to after the folder interlayer stated form with the coating process that applies liquid etc.; At random determine to get final product in forming with the scope of pattern can forming the good folder interlayer of flatness; But as a rule, in the scope of preferred 0.01 quality %～30 quality %, wherein more preferably in the scope of 0.1 quality %～15 quality %.
As employed metal-oxide semiconductor (MOS) particulate in this operation and since with the part of said " A. oxide semiconductor electrode " in the content put down in writing identical, therefore the explanation is here omitted.
(b) organic substance
Below, employed organic substance describes in the liquid with applying to said folder interlayer formation.Form with applying employed organic substance in the liquid as said folder interlayer, so long as after the material that is decomposed easily in the firing process stated, just not special the qualification.Wherein, in this operation, preferably use synthetic resin as said organic substance.This is because when using synthetic resin, because can be through at random selecting molecular weight or material, and obtain to possess the compound of required pyrolytic, the restriction of the treatment conditions of stating after therefore having of burning till processing advantage such as tail off.
As said synthetic resin, so long as the oxide semiconductor layer of stating after being difficult to be dissolved in forms with applying the resin in the employed solvent in the liquid, just not special the qualification.Wherein, in this operation, in the scope of the weight average molecular weight of synthetic resin preferred 2000～600000, in preferred especially 5000～300000 the scope, wherein more preferably in 10000～200000 the scope.This be because; When the said scope of the molecular weight ratio of synthetic resin is bigger; Thermal decomposition in the firing process of stating after then the having inadequate situation that becomes, in addition, when the said scope of molecular weight ratio more hour; The folder interlayer is formed with the viscosity that applies liquid reduce the metal-oxide semiconductor (MOS) particle coagulation.
As the concrete example of employed synthetic resin in this operation, can enumerate polyalcohols such as acrylic resin that cellulosic resins such as ethyl cellulose, methylcellulose, NC Nitroncellulose, acetyl group cellulose, acetyl group ethyl cellulose, cellulose propionate, hydroxypropyl cellulose, butyl cellulose, benzylcellulose, NC Nitroncellulose or methyl methacrylate, EMA, methacrylic acid tertiary butyl ester, methacrylic acid n-butyl, isobutyl methacrylate, isopropyl methacrylate, 2 ethyl methacrylate, methacrylic acid 2-ethylhexyl, methacrylic acid 2-hydroxyethyl ester etc. be made up of polymer or copolymer, polyethylene glycol etc.In this operation, both can a kind of independent use of these synthetic resin also can be mixed two or more synthetic resin in addition and use.
Though forming with the concentration that applies liquid with respect to the folder interlayer of said synthetic resin is not specially limited, in the scope of preferred 0.01 quality %～30 quality %, in the scope of preferred especially 0.1 quality %～15 quality %.
(c) solvent
Employed folder interlayer formation both can be the coating liquid that does not contain solvent with applying liquid in this operation, also can be the coating liquid that contains solvent.Form with applying in the liquid at the folder interlayer and to contain under the situation of solvent, preferably with respect to organic optimum solvent, employed solvent selected main considered the volatility of solvent, employed organic dissolubility and suitably selected in this operation.Specifically, can enumerate ketone, hydro carbons, ester class, alcohols, halogenated hydrocarbons, ethylene glycol derivative, ethers, ether-ether class, amide-type, acetates, ketone ester class, gylcol ether, sulfone class, sulfoxide class etc.They can use a kind, or mix and use more than 2 kinds.Wherein, more preferably organic solvents such as acetone, methyl ethyl ketone, toluene, methyl alcohol, isopropyl alcohol, normal propyl alcohol, n-butanol, isobutanol, terpinol, ethyl cellosolve, butyl cellosolve, BC.This is because be applied on the heat resistant substrate with coating liquid because the folder interlayer forms, so through using said organic solvent, just can wettability coat on the heat resistant substrate well.
(d) additive
In addition, in this operation, form with the coating adaptability that applies liquid, also can use various additives in order to improve said folder interlayer.As additive, for example can use surfactant, viscosity modifier, dispersing aid, pH conditioning agent etc.As said pH conditioning agent, for example can enumerate nitric acid, hydrochloric acid, acetic acid, dimethyl formamide, ammonia etc.In addition, as dispersing aid, for example can enumerate polymer such as polyethylene glycol, hydroxyethylcellulose, carboxymethyl cellulose, surfactant, acid, chelating agent etc.
(2) heat resistant substrate
As employed heat resistant substrate in this operation, so long as have to after the stable on heating substrate that burns till the heating-up temperature when handling stated, just not special the qualification.As this kind heat resistant substrate, can enumerate the heat resistant substrate of processing by glass, pottery or metallic plate etc.Wherein, in this operation, more preferably use metallic plate as heat resistant substrate with flexibility.This is because through using this kind heat resistant substrate, that states after can at high temperature carrying out fully burns till processing, therefore can improve the caking property between the metal-oxide semiconductor (MOS) particulate.In addition, said heat resistant substrate is preferably reused.
As the thickness of said heat resistant substrate, though according to the material of heat resistant substrate and different, in the scope of for example preferred 10 μ m～1mm, wherein more preferably in the scope of 50～500 μ m, in the scope of preferred especially 80～300 μ m.
In addition, said heat resistant substrate preferably has flexibility.Make oxide semiconductor electrode etc. because so just can utilize Roll to Roll mode.
In addition, said heat resistant substrate preferably has acid resistance.What is called of the present invention " acid resistance " is meant; After the folder interlayer stated form use apply liquid or after the oxide semiconductor layer stated form and use under the situation of coating liquid as acidity; The acid resistance that belongs to not the degree that can corrode because of its constituent; Even perhaps what are when corroding to some extent, its sour decomposition product can not produce the acidity of the degree that goes bad, peels off etc. of folder interlayer, oxide semiconductor layer etc. yet.
In addition, as material, though not special the qualification for example can be enumerated metals such as metal monomer, metal alloy and metal oxide etc. with the acid proof heat resistant substrate of this kind.As said metal monomer, for example can enumerate Ti, W, Mo, Nb, Cr, Ni, Ag, Zr, Pt, Ta, Au etc., wherein more preferably Ti, W, Pt, Au.As said metal alloy, for example can enumerate SUS, Ti alloy, Fe alloy, Ni alloy, Al alloy, W alloy, Mg alloy, Co alloy, Cr alloy etc., wherein more preferably SUS, Ti alloy, Al alloy.As said metal oxide, for example can enumerate Si oxide, Al oxide, Ti oxide, Zr oxide, Sn oxide, Cr oxide, W oxide etc., wherein, more preferably Si oxide, Al oxide, Ti oxide.
In addition, having said acid proof heat resistant substrate both can be individual layer, also can be multilayer.As having the concrete example that acid proof heat resistant substrate is the situation of multilayer, for example can enumerate the examples such as lip-deep acid resistance layer that said heat resistant substrate has the thermal endurance layer, is formed at least one side of said thermal endurance layer.Under this situation, as a rule, on the acid resistance layer, be coated with the cloth clamp interlayer and form with applying liquid etc.
Said thermal endurance layer since quilt with after the acid resistance layer stated use, therefore said thermal endurance layer self need not have acid resistance, as long as have enough thermal endurances, can use material arbitrarily.As the material of this kind thermal endurance layer, for example can enumerate metal, glass, pottery etc., wherein more preferably metal.In addition, as said metal, specifically, can enumerate metal monomer, metal alloy and metal oxide etc.In addition, in general said metal monomer, metal alloy and metal oxide owing to have enough thermal endurances, so not special qualification the such as its kind.And, as said metal monomer, specifically, preferred Ti, W, Pt, Au etc.; As said metal alloy, specifically, preferred SUS, Ti alloy, Al alloy etc.; As said metal oxide, specifically, preferred Si oxide, Al oxide, Ti oxide etc.
In addition, as the thickness of said thermal endurance layer, though not special the qualification, in the scope of for example preferred 10 μ m～10mm, wherein more preferably in the scope of 50 μ m～5mm, in the scope of preferred especially 80 μ m～2mm.
On the other hand, said acid resistance layer is the lip-deep layer that is formed at least one side of said thermal endurance layer.As the material of this kind acid resistance layer, not special the qualification can be used and described " material with acid proof heat resistant substrate " identical materials.In addition, as the thickness of said acid resistance layer, though not special the qualification, in the scope of for example preferred 10 μ m～10mm, wherein more preferably in the scope of 50 μ m～5mm, in the scope of preferred especially 80 μ m～2mm.
In addition, as the combination of said thermal endurance layer and said acid resistance layer, not special the qualification can at random be selected.For example, the material that can enumerate the thermal endurance layer is metal, glass or pottery, and the material of acid resistance layer is the combination of metal, and wherein, the material of more preferably said thermal endurance layer and said acid resistance layer is the combination of metal.
Material as said thermal endurance layer and said acid resistance layer is the combination of metal; The material that for example can enumerate the thermal endurance layer is metal monomer, metal alloy or metal oxide, and the material of acid resistance layer is the combination of metal monomer, metal alloy or the metal oxide beyond the employed metal in the said thermal endurance layer.Specifically, as the combination of the material of the material/acid resistance layer of thermal endurance layer, can enumerate Ti monomer/Ti oxide, SUS/Cr monomer, SUS/Si oxide, SUS/Ti oxide, SUS/Al oxide, SUS/Cr oxide etc.
In addition, when the material of said thermal endurance layer and said acid resistance layer is metal, in the best said thermal endurance layer in contained metallic element and the said acid resistance layer contained metallic element different.And so-called here " in the thermal endurance layer contained metallic element " is meant contained maximum metallic element in the thermal endurance layer.So even for example when SUS contains Cr, Ni etc., " in the thermal endurance layer contained metallic element " still is Fe.In addition, also identical for " in the acid resistance layer contained metallic element ".As the combination of this kind thermal endurance layer and acid resistance layer,, can enumerate SUS/Cr monomer, SUS/Si oxide, SUS/Ti oxide, SUS/Al oxide, SUS/Cr oxide etc. as the combination of the material of the material/acid resistance layer of thermal endurance layer.
As the method that on the thermal endurance layer, forms the acid resistance layer; Though not special the qualification for example can be enumerated dry types such as CVD method such as PVD method such as vacuum vapour deposition, sputtering method, ion plating method and plasma CVD, hot CVD, atmospheric pressure CVD and become wet types such as embrane method, coating method, sol-gal process to become embrane method etc.In addition; For example in the thermal endurance layer, use under the situation of metal monomer or metal alloy; Also can carry out chemical membranes such as pellumina processing, chromate gloss finish, the processing of manganese phosphate coverlay to its surface and handle, the layer that utilizes the chemical membrane processing to obtain is used as the acid resistance layer.In addition, also can use spray heating decomposition etc.
In addition, employed heat resistant substrate is preferably in the surface and possesses the wettability change layer that wettability is changed because of the light-catalysed effect that is accompanied by energy exposure in this operation.This be because, can be along said wettability change pattern, precision forms the folder interlayer goodly and forms and to use pattern.Specifically, can enumerate following method etc., that is,, make the wettability change pattern that specific part is made as hydrophilic region, form the formation of folder interlayer along this wettability change pattern and use pattern through carry out energy exposure to the wettability change layer.When heat resistant substrate possesses said wettability change layer, be preferably in and carry out said folder interlayer and form with pattern and form before the operation, earlier said wettability change layer is carried out energy exposure, form the wettability change pattern.
In addition, as the formation of said wettability change layer, so long as the formation that wettability changes just do not limit especially because of the light-catalysed effect that is accompanied by energy exposure makes.For example; Can enumerate the wettability change layer has photochemical catalyst and contains layer, is formed at this photochemical catalyst and contains that layer is gone up and the formation, the wettability change layer that contain said characteristic variations properties of materials change layer is not contain photochemical catalyst to contain said characteristic variations properties of materials change layer because of the light-catalysed effect that is accompanied by energy exposure makes formation, the wettability change layer of the characteristic variations material of characteristic variations have the photochemical catalyst that contains photochemical catalyst at least; And the photochemical catalyst that contains photochemical catalyst that makes other formation contains layer to be faced with near the of said wettability change layer mutually; Utilize this photochemical catalyst to contain the effect of the photochemical catalyst in the layer, in the wettability change layer, form the formation of wettability change pattern etc.For this kind photochemical catalyst and characteristic variations material etc., for example can use the spy to open 2001-074928 communique, spy and open 2003-209339 communique and special and open the material of being announced in the 2003-222626 communique etc.
(3) the folder interlayer forms the formation method with pattern
In this operation,, use method of patterning so long as can obtain required folder interlayer formation as on said heat resistant substrate, said folder interlayer being formed with applying the method for liquid with the pattern-like coating; Just not special the qualification for example can be enumerated following method, promptly; Form with applying liquid through use known coating process to be coated with the cloth clamp interlayer comprehensively, form with layer and on heat resistant substrate, form the folder interlayer, then at heat resistant substrate; Formation is carried out mask process with layer to the folder interlayer, makes it to have given pattern, thereafter; Use can be dissolved the folder interlayer and formed the solvent with layer, and the zone of not carried out mask process is removed.As said known coating process; Specifically, can enumerate mould cladding process, intaglio plate cladding process, reverse intaglio plate cladding process, cylinder cladding process, reverse cylinder cladding process, excellent cladding process, scraper cladding process, knife coating, air-blade type cladding process, slit die cladding process, sliding die cladding process, immersion coating method, fine excellent cladding process, the fine excellent cladding process of reverse, stencil printing (rotation mode) etc.In addition, form solvent, for example can enumerate the folder interlayer and form with applying in the liquid employed solvent etc. with layer as dissolving the folder interlayer.
In addition; As on said heat resistant substrate, said folder interlayer being formed with applying other the method for liquid with the pattern-like coating, for example can enumerate following method etc., promptly; Mask process is carried out on the heat resistant substrate surface; Use the coating comprehensively on heat resistant substrate and mask of known coating process then, thereafter, mask is removed.Known coating process is identical with described method.In addition, use mould cladding process and woodburytype etc. directly to form the folder interlayer to form and use method of patterning as on said heat resistant substrate, said folder interlayer being formed with applying the method for distinguishing of liquid with the pattern-like coating, for example can enumerating.This method is not use mask ground to form the formation of folder interlayer to use method of patterning, is method good in industry.In addition, have described wettability change layer, and be pre-formed under the situation of wettability change pattern, be coated with comprehensively, form along the folder interlayer formation of wettability change pattern and use pattern through utilizing known coating process at said heat resistant substrate.
(4) the folder interlayer forms and uses pattern
The folder interlayer that utilizes this operation to obtain forms the shape with pattern, can be according to the at random decisions such as purposes of the oxide semiconductor electrode that utilizes manufacturing approach of the present invention to obtain with laminated body.Wherein, in the present invention, specifically, can enumerate rectangle, square, circle, ellipse, trapezoidal or figure, literal, picture or mark etc., wherein, consider from the viewpoint that current collecting efficiency improves, more preferably rectangle with design.
In addition, particularly form and be made under the rectangular situation, form in the scope with the preferred 5～150mm of live width of pattern, wherein more preferably in the scope of 8～100mm as the folder interlayer with pattern at the folder interlayer that utilizes this operation to obtain.This be because, when having surpassed said scope, then the ohmic loss of the 1st electrode layer increases, current collecting efficiency might reduce, and when less than said scope, then might guarantee mechanical strength fully.In addition, form interval, in the scope of preferred 0.1～100mm, wherein more preferably in the scope of 1～50mm with pattern as the folder interlayer.This is because when surpassing said scope, then module might large tracts of landization, when less than said scope, then is difficult to precision and forms the folder interlayer and form and use pattern goodly.
In addition; Form thickness as the folder interlayer that utilizes this operation to obtain with pattern; Though not special the qualification, after be used as porous body in the firing process stated when forming, preferably adjust decision according to the mode of thickness of putting down in writing in " the 3. firing process " stated after reaching.Specifically, in the scope of preferred 0.01 μ m～50 μ m, wherein more preferably in the scope of 0.01 μ m～30 μ m.
2. oxide semiconductor layer forms with layer and forms operation
Below, oxide semiconductor layer formation is formed an operation with layer describe.Oxide semiconductor layer of the present invention forms and forms operation with layer is following operation; Promptly; On said heat resistant substrate and said folder interlayer form with pattern; Coating forms with applying liquid phase with said folder interlayer and forms with applying liquid at the solid higher oxide semiconductor layer of concentration that forms in dividing than metal-oxide semiconductor (MOS) particulate, makes it to be solidified to form oxide semiconductor layer and forms with layer.
And said here oxide semiconductor layer forms with layer, is meant through the coating oxide semiconductor layer to form with the layer that applies liquid and make it to be solidified to form.In addition; When the oxide semiconductor electrode that will utilize manufacturing approach of the present invention to obtain was used for dye-sensitized solar cell with laminated body, dye-sensitized dose of stating after also referring to utilize of oxide semiconductor layer supported any one situation that operation has supported dye-sensitized dose layer or do not supported dye-sensitized dose layer.
(1) oxide semiconductor layer forms with applying liquid
Employed oxide semiconductor layer formation in this operation is described with coating liquid.Employed oxide semiconductor layer formation is the liquid that contains metal-oxide semiconductor (MOS) particulate and resin at least with coating liquid in this operation; Form with applying the liquid phase ratio with said folder interlayer, the metal-oxide semiconductor (MOS) particulate is adjusted De Genggao in the solid concentration that forms in dividing.
(a) metal-oxide semiconductor (MOS) particulate
Employed metal-oxide semiconductor (MOS) particulate in this operation is that in the end oxide semiconductor layer forms when layer becoming oxide semiconductor layer, has the particulate of the function of conduct charges.
Form with applying the concentration of metal-oxide semiconductor (MOS) particulate in solid formation divides in the liquid as said oxide semiconductor layer; So long as form with applying liquid higher than said folder interlayer; Just not special the qualification, yet, as a rule; In the scope of preferred 50 quality %～100 quality %, in the scope of preferred especially 65 quality %～90 quality %.This be because; For example; When the oxide semiconductor electrode that will utilize manufacturing approach of the present invention to obtain is used for dye-sensitized solar cell with laminated body; Owing to, in the oxide semiconductor layer that the porous body that after being used as firing process, obtains forms, can support dye-sensitized dose of q.s on its pore surface through using this kind oxide semiconductor layer to form with applying liquid; Therefore in the oxide semiconductor layer that in the end obtains, can obtain to conduct the function of the electric charge that utilizes rayed and from dye-sensitized dose, produce fully.
In addition; Though forming with the concentration that applies liquid according to coating process etc. and different of said metal-oxide semiconductor (MOS) particulate with respect to oxide semiconductor layer; But specifically, in the scope of preferred 5 quality %～50 quality %, wherein more preferably in the scope of 10 quality %～40 quality %.This is because through using the formation of this kind oxide semiconductor layer with applying liquid, oxide semiconductor layer is formed with a layer film forming.
In addition, do not limit though the particle diameter of said metal-oxide semiconductor (MOS) particulate is special, specifically, preferably in the scope of 1nm～10 μ m, wherein more preferably in the scope of 10nm～1000nm.When the said scope of size ratio more hour, then, have each particle coagulation owing to self be difficult to make this kind particulate, form the situation of offspring, therefore not ideal enough.On the other hand; When the said scope of size ratio was bigger, then because the surface area of oxide semiconductor layer reduces, the oxide semiconductor electrode that therefore for example utilizes manufacturing approach of the present invention to obtain in use was used laminated body; Made under the situation of dye-sensitized solar cell; Because the pigment loading of oxide semiconductor layer reduces, might make performance reduce, therefore not ideal enough.
In addition, also can be with having the interior particle diameter of said scope and the different of the same race or dissimilar metal oxide semiconductor particulate mixing use of particle diameter.This is because like this, owing to can improve light scattering effect, close more light in the oxide semiconductor layer that can in the end obtain, so can carry out dye-sensitized dose light absorption effectively.For example, can enumerate the metal-oxide semiconductor (MOS) particulate in the scope that is in 10～50nm, the metal-oxide semiconductor (MOS) particulate that is in the scope of 50～800nm are mixed situation about using.
In addition, as this kind metal-oxide semiconductor (MOS) particulate since with said " 1. folder interlayer form form operation " with pattern among the content put down in writing identical, therefore the explanation is here omitted.
(b) resin
The emptying aperture that employed resin is given porous body for the firing process of stating after utilizing in this operation uses.In addition, through changing the use amount of resin, can adjust oxide semiconductor layer and form with the viscosity that applies liquid.
Though said resin does not form with the concentration that applies liquid is special with respect to oxide semiconductor layer and limits; But as a rule; In the scope of preferred 0.1 quality %～30 quality %; In the scope of preferred especially 0.5 quality %～20 quality %, wherein more preferably in the scope of 1 quality %～10 quality %.
As this kind resin; For example except cellulosic resin, polyester resin, polyamide-based resin, polyacrylate resinoid, polyacrylic acid resinoid, polycarbonate resin, polyurethane resin, polyolefin resin, polyvinyl acetal resinoid, fluorine-type resin, gather inferior imide resin etc., can also enumerate the polyalcohols of polyethylene glycol and so on etc.
(c) solvent
Employed oxide semiconductor layer formation both can be the coating liquid that does not contain solvent with applying liquid in this operation, also can be the coating liquid that contains solvent., used under the situation of solvent oxide semiconductor layer in forming with coating liquid, so long as dissolve the solvent of said resin, and described folder interlayer forms the solvent that employed organic substance is difficult to dissolve in the formation with pattern, just not special qualification.Specifically, can enumerate all kinds of solvents such as water or methyl alcohol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, terpinol, carrene, acetone, acetonitrile, ethyl acetate, the tert-butyl alcohol.Wherein, the more preferably solvent of water or alcohols.This is because employed organic solvent mixes the solvent of water or alcohols in the liquid with applying owing to not forming with said folder interlayer, can prevent that therefore said folder interlayer from forming a situation of mixing with layer with pattern and oxide semiconductor layer formation.
(d) additive
In addition, in this operation, form with the coating adaptability that applies liquid, also can use various additives in order to improve said oxide semiconductor layer.For example,, can use surfactant, viscosity modifier, dispersing aid, pH conditioning agent etc. as additive, however since with said " 1. folder interlayer form form operation " with pattern in employed additive identical, therefore the explanation is here omitted.In addition, in this operation,, especially preferably use polyethylene glycol as dispersing aid.This be because, through changing the molecular weight of polyethylene glycol, the viscosity that just can regulate dispersion liquid, the adjustment of the formation of the oxide semiconductor layer that can be difficult to peel off, the void content of oxide semiconductor layer etc.
(2) oxide semiconductor layer forms the formation method with layer
In this operation; Coat said folder interlayer formation with the method on the pattern as said oxide semiconductor layer being formed with coating liquid; So long as known coating process; Just not special the qualification; Yet specifically, can enumerate mould cladding process, intaglio plate cladding process, reverse intaglio plate cladding process, cylinder cladding process, reverse cylinder cladding process, excellent cladding process, scraper cladding process, knife coating, air-blade type cladding process, slit die cladding process, sliding die cladding process, immersion coating method, fine excellent cladding process, the fine excellent cladding process of reverse, stencil printing (rotation mode) etc.
(3) oxide semiconductor layer forms with layer
Form thickness as the oxide semiconductor layer that utilizes this operation to obtain with layer, preferably according to after be used as porous body in the firing process stated when forming, the mode of the thickness of being put down in writing in " the 3. firing process " stated after reaching is adjusted decision.Specifically, in the scope of preferred 1 μ m～65 μ m, wherein more preferably in the scope of 5 μ m～30 μ m.And; Here the thickness that said oxide semiconductor layer forms with layer is meant; Form upper end from the folder interlayer that is formed on the heat resistant substrate, form thickness with the upper end of the oxide semiconductor layer on the pattern to being formed on the heat resistant substrate and pressing from both sides interlayer with pattern.
3. firing process
Below, firing process of the present invention is described.Firing process of the present invention is to process porous body through said folder interlayer formation is burnt till with layer with pattern and oxide semiconductor layer formation, forms the operation of folder interlayer and oxide semiconductor layer.Utilize this operation, can form the folder interlayer and the oxide semiconductor layer that are used as porous body formation with intercommunicating pore.
In this operation; The temperature of burning till is so long as can form said folder interlayer formation in the scope of using organic substance contained in the layer and resin thermal decomposition with pattern and said oxide semiconductor layer; Just not special the qualification; Yet as a rule, in preferred 300 ℃～700 ℃ scope, in preferred especially 350 ℃～600 ℃ scope.
In addition; In this operation; Form with pattern and oxide semiconductor layer and form the heating means when burning till as pressing from both sides interlayer, will press from both sides interlayer unevenly and form with pattern and oxide semiconductor layer and form heating means of burning till, just not special qualification with layer so long as can not produce heating with layer.Specifically, can use known heating means.
In addition, as the folder interlayer that utilizes this operation to form as porous body and the thickness of oxide semiconductor layer, in the scope of the preferred 1 μ m of thickness～100 μ m that both have been merged, wherein more preferably in the scope of 5 μ m～30 μ m.This be because, through thickness being made as in the said scope, just can be behind firing process, acquisition is not peeled off or the high oxide semiconductor layer of mechanical strength of the generation in crack etc.
In addition, oxide semiconductor layer and the thickness of folder interlayer are than in preferred 10: 0.1～10: 5 scope, wherein more preferably in 10: 0.1～10: 3 the scope.Among the present invention, side's void content of the oxide semiconductor layer that the concentration of metal-oxide semiconductor (MOS) particulate in solid formation divides is high is lower, and mechanical strength is higher.So,, just can having good connecting airtight property and fissility with respect to heat resistant substrate when, increase mechanical strength through Film Thickness Ratio being made as said scope.
4. the 1st electrode layer forms operation
Below, the 1st electrode layer of the present invention is formed operation describe.It is the operation that the 1st electrode layer is set on said oxide semiconductor layer that the 1st electrode layer of the present invention forms operation.And, utilize the 1st electrode layer that this operation obtains because of after the 1st electrode pattern stated form to handle to wait and become the 1st electrode pattern.
In this operation; As the method that the 1st electrode layer is set on said oxide semiconductor layer; So long as can form the method for high conductive the 1st electrode layer; Just not special the qualification for example can be enumerated dry types such as CVD method such as PVD method such as vacuum vapour deposition, sputtering method, ion plating method and plasma CVD, hot CVD, atmospheric pressure CVD and become embrane method, solution spray method, spray-on process etc., wherein more preferably solution spray method and spray-on process.This is because can obtain the 1st fine and close electrode layer.
Below, will the solution spray method and the spray-on process of this operation be elaborated.
(1) solution spray method
The solution spray method of this operation is following method, that is, carry out solution-treated operation and spraying treatment process, thereby the 1st electrode layer is set on oxide semiconductor layer.Dissolved slaine or substrate the 1st electrode layer of metal complex forms with applying liquid through making in the said solution-treated operation with the metallic element that constitutes the 1st electrode layer; Contact with said oxide semiconductor layer; And substrate the 1st electrode layer is set on the inside or the surface of said oxide semiconductor layer, on said substrate the 1st electrode layer, upside the 1st electrode layer is set in the said spraying treatment process.
In said solution spray method; At first; In said solution-treated operation; Through using substrate the 1st electrode layer to form with applying liquid, said substrate the 1st electrode layer is formed with coating liquid soak into to inside as the said oxide semiconductor layer of porous body, just can be at set inside substrate the 1st electrode layer of said oxide semiconductor layer.In spraying treatment process, through on said substrate 1st electrode layer upside 1st electrode layer be set, just can obtain fine and close 1st electrode layer thereafter.In said solution spray method, the 1st electrode layer is the notion of basidigitale the 1st electrode layer and upside the 1st electrode layer.
Below, will the solution-treated operation and the spraying treatment process of said solution spray method be described.
(a) solution-treated operation
The solution-treated operation of said solution spray method is following operation; Promptly; Dissolved slaine or substrate the 1st electrode layer of metal complex forms with applying liquid through making with the metallic element that constitutes the 1st electrode layer; Contact with said oxide semiconductor layer, and the operation that substrate the 1st electrode layer is set on the inside or the surface of said oxide semiconductor layer.
(i) substrate the 1st electrode layer forms with applying liquid
At first, employed substrate the 1st electrode layer formation in the said solution-treated operation is described with coating liquid.Employed substrate the 1st electrode layer formation is in solvent, to have dissolved slaine or metal complex (following sometimes it is called " source metal " that has the metallic element that constitutes the 1st electrode layer at least with coating liquid in the said solution-treated operation.) solution.In addition, substrate the 1st electrode layer forms at least one side of preferably containing oxidant and reducing agent with coating liquid.This be because, utilize the effect of oxidant and/or reducing agent, can form the environment that is easy to generate substrate the 1st electrode layer.
(source metal)
Substrate the 1st electrode layer forms to use and applies employed source metal in the liquid so long as have the material of the metallic element that constitutes the 1st electrode layer, is the material that can form substrate the 1st electrode layer, both can be slaine, also can be metal complex.And what is called of the present invention " metal complex " has comprised with respect to metallic ion coordination inorganic matter or organic material or in molecule, has had the material of the so-called organo-metallic compound of metal-carbon key.
Form with the metallic element that applies employed source metal in the liquid as constituting substrate the 1st electrode layer; So long as can obtain the element of high conductive the 1st electrode layer; Just not special the qualification; For example can enumerate the metallic element more than from constitute by Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Ce, Sm, Pb, La, Hf, Sc, Gd and Ta one group, select at least a; Wherein, select more preferably constitute from Zn, Zr, Al, Y, Fe, Ga, La, Sb, In, Sn one group at least a more than metallic element.
In addition, as the slaine that contains said metallic element, specifically, can enumerate the chloride that contains said metallic element, nitrate, sulfate, perchlorate, acetate, phosphate, bromate etc.Wherein, in the present invention, more preferably use chloride, nitrate, acetate.This is because these compounds obtain as general article more easily.
In addition; As said metal complex; Specifically, can enumerate diethyl magnesium alkoxide, aluminium acetylacetonate, acetylacetone,2,4-pentanedione calcium dihydrate, two (methoxy ethoxy) calcium, calcium gluconae monohydrate, calcium citrate tetrahydrate, calcium salicylate dihydrate, lactic acid titanium, titanium acetylacetone, metatitanic acid tetra isopropyl ester, metatitanic acid tetra-n-butyl ester, metatitanic acid four (2-ethylhexyl) ester, butyltitanate dimer, two (ethyl hexyl oxies) two (the own oxygen base of 2-ethyl-3-hydroxyl) titanium, diisopropoxy titanium two (triethanolamine), two (ammonium lactate) titaniums of dihydroxy, diisopropoxy titanium two (ethyl acetoacetate), titanium peroxidating ammonium citrate tetrahydrates, ferrocene (II), ferric lactate (II) trihydrate, ferric acetyl acetonade (III), acetylacetone cobalt (II), nickel acetylacetonate (II) dihydrate, acetylacetone copper (II), two (pivaloyl) copper formate (II), oacetic acid copper (II), zinc acetylacetonate, zinc lactate trihydrate, zinc salicylate trihydrate, zinc stearate, two (pivaloyl) strontium formate, two (pivaloyl) formic acid iridium, four-n-butoxy zirconium, ethyoxyl zirconium (IV), n Propanoic acid zirconium, n-butyric acie zirconium, tetrem acyl acetone zirconium, single acetyl acetone zirconium, the two oacetic acid zirconiums of acetylacetone,2,4-pentanedione, acetic acid zirconium, monostearate zirconium, five-n-butoxy niobium, five ethyoxyl niobiums, five isopropoxy niobiums, tri acetylacetonato indium (III), 2 ethyl hexanoic acid indium (III), tetraethyl tin, dibutyltin oxide (IV), thricyclohexyl tin (IV) hydroxylate, acetylacetone,2,4-pentanedione lanthanum dihydrate, three (methoxy ethoxy) lanthanum, five isopropoxy tantalums, five ethoxy-tantalum, ethanol tantalum (V), acetylacetone,2,4-pentanedione cerium (III) n hydrate, lead citrate (II) trihydrate, cyclohexane plumbous chromate etc.Wherein, In said solution-treated operation, more preferably use diethyl magnesium alkoxide, aluminium acetylacetonate, acetylacetone,2,4-pentanedione calcium dihydrate, lactic acid titanium, titanium acetylacetone, tetraisopropyl titanate, tetra-n-butyl titanate, metatitanic acid four (2-ethylhexyl) ester, butyltitanate dimer, diisopropoxy titanium two (ethyl acetoacetic ester), ferric lactate (II) trihydrates, ferric acetyl acetonade (III), zinc acetylacetonate, zinc lactate trihydrate, two (pivaloyl) strontium formate, five ethyoxyl niobiums, tri acetylacetonato indium (III), 2 ethyl hexanoic acid indium (III), tetraethyl tin, dibutyltin oxide (IV), acetylacetone,2,4-pentanedione lanthanum dihydrate, three (methoxy ethoxy) lanthanum, acetylacetone,2,4-pentanedione cerium (III) n hydrate.
As the concentration of this kind source metal, as long as can obtain required substrate the 1st electrode layer, just not special the qualification; Yet for source metal is the situation of slaine; Be generally 0.001～1mol/l, wherein more preferably 0.01～0.1mol/l is the situation of metal complex for source metal; Be generally 0.001～1mol/l, wherein more preferably 0.01～0.1mol/l.
(oxidant)
Substrate the 1st electrode layer form with apply employed oxidant in the liquid be have promote described source metal dissolving and the material of effect of oxidation of metal ion etc.Through changing the valence mumber of metal ion etc., just can form the environment that is easy to generate substrate the 1st electrode layer.
As the concentration of this kind oxidant, as long as can obtain required substrate the 1st electrode layer, just not special the qualification, however as a rule be 0.001～1mol/l, more preferably 0.01～0.1mol/l wherein.This be because, when concentration when said scope is following, then might can't bring into play effect by oxidant, when concentration when said scope is above, then in the effect of gained, can't see very big difference, not ideal enough on cost.
In addition; As this kind oxidant; So long as in the solvent of stating after can being dissolved in, promote the material of the oxidation of said metal ion etc., just not special the qualification; Yet for example can enumerate hydrogen peroxide, natrium nitrosum, potassium nitrite, sodium bromate, potassium bromate, silver oxide, two chromic acid, potassinm permanganate etc., wherein more preferably use hydrogen peroxide, natrium nitrosum.
(reducing agent)
It is the material with following effect that substrate the 1st electrode layer forms with employed reducing agent in the coating liquid,, utilizes the decomposition reaction ejected electron that is, utilizes the electricity decomposition of water to produce hydroxide ion, improves substrate the 1st electrode layer and forms the pH value of using coating liquid.Improve because of substrate the 1st electrode layer forms with the pH value that applies liquid, just can form the environment that is easy to generate substrate the 1st electrode layer.
As the concentration of this kind reducing agent, as long as can obtain required substrate the 1st electrode layer, just not special the qualification; Yet for source metal is the situation of slaine; As a rule be 0.001～1mol/l, wherein more preferably 0.01～0.1mol/l is the situation of metal complex for source metal; As a rule be 0.001～1mol/l, more preferably 0.01～0.1mol/l wherein.This be because, when concentration when said scope is following, then might can't bring into play effect by reducing agent, when concentration when said scope is above, then in the effect of gained, can't see very big difference, not ideal enough on cost.
In addition; As this kind reducing agent, so long as in the solvent of stating after can being dissolved in, utilize the material of decomposition reaction ejected electron; Just not special the qualification; Yet can enumerate for example borine-tert-butylamine complex compound, borine-N, boranes complex compounds such as N-diethylbenzene amine complex, borine-dimethyl amine complex compound, borine-Trimethylamine complex compound, hydroxide cyanic acid boron sodium, boron hydroxide sodium etc., wherein more preferably boranes complex compound.
In addition, employed substrate the 1st electrode layer formation also can be the solution that contains reducing agent and oxidant with applying liquid in the said solution-treated.Combination as this kind oxidant and reducing agent; Though not special the qualification; Yet for example can enumerate hydrogen peroxide or natrium nitrosum and combination, the combination etc. of oxidant and boranes complex compound arbitrarily of reducing agent arbitrarily, the wherein more preferably combination of hydrogen peroxide and boranes complex compound.
(solvent)
Substrate the 1st electrode layer forms with applying employed solvent in the liquid so long as can dissolve the solvent of described slaine etc.; Just not special the qualification; It for example is the situation of slaine for source metal; Can enumerate total carbon number such as water, methyl alcohol, ethanol, isopropyl alcohol, 1-propyl alcohol, butanols is lower alcohol, toluene and their mixed solvent etc. below 5, is the situation of metal complex for source metal, can enumerate described lower alcohol, toluene and their mixed solvent.
(additive)
In addition, substrate the 1st electrode layer forms with applying liquid and also can contain additives such as assisting ion source or surfactant.
Said assisting ion source is the material that produces hydroxide ion with electron reaction, can improve substrate the 1st electrode layer and form with the pH value that applies liquid, forms the environment that forms substrate the 1st electrode layer easily.In addition, the use amount in said assisting ion source is preferably suitably selected to use with employed slaine or reducing agent accordingly.
As this kind assisting ion source, specifically, can enumerate from by the chlorate ions, cross the ion species of selecting a group that chlorate ions, chlorous acid ion, inferior chlorous acid ion, bromic acid ion, hypobromous acid ion, nitrate ion and nitrite ion constitute.
In addition, said surfactant is to act on substrate the 1st electrode layer to form the interface with the porous body surface that applies liquid and oxide semiconductor layer, has the material that generates the effect of metal oxide film (substrate the 1st electrode layer) on the porous body surface easily.The use amount of said surfactant is preferably suitably selected to use with employed slaine or reducing agent accordingly.
This kind surfactant can be enumerated サ one Off イ ノ one Le 485 specifically; サ one Off イ ノ one Le SE; サ one Off イ ノ one Le SE-F; サ one Off イ ノ one Le 504; サ one Off イ ノ one Le GA; サ one Off イ ノ one Le 104A; サ one Off イ ノ one Le 104BC; サ one Off イ ノ one Le 104PPM; サ one Off イ ノ one Le 104E; サ one Off イ ノ one Le such as サ one Off イ ノ one Le 104PA series (above) all by day letter chemical industry (strain) manufacturing; NIKKOL AM301; NIKKOLAM313ON (above) etc. all by daylight chemical manufactured.
(ii) oxide semiconductor layer and substrate the 1st electrode layer form with the contact method that applies liquid
Below, oxide semiconductor layer in the said solution-treated operation and the formation of substrate the 1st electrode layer are described with the contact method that applies liquid.As this kind contact method; So long as described oxide semiconductor layer and described substrate the 1st electrode layer are formed with applying the method that liquid contacts; Just not special the qualification specifically, can be enumerated infusion process, utilizes the method for vane type, solution processed the method for vaporific and coating etc.
For example, infusion process is to impregnated in substrate the 1st electrode layer through the heat resistant substrate that will possess oxide semiconductor layer to form with applying in the liquid method that forms substrate the 1st electrode layer on the inside or the surface of oxide semiconductor layer.For example shown in figure 13, be to impregnated in substrate the 1st electrode layer through the heat resistant substrate 61 that will possess said oxide semiconductor layer etc. to form with applying in the liquid 81, and obtain the method for substrate the 1st electrode layer.
In addition, in said solution-treated operation, be preferably in when oxide semiconductor layer and the formation of substrate the 1st electrode layer are contacted with coating liquid, heat.This be because, through heating, just can the accelerating oxidation agent and the activity of reducing agent, the formation speed of raising substrate the 1st electrode layer.As the method that heats, though not special the qualification, wherein more preferably with the oxide semiconductor layer heating, especially preferably oxide semiconductor layer and substrate the 1st electrode layer are formed with applying the liquid heating.This be because, near the reaction of formation of substrate the 1st electrode layer can accelerating oxidation thing semiconductor layer.
As this kind heating-up temperature, preferably suitably select accordingly with the characteristic of employed oxidant, reducing agent etc., specifically, in preferred 50～150 ℃ scope, wherein more preferably in 70～100 ℃ the scope.
(iii) substrate the 1st electrode layer
Below, substrate the 1st electrode layer that utilizes said solution-treated operation to form is described.As long as being located at substrate the 1st electrode layer in inside of oxide semiconductor layer etc., the method for stating after the utilization can utilize other spraying treatment process; Acquisition has the 1st electrode layer of required compactness; Just not special the qualification for example, both can be all to exist until the surface from oxide semiconductor layer inside; With the film that oxide semiconductor layer fully covers, also can be the layer that said oxide semiconductor layer surface portion ground is covered.As the concrete example of substrate the 1st electrode layer that said oxide semiconductor layer surface portion ground is covered, for example can enumerate the situation that is the existence of island ground in inside etc. as the said oxide semiconductor layer of porous body.In addition; Though employed solution spray method is after said solution-treated operation in this operation; The spraying treatment process of stating after carrying out, yet owing to can utilize said solution-treated operation to obtain substrate the 1st electrode layer on inside or surface as the oxide semiconductor layer of porous body, the spraying treatment process of stating after therefore being not limited to; Even used the situation of known film build method, also can obtain the 1st fine and close electrode layer.
(b) spraying treatment process
The spraying treatment process of said solution spray method is on substrate the 1st electrode layer that utilizes described solution-treated operation to form, to utilize spray-on process that the operation of upside the 1st electrode layer is set.Below, said spray-on process is described.
Said spray-on process is following method; Promptly; Said substrate the 1st electrode layer is heated to the temperature more than upside the 1st electrode layer formation temperature; Contact through making it to form with coating liquid, the method for upside the 1st electrode layer is set on said substrate the 1st electrode layer with upside the 1st electrode layer that has dissolved slaine with the metallic element that constitutes the 1st electrode layer or metal complex.
And; In said spray-on process; So-called " upside the 1st electrode layer formation temperature " is meant; After upside the 1st electrode layer stated form that contained metallic element can combine with oxygen in the liquid with applying, form temperature as the metal oxide film of upside the 1st electrode layer etc., be the temperature that the kind of the metal ion that dissolve according to source metal etc., the composition that coating liquid is used in the formation of upside the 1st electrode layer etc. have a great difference.In said spray-on process, this kind " upside the 1st electrode layer formation temperature " can utilize following method to measure.Promptly; Upside the 1st electrode layer formation of preparing in fact to have dissolved required source metal is with applying liquid; The heating-up temperature that has possessed the heat resistant substrate of said substrate the 1st electrode layer through change makes it contact, and mensuration can form the minimum base material heating-up temperature as the metal oxide film of upside the 1st electrode layer.Base material heating-up temperature that can this is minimum is as " upside the 1st electrode layer formation temperature " of said spray-on process.At this moment; For whether having formed metal oxide film, as a rule, according to utilizing X-ray diffraction device (system of science; RINT-1500) result who obtains judges; For the situation that does not have crystalline amorphous membrance, judge according to the result who obtains by photoelectron spectroscopy apparatus (V.G.Scientific corporate system, ESCALAB 200i-XL).
In said spray-on process; Through said substrate the 1st electrode layer is heated to the temperature more than upside the 1st electrode layer formation temperature; Make it to contact with applying liquid with said upside the 1st electrode layer formation; Just can on said substrate the 1st electrode layer, form upside the 1st electrode layer, consequently, can on as the said oxide semiconductor layer of porous body, obtain the 1st fine and close electrode layer.
(i) upside the 1st electrode layer forms with applying liquid
At first, employed upside the 1st electrode layer formation in the said spray-on process is described with coating liquid.Employed upside the 1st electrode layer formation is in solvent, to have dissolved the slaine of the metallic element with formation the 1st electrode layer or the solution of metal complex with coating liquid in the said spray-on process.
In addition, upside the 1st electrode layer forms at least one side of preferably containing oxidant and reducing agent with coating liquid.This is because through making it to contain at least one side of oxidant and reducing agent, just can under lower heating-up temperature, obtain upside the 1st electrode layer.
(source metal)
Upside the 1st electrode layer forms to use and applies employed source metal in the liquid so long as have the material of the metallic element that constitutes upside the 1st electrode layer, is the material that can form upside the 1st electrode layer, then both can be slaine, also can be metal complex.The kind of said source metal can use with described solution-treated operation in substrate the 1st electrode layer put down in writing form with the identical kind of slaine that applies liquid; Yet wherein, more preferably can obtain to have the source metal of upside the 1st electrode layer of permeability, conductivity.This is because upside the 1st electrode layer particularly plays a role as collecting electrodes.As the metal oxide that constitutes this kind upside the 1st electrode layer; So long as can constitute had permeability, the material of upside the 1st electrode layer of conductivity; Just not special the qualification, however for example can enumerate ITO, ZnO, FTO (fluorine-doped tin oxide), ATO (antimony-doped tin oxide), SnO 2(TO) etc.As the source metal that constitutes this kind metal oxide,, for example can use tri acetylacetonato indium (III), 2 ethyl hexanoic acid indium (III), tetraethyl tin, dibutyltin oxide (IV), thricyclohexyl tin (IV) hydroxylate etc. for the situation of ITO.In addition, for the situation of said ZnO, can use zinc acetylacetonate, zinc lactate trihydrate, zinc salicylate trihydrate, zinc stearate etc.In addition,, for example can use tetraethyl tin, dibutyltin oxide (IV), thricyclohexyl tin (IV) hydroxylate etc., can use ammonium fluoride etc. as fluorine dopant for the situation of said FTO.In addition, for the situation of said ATO, for example can use butanols antimony (III), ethanol antimony (III), tetraethyl tin, dibutyltin oxide (IV), thricyclohexyl tin (IV) hydroxylate etc.In addition, for said SnO 2(TO) situation can be used tetraethyl tin, dibutyltin oxide (IV), thricyclohexyl tin (IV) hydroxylate etc.
In addition; Employed source metal can obtain the 1st required electrode layer in the liquid with applying as long as upside the 1st electrode layer forms; Just there be not special the qualification, both can be identical with employed source metal in the coating liquid with described substrate the 1st electrode layer formation, also can be different.And, for the combination of upside the 1st electrode layer and substrate the 1st electrode layer, owing in " (iii) upside the 1st electrode layer " stated after being recorded in, therefore the explanation is here omitted.
In addition, form with the concentration that applies source metal in the liquid, as long as can obtain required upside the 1st electrode layer as upside the 1st electrode layer; Just not special the qualification, however be the situation of slaine for source metal, as a rule be 0.001～1mol/l; More preferably 0.01～0.5mol/l wherein; For source metal is the situation of metal complex, as a rule is 0.001～1mol/l, wherein more preferably 0.01～0.5mol/l.This be because, when concentration when said scope is following, time that then might the overspending in formation of upside the 1st electrode layer, when concentration when said scope is above, then might can't obtain upside the 1st electrode layer of uniform thickness.
(other)
In addition, form with applying employed oxidant, reducing agent, solvent and additive in the liquid for upside the 1st electrode layer and since with described solution-treated operation in the content put down in writing identical, therefore the explanation is here omitted.
(ii) upside the 1st electrode layer forms with the contact method that applies liquid and substrate the 1st electrode layer
Below, use the contact method that applies liquid and said substrate the 1st electrode layer to describe to upside the 1st electrode layer formation of said spray-on process.As this kind contact method; So long as described upside the 1st electrode layer is formed with applying the method that liquid contacts with described substrate the 1st electrode layer; Just not special the qualification; Yet preferably form method with the temperature reduction that applies liquid when contacting, can not make substrate the 1st electrode layer that has been heated with said substrate the 1st electrode layer at said upside the 1st electrode layer.This is because when the temperature of substrate the 1st electrode layer reduces, just might can't obtain the 1st required electrode layer.
Can not reduce method of temperature as this kind; Though not special the qualification, yet for example can enumerate through said upside the 1st electrode layer being formed with applying method that the liquid ejection makes it contact with said substrate the 1st electrode layer, making method that said substrate the 1st electrode layer passes etc. in the vaporific space in that said upside the 1st electrode layer formation has been processed with coating liquid as drop.
Though through said upside the 1st electrode layer being formed with applying not special qualification of method that the liquid spraying makes it to contact, yet for example can enumerate the method for using sprayings such as sprayer unit etc.As this kind method; For example can enumerate following method, that is, shown in figure 14; Heat resistant substrate 61 through having possessed substrate the 1st electrode layer etc. is heated to the temperature more than upside the 1st electrode layer formation temperature; To this heat resistant substrate 61, use sprayer unit 82 ejection upsides the 1st electrode layer to form, and form upside the 1st electrode layer with coating liquid.
When using said sprayer unit spraying, drop typically have a diameter from 0.1～1000 μ m, more preferably 0.5～300 μ m wherein.This is because if the diameter of drop in said scope, then can suppress the reduction of temperature, can obtain uniform upside the 1st electrode layer.In addition, as the spray gas of said sprayer unit, for example can enumerate air, nitrogen, argon gas, helium, oxygen etc.In addition, as the spray amount of said spray gas, be 0.1～50l/min, more preferably 1～20l/min wherein.
On the other hand, as the method that substrate the 1st electrode layer is passed is being processed in the vaporific space in described upside the 1st electrode layer formation with coating liquid; For example can enumerate following method; That is, shown in figure 15, the formation of upside the 1st electrode layer is being processed in the vaporific space with applying liquid 81; The heat resistant substrate 61 that is heated to the above temperature of upside the 1st electrode layer formation temperature and has possessed substrate the 1st electrode layer etc. is passed, and form upside the 1st electrode layer.In this kind method, drop typically have a diameter from 0.1～300 μ m, more preferably 1～100 μ m wherein.This is because if the diameter of drop in said scope, then can suppress the temperature reduction of substrate the 1st electrode layer, can obtain uniform upside the 1st electrode layer.
In addition, in said spray-on process, said upside the 1st electrode layer is formed with applying liquid when contacting with substrate the 1st electrode layer that has been heated, said substrate the 1st electrode layer is heated to the temperature more than " upside the 1st electrode layer formation temperature ".This kind " upside the 1st electrode layer formation temperature " has a great difference though can dissolve the kind of the metal ion that gets, the composition that coating liquid is used in the formation of upside the 1st electrode layer etc. according to source metal; Yet when when form at upside the 1st electrode layer in, not adding oxidant and/or reducing agent with coating liquid; Usually can be made as in 400～600 ℃ the scope, wherein more preferably in 450～550 ℃ the scope.On the other hand, when when form at upside the 1st electrode layer in, having added oxidant and/or reducing agent, can be made as usually in 150～600 ℃ the scope, wherein more preferably in 250～400 ℃ the scope with coating liquid.In addition, particularly when using said spray-on process to form the 1st electrode layer of ITO film, preferably be made as in 300～500 ℃ the scope, wherein more preferably be made as in 350～450 ℃ the scope.
In addition; As this kind heating means; Though not special the qualification for example can not enumerated heating means such as hotplate (hot plate), baking oven, firing furnace, infrared lamp, hot air blower, form the method for using coating liquid to contact with upside the 1st electrode layer when wherein more preferably can remain said temperature in temperature with substrate the 1st electrode layer; Specifically, the method for preferably utilizing hotplate to heat from the heat resistant substrate rear side.
(iii) upside the 1st electrode layer
Below, upside the 1st electrode layer that in said spray-on process, forms is described.In the said spray-on process; Said upside the 1st electrode layer is obtained by following; Promptly; Through said substrate the 1st electrode layer is heated to the temperature more than upside the 1st electrode layer formation temperature, makes it to contact with applying liquid, and on said substrate the 1st electrode layer, obtain with upside the 1st electrode layer formation of slaine that has dissolved metallic element or metal complex with formation the 1st electrode layer.
In addition; Among the present invention; As long as the metal oxide of formation substrate the 1st electrode layer and the 1st electrode layer that the combination of the metal oxide that constitutes upside the 1st electrode layer can obtain to have required compactness just do not limit especially, yet wherein; The combination that the crystallographic system of preferable alloy oxide is approaching, the special more preferably identical combination of metallic element.
For example, when upside the 1st electrode layer was made as the ITO film, as substrate the 1st electrode layer, as long as can form fine and close ITO film as upside the 1st electrode layer, just not special the qualification for example can be enumerated ZnO, ZrO 2, Al 2O 3, Y 2O 3, Fe 2O 3, Ga 2O 3, La 2O 3, Sb 2O 3, ITO, In 2O 3, SnO 2Deng, wherein, consider preferred Al from ITO film and the approaching viewpoint of crystallographic system 2O 3, Y 2O 3, Fe 2O 3, Ga 2O 3, La 2O 3, Sb 2O 3, ITO, In 2O 3, SnO 2, particularly consider, more preferably ITO, In from the identical viewpoint of metallic element (In, Sn) that constitutes metal oxide film (ITO film) 2O 3, SnO 2
As the thickness of formed the 1st electrode layer in this operation, so long as can bring into play the thickness of good conductivity, just not special the qualification, however specifically, be preferably in the scope of 5nm～2000nm, wherein, more preferably in the scope of 10nm～1000nm.
(2) spray-on process
Below, the spray-on process of this operation is described.The spray-on process of this operation is following method; Promptly; Through said oxide semiconductor layer being heated to the temperature more than the 1st electrode layer formation temperature; Make it to contact with applying liquid, and on said oxide semiconductor layer, obtain the 1st electrode layer with the 1st electrode layer formation of slaine that has dissolved metallic element or metal complex with formation the 1st electrode layer.
Said spray-on process is in described solution spray method, not carry out the solution-treated operation, and the method for the 1st electrode layer directly is set on oxide semiconductor layer.Owing to do not carry out said solution-treated operation, therefore can on oxide semiconductor layer, utilize easy method to obtain the 1st electrode layer as porous body.And, the spray-on process of this operation since with the spraying treatment process of described solution spray method in employed spray-on process identical, therefore the explanation is here omitted.And the 1st electrode layer formation temperature of the spray-on process of this operation can likewise be tried to achieve with upside the 1st electrode layer formation temperature of employed spray-on process in the described solution spray method.
As the thickness of formed the 1st electrode layer in this operation, so long as can bring into play the thickness of good conductivity, just not special the qualification, however specifically, be preferably in the scope of 5nm～2000nm, wherein, more preferably in the scope of 10nm～1000nm.
Other
In the manufacturing approach of oxide semiconductor electrode of the present invention with laminated body, after said the 1st electrode layer forms operation, also can carry out the 1st electrode layer is processed pattern-like, the 1st electrode pattern that forms the 1st electrode pattern forms operation.Form operation for the 1st electrode pattern, will after detailed description in " manufacturing approach of G. dye-sensitized solar cell " stated.In addition, among the present invention,, may also be referred to as oxide semiconductor electrode and use laminated body even said the 1st electrode layer is the 1st electrode pattern.For after the oxide semiconductor electrode that has heat resistant substrate, oxide semiconductor electrode, the dye-sensitized solar cell base material stated identical to also.
6. oxide semiconductor electrode is used laminated body
Below, the oxide semiconductor electrode that utilizes the present invention to obtain is described with laminated body.Utilize oxide semiconductor electrode that the present invention obtains with laminated body for example shown in Figure 12 (d), be have heat resistant substrate 61, be formed at folder interlayer 62 ' on the said heat resistant substrate 1, be formed on the said heat resistant substrate 61 and said folder interlayer 62 ' on oxide semiconductor layer 63 ', be formed at the laminated body of the 1st electrode layer 64 on the said oxide semiconductor layer 63 '.Constitute for the oxide semiconductor electrode that utilizes the present invention to obtain each with laminated body and since with described each operation in put down in writing identical, therefore the explanation is here omitted.
Utilize oxide semiconductor electrode that manufacturing approach of the present invention obtains with laminated body can be used for coloring matter sensitization type light charging capacitor with the making of electrode, electroluminescent display with the making of electrode, making that pollutant decomposes substrate and dye-sensitized solar cell with the making of base material etc., yet wherein more be applicable to the making of dye-sensitized solar cell with base material.
E. the manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate
Below, the manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate of the present invention is described.As the manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate of the present invention, can enumerate two following modes.
Promptly comprise mode one and mode two; Wherein the characteristic of mode one is; Carry out on 1st electrode layer of oxide semiconductor electrode that the manufacturing approach of utilizing said oxide semiconductor electrode with laminated body obtains, being provided with the base material formation operation of base material with laminated body; The characteristic of mode two is through carrying out following operation, to form the oxide semiconductor substrate; Use said oxide semiconductor substrate, possessed the electrode base material of base material and the 1st electrode layer, said oxide semiconductor layer and said the 1st electrode layer are overlapped.Wherein said operation comprises: the folder interlayer that on heat resistant substrate, will contain organic substance and metal-oxide semiconductor (MOS) particulate forms with applying liquid and is coated with pattern-like, makes it to be solidified to form the folder interlayer formation that the folder interlayer forms with pattern and forms operation with pattern; On the said heat resistant substrate and said folder interlayer form with pattern on coating form with applying liquid phase with said folder interlayer and form with applying liquid at the solid higher oxide semiconductor layer of concentration that forms in dividing than metal-oxide semiconductor (MOS) particulate, make it to be solidified to form oxide semiconductor layer and form oxide semiconductor layer with layer and form with layer and form an operation; Process porous body through said folder interlayer formation is burnt till with layer with pattern and oxide semiconductor layer formation, form the firing process of folder interlayer and oxide semiconductor layer.
According to the present invention, for example be used under the situation of dye-sensitized solar cell at the oxide semiconductor electrode that has heat resistant substrate that will utilize said manufacturing approach to obtain, can obtain the good dye-sensitized solar cell of energy conversion efficiency.
Below, will be elaborated to said mode one and said mode two.
1. mode one
The manufacturing approach of the oxide semiconductor electrode that has heat resistant substrate of this mode is the mode with following characteristic; That is, carry out on 1st electrode layer of oxide semiconductor electrode that the manufacturing approach of utilizing said oxide semiconductor electrode with laminated body obtains, being provided with the base material formation operation of base material with laminated body.
The manufacturing approach of the oxide semiconductor electrode that has heat resistant substrate of this mode is following method; Promptly; For example shown in figure 16; Through carrying out on 1st electrode layer 64 of oxide semiconductor electrode that the manufacturing approach of utilizing said oxide semiconductor electrode with laminated body obtains, the base material formation operation of base material 65 is set, and forms the oxide semiconductor electrode B (Figure 16 (b)) that has heat resistant substrate with laminated body A (Figure 16 (a)).
Below, will form operation to the base material of this mode and be elaborated.
(1) oxide semiconductor electrode is used laminated body
At first, employed oxide semiconductor electrode in this operation is described with laminated body.Constitute for each of employed oxide semiconductor electrode in this operation with laminated body and since with the part of said " the D. oxide semiconductor electrode is with the manufacturing approach of laminated body " in the content put down in writing identical, the explanation omission therefore will be here.
(2) base material
The base material that can in this operation, use and since with the part of said " oxide semiconductor electrode of A-1. mode one " in the content put down in writing identical, therefore the explanation is here omitted.
In addition, in order to improve the connecting airtight property with said the 1st electrode layer, employed base material also can possess adhesive linkage in this mode.As the material that constitutes this kind adhesive linkage; So long as improve the material of the connecting airtight property of base material and the 1st electrode layer; Just not special the qualification; Yet specifically, can enumerate thermoplastic resin, heat-curing resin, uv curing resin, electronic curing property resin etc., wherein more preferably thermoplastic resin.This be because, good aspect the connecting airtight property of the 1st electrode layer, be difficult to produce peel off, crackle etc., the tolerance to employed photoresist ion, solvent etc. in the electrolyte is high in addition, the durability aspect is good.As employed thermoplastic resin in this mode and since with the part of said " oxide semiconductor electrode of A-2. mode two " in the content put down in writing identical, therefore the explanation is here omitted.
In this operation, in described thermoplastic resin, preferably use silane-modified resin.This be because, through using silane-modified resin, can be so that the bonding force that adhesive linkage showed be more firm.
As long as employed silane-modified resin has said fusing point in this operation, just not special the qualification.As the silane-modified resin of this kind, can be suitable for the resin of being put down in writing in the part of said " oxide semiconductor electrode of A-1. mode one ".
In the adhesive linkage of this operation, as required, can also contain other the compound beyond the silane-modified resin.As other compound of this kind, can be suitable for the compound of being put down in writing in the part of said " oxide semiconductor electrode of A-1. mode one ".
(3) the formation method of base material
Below, the method that forms base material at said oxide semiconductor electrode on the 1st electrode layer of laminated body is described.As the method that on said the 1st electrode layer, forms base material; So long as can be on the 1st electrode layer connecting airtight property form the method for base material well; Just not special the qualification for example can be enumerated said oxide semiconductor electrode with the 1st electrode layer of laminated body and the method for said base material thermal welding etc.Heating means when carrying out thermal welding; Though not special the qualification; Yet specifically; Can enumerate the method for method, the method for using lamp of using heating rod, the method for using laser, the method for using electromagnetic induction heating, use ultrasonic wave friction heating etc., wherein, more preferably use the method for laser.As employed laser in the said method, for example can enumerate solid state laser (YAG laser), semiconductor laser etc.
2. mode two
The characteristic of the manufacturing approach of the oxide semiconductor electrode that has heat resistant substrate of this mode is; Through carrying out following operation; Promptly; The folder interlayer formation that on heat resistant substrate, contains organic substance and metal-oxide semiconductor (MOS) particulate with the pattern-like coating is with applying liquid; Make it to be solidified to form the folder interlayer form folder interlayer with pattern form with pattern form operation, on the said heat resistant substrate and the formation of said folder interlayer with pattern on; Coating forms with applying liquid phase with said folder interlayer and forms with applying liquid at the solid higher oxide semiconductor layer of concentration that forms in dividing than metal-oxide semiconductor (MOS) particulate; Make it to be solidified to form oxide semiconductor and form oxide semiconductor layer with layer and form with layer and form an operation, process porous body through said folder interlayer being formed form to burn till with layer with pattern and oxide semiconductor layer, the firing process of interlayer and oxide semiconductor layer is pressed from both sides in formation, forms the oxide semiconductor substrate; Use said oxide semiconductor substrate, possessed the electrode base material of base material and the 1st electrode layer, said oxide semiconductor layer is overlapped with said the 1st electrode layer.
The manufacturing approach of the oxide semiconductor electrode that has heat resistant substrate of this mode is following method; Promptly; For example shown in figure 17; Through on the oxide semiconductor substrate X (Figure 17 (a)) that utilizes the folder interlayer to form to form operation, oxide semiconductor layer to form to form operation and firing process to obtain, the electrode base material that has possessed base material 65 and the 1st electrode layer 64 is set, and forms the oxide semiconductor electrode B (Figure 17 (b)) that has heat resistant substrate with layer with pattern.
Below, will the method to set up of employed oxide semiconductor substrate and electrode base material in this mode be elaborated.
(1) oxide semiconductor substrate
At first, employed oxide semiconductor substrate in this operation is described.In this operation employed oxide semiconductor substrate for example shown in Figure 17 (a), have heat resistant substrate 61, be formed at folder interlayer 62 ' on the said heat resistant substrate 61, be formed on the said heat resistant substrate 61 and said folder interlayer 62 ' on oxide semiconductor layer 63 '.Employed oxide semiconductor substrate can pass through heat resistant substrate in this mode; Pressing from both sides interlayer forms and to form operation, oxide semiconductor layer with pattern and form with layer formation operation and firing process and form; For heat resistant substrate and said operation; Since identical with the content of being put down in writing in described " the D. oxide semiconductor electrode is with the manufacturing approach of laminated body ", therefore the explanation is here omitted.
(2) electrode base material
Below, employed electrode base material in this mode is described.Employed electrode base material possesses base material and the 1st electrode layer in this mode.For said base material and said the 1st electrode layer and since with said mode one in employed material identical, therefore the explanation is here omitted.
In addition,, known method can be used, specifically, wet type coating, vapour deposition method, sputtering method, CVD method etc. can be enumerated as the method for employed electrode base material in this mode of manufacturing.Wherein, more preferably vapour deposition method, sputtering method, CVD method.
In addition, employed base material electrode also can be provided with the adhesive linkage with conductivity in this mode on the 1st electrode layer.Said adhesive linkage with conductivity is so long as the good layer of conductivity and cementability, just not special the qualification, however specifically, can enumerate the adhesive linkage that in transparent resin, disperseed inorganic conductive property material etc.As said transparent resin; Though not special the qualification; Yet specifically, can enumerate polyester, ethylene-vinyl acetate copolymer, acrylic resin, polypropylene, chlorinated polypropylene, polyethylene, ethylene chloride resin, Vingon, polystyrene, polyvinyl acetate, fluororesin, silicones etc.In addition; As said inorganic conductive property material; Though not special the qualification for example can be enumerated (following they are referred to as " electrically conductive microparticles " such as the particulate processed by high inorganic conductive property materials of conductivity such as the tin oxide (ATO) of ITO, tin oxide, antimony dopant, antimony oxide, gold, silver, palladiums, spicule, club, flakey thing.)。For electrically conductive microparticle is the situation of sphere, and when considering dispersiveness, light transmission etc., its particle diameter is suitably selected in can the scope about 5～1000nm, more preferably suitably selectes in the scope about 10～500nm.As the content of the said inorganic conductive property material in the said transparent resin, though not special the qualification, be preferably in the scope of 5～50 quality %, wherein more preferably in the scope of 10～40 quality %.In addition, as said thickness, in the scope of preferred 0.1～10 μ m with adhesive linkage of conductivity.
(3) method to set up of electrode base material
Below, the method that on the oxide semiconductor layer of said oxide semiconductor substrate, forms electrode base material is described.As the method that on said oxide semiconductor layer, forms base material; So long as can be on oxide semiconductor layer connecting airtight property form the method for electrode base material well; Just not special the qualification; Yet the oxide semiconductor layer that for example can enumerate said oxide semiconductor substrate utilizes optionally heating such as microwave, the method that the 1st electrode layer of oxide semiconductor layer and said electrode base material is bondd etc.
3. the oxide semiconductor electrode that has heat resistant substrate
Below, the oxide semiconductor electrode that has heat resistant substrate that utilizes the present invention to obtain is described.Utilize the oxide semiconductor electrode that has heat resistant substrate that the present invention obtains for example shown in Figure 16 (a), have heat resistant substrate 61, be formed at folder interlayer 62 ' on the said heat resistant substrate 1, be formed on the said heat resistant substrate 61 and said folder interlayer 62 ' on oxide semiconductor layer 63 ', be formed at the 1st electrode layer 64 on the said oxide semiconductor layer 63 ', be formed at the base material 65 on said the 1st electrode layer 64.Constitute for each of the oxide semiconductor electrode that has heat resistant substrate that utilizes the present invention to obtain and since with described each operation in put down in writing identical, therefore the explanation is here omitted.In addition, in the present invention, in said mode one, when base material possesses said adhesive linkage, can be made as the oxide semiconductor electrode that has heat resistant substrate that between the 1st electrode layer and base material, has possessed adhesive linkage.In addition, in said mode two, when electrode base material possesses said adhesive linkage with conductivity, can be made as the oxide semiconductor electrode that has heat resistant substrate that between oxide semiconductor layer and the 1st electrode layer, has possessed adhesive linkage with conductivity.
The oxide semiconductor electrode that has heat resistant substrate that utilizes manufacturing approach of the present invention to obtain can be used for coloring matter sensitization type light charging capacitor with the making of electrode, electroluminescent display with the making of electrode, making that pollutant decomposes substrate and dye-sensitized solar cell with the making of base material etc.; Yet wherein, more be applicable to the making of dye-sensitized solar cell with base material.
F. the manufacturing approach of oxide semiconductor electrode
The characteristic of the manufacturing approach of oxide semiconductor electrode of the present invention is; Carry out from utilize the oxide semiconductor electrode that has heat resistant substrate that the said manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate obtains the stripping process that heat resistant substrate is peeled off.
According to the present invention, for example be used at the oxide semiconductor electrode that will utilize said manufacturing approach to obtain under the situation of dye-sensitized solar cell, can obtain the good dye-sensitized solar cell of energy conversion efficiency.
The manufacturing approach of oxide semiconductor electrode of the present invention is for example shown in figure 18, and the heat resistant substrate 61 of the oxide semiconductor electrode B that has heat resistant substrate that utilizes the said manufacturing approach that has the oxide semiconductor electrode of heat resistant substrate to obtain (Figure 18 (a)) is peeled off.At this moment, heat resistant substrate 61 contacts with folder interlayer 62 ' and oxide semiconductor layer 63 '.Described in above-mentioned " the D. oxide semiconductor electrode is with the manufacturing approach of laminated body "; Because folder interlayer 62 ' is compared with oxide semiconductor layer 63 '; The concentration of metal-oxide semiconductor (MOS) particulate is lower, therefore heat resistant substrate 61 is had good fissility, in contrast; Oxide semiconductor 63 ' is owing to the concentration of comparing the metal-oxide semiconductor (MOS) particulate with folder interlayer 62 ' is higher, therefore strong with the connecting airtight property of heat resistant substrate 61.Thus; Under situation about from the oxide semiconductor electrode B that has heat resistant substrate, heat resistant substrate 61 being peeled off; Folder interlayer 62 ' with the interface of heat resistant substrate 61 on peel off; And in contrast, oxide semiconductor layer 63 ' not with the interface of heat resistant substrate 61 on peel off, and with the interface of lower the 1st electrode layer 64 of connecting airtight property on peel off.Consequently, form the oxide semiconductor electrode C (Figure 18 (b)) that has along the oxide semiconductor layer 63 ' of the pattern that presss from both sides interlayer 62 '.
Below, will be elaborated to stripping process of the present invention.
1. the oxide semiconductor electrode that has heat resistant substrate
At first, the employed oxide semiconductor electrode that has heat resistant substrate in this operation is described.Constitute for each of the employed oxide semiconductor electrode that has a heat resistant substrate in this operation and since with said " B. has the manufacturing approach of the oxide semiconductor electrode of heat resistant substrate " in the content put down in writing identical, therefore the explanation is here omitted.
2. the stripping means of heat resistant substrate
Below, the method that the said heat resistant substrate that has the oxide semiconductor electrode of heat resistant substrate is peeled off from the folder interlayer is described.As the said method that heat resistant substrate is peeled off, so long as can and press from both sides the method that interlayer is peeled off with heat resistant substrate, just not special qualification; Yet, when for example heat resistant substrate is flexible substrate, when utilizing Roll to Roll mode to carry out; Can enumerate following method etc.; That is, said heat resistant substrate and the different separately warm-up mill of base material utilization that has the oxide semiconductor electrode of heat resistant substrate fitted, thereafter heat resistant substrate and oxide semiconductor electrode are reeled respectively.In addition, when for example heat resistant substrate is the substrate of rigidity, can enumerates the said substrate that has the oxide semiconductor electrode of heat resistant substrate is fitted with warm-up mill, and the method for coiling oxide semiconductor electrode.And; Among the present invention; With heat resistant substrate and folder interlayer when peeling off, according to the kind of heat resistant substrate and folder interlayer etc., situation, the folder interlayer that has heat resistant substrate and a folder interlayer generation interface peel take place cohesion damaged and on heat resistant substrate the situation of the part of residual folder interlayer.
In addition, in this operation, also can utilize the grinding of machinery to remove, utilize the chemistry of etching etc. to remove heat resistant substrate is peeled off.
Other
In the manufacturing approach of oxide semiconductor electrode of the present invention, behind said stripping process, also can carry out the 1st electrode layer is processed pattern-like, the 1st electrode pattern that forms the 1st electrode pattern forms operation.Form operation for the 1st electrode pattern, will after detailed description in " manufacturing approach of G. dye-sensitized solar cell " stated.In addition, among the present invention,, may also be referred to as oxide semiconductor electrode even said the 1st electrode layer is the 1st electrode pattern.
4. oxide semiconductor electrode
Below, the oxide semiconductor electrode that utilizes the present invention to obtain is described.Utilize oxide semiconductor electrode that the present invention obtains for example shown in Figure 18 (b); Be from base material 65 beginning, the electrode that forms with the sequential cascade of the 1st electrode layer 64, the oxide semiconductor layer 63 ' that has been patterned and the folder interlayer 62 ' that has been patterned successively.Constitute for each of the oxide semiconductor electrode that utilizes the present invention to obtain and since with described operation in the content put down in writing identical, therefore the explanation is here omitted.In addition; Among the present invention; When said heat resistant substrate has possessed the wettability change layer of being put down in writing in described " the D. oxide semiconductor electrode is with the manufacturing approach of laminated body " on the surface, can be made as the oxide semiconductor electrode that in said folder interlayer, has contained said photochemical catalyst and/or said characteristic variations material.
Utilize the purposes of the oxide semiconductor electrode that manufacturing approach of the present invention obtains to can be used as employed coloring matter sensitization type light charging capacitor in the coloring matter sensitization type light charging capacitor and decompose in substrate and the dye-sensitized solar cell employed dye-sensitized solar cell with uses such as base materials with base material, the pollutant that can use light-catalyzed reaction to decompose the pollutant in the atmosphere with employed electroluminescent display in base material, the electroluminescent display; Yet wherein, be applicable to that more employed dye-sensitized solar cell is used base material in the dye-sensitized solar cell.
G. the manufacturing approach of dye-sensitized solar cell
Below, the manufacturing approach of dye-sensitized solar cell of the present invention is described.The characteristic of the manufacturing approach of dye-sensitized solar cell of the present invention is; Comprise: use oxide semiconductor electrode that the manufacturing approach utilize said oxide semiconductor electrode obtains, possessed the 2nd electrode pattern and opposed base material to electrode base material, make said folder interlayer and said the 2nd electrode pattern mutually in the face of and form dye-sensitized solar cell with base material right to electrode base material formation operation; For said oxide semiconductor electrode with laminated body, it is said that to have the oxide semiconductor electrode of heat resistant substrate, said oxide semiconductor electrode or said dye-sensitized solar cell right with base material; Fill processing, this filling is handled and comprised: support dye-sensitized dose on the pore surface of said folder interlayer and said oxide semiconductor layer dye-sensitized dose supports operation; And after said dye-sensitized dose supports operation, between said the 2nd electrode pattern and said folder interlayer, and the porous body pore of said oxide semiconductor layer and said folder interlayer inner, the dielectric substrate that forms dielectric substrate forms operation.
According to the present invention,, can obtain the good dye-sensitized solar cell of energy conversion efficiency through using described oxide semiconductor electrode etc.
In addition, among the present invention, preferably said the 1st electrode layer is processed pattern-like, said oxide semiconductor electrode is formed processing with the 1st electrode pattern that laminated body or said oxide semiconductor electrode form the 1st electrode pattern.This is because through using said the 1st electrode pattern, can form the good dye-sensitized solar cell of energy conversion efficiency.
Below, to an example of the manufacturing approach of dye-sensitized solar cell of the present invention, use Figure 19 to describe.The manufacturing approach of dye-sensitized solar cell of the present invention for example supports operation and the 1st electrode pattern formation processing through carrying out dye-sensitized dose in advance; Support dye-sensitized dose at the folder interlayer 62 ' that has been patterned and the pore surface of oxide semiconductor layer 63 '; Then use oxide semiconductor electrode C with the 1st electrode pattern 64 ', possessed the 2nd electrode pattern 66 and opposed base material 67 to electrode base material 68; The mode that has given gap according to folder interlayer that makes said oxide semiconductor electrode C 62 ' and said the 2nd electrode pattern 66 configuration over the ground of practising physiognomy; Then use sealant 60; Form battery unit accordingly with the shape of the folder interlayer 62 ' that has been patterned and the 2nd electrode pattern 66 etc., thus form dye-sensitized solar cell with base material to (Figure 19 (a)).Then, shown in Figure 19 (b), dielectric substrate formation is injected in the gap that is formed at 66 of folder interlayer 62 ' and the 2nd electrode patterns with applying liquid.Like this, shown in Figure 19 (c), between folder interlayer 62 ' and the 2nd electrode pattern 66, just can form dielectric substrate 69.In addition; Be under the liquid or gelatinous situation particularly, for the volatilization that prevents solvent, the loss of dielectric substrate etc., for another example shown in Figure 19 (d) at said dielectric substrate; Through utilizing sealant 60 grades to seal, make dye-sensitized solar cell.
In addition, in the dye-sensitized solar cell that utilizes the present invention to obtain, both can the electrode that be formed at a plurality of battery units on the base material externally be connected, also can connect in inside.As the dye-sensitized solar cell that the electrode of battery unit is connected in inside; For example shown in figure 20; Can enumerate the sealant 60 and the conductive connector 84 that use insulating properties, with the 1st electrode pattern 64 ' and the 2nd electrode pattern 66 at the dye-sensitized solar cell of internal series-connection etc.
In addition; The manufacturing approach of dye-sensitized solar cell of the present invention; Be through carrying out dye-sensitized solar cell with the right formation of base material; With to oxide semiconductor electrode with laminated body, the oxide semiconductor electrode that has heat resistant substrate, oxide semiconductor electrode or dye-sensitized solar cell with base material to filling processing; And oxide semiconductor electrode is carried out the formation of the 1st electrode pattern with laminated body or oxide semiconductor electrode handle, and the method for formation dye-sensitized solar cell.Below, will to employed dye-sensitized solar cell among the present invention with base material to, fill to handle and the 1st electrode pattern forms to handle and is elaborated.
1. dye-sensitized solar cell is right with base material
At first, to employed dye-sensitized solar cell base material among the present invention to describing.Among the present invention employed dye-sensitized solar cell with base material to be through use utilize oxide semiconductor electrode that described " manufacturing approach of F. oxide semiconductor electrode " obtain, possessed the 2nd electrode pattern and opposed base material to electrode base material, what make that said folder interlayer and said the 2nd electrode pattern face mutually forms operation to electrode base material and obtains.
Below, will describe electrode base material formation operation of the present invention.
(1) opposed base material
At first, employed opposed base material in this operation is described.Employed opposed base material is the base material of the 2nd electrode pattern stated after supporting in this operation.As employed opposed base material in this operation; Both can be material transparent, also can be opaque material, not special the qualification; Yet for example in dye-sensitized solar cell, become under the situation of sensitive surface preferably transparent excellent material at said opposed base material.In addition, in the present invention, preferably use thermal endurance, weatherability, to the good base material of gas-barrier property of steam etc.As the opposed base material of this kind and since with above-mentioned " E. has the manufacturing approach of the oxide semiconductor electrode of heat resistant substrate " in the content put down in writing identical, therefore the explanation is here omitted.
(2) the 2nd electrode patterns
Below, employed the 2nd electrode pattern in this operation is described.Employed the 2nd electrode pattern is to face mutually with the folder interlayer of said oxide semiconductor electrode in this operation, the part of the electric charge current collection that will produce because of rayed.Said the 2nd electrode pattern is when making dye-sensitized solar cell, usually according to after the 1st electrode pattern the stated mode faced mutually form.As the metal oxide that constitutes employed the 2nd electrode pattern in this operation; So long as excellent conductivity and not to electrolytical corrosive material; Just not special the qualification, yet under the situation of the sensitive surface side that is positioned at light, the material that the permeability of preferred light is good.The metal oxide that can be used for this kind the 2nd electrode pattern is because identical with the metal oxide of formation the 1st electrode layer put down in writing in above-mentioned " the D. oxide semiconductor electrode is with the manufacturing approach of laminated body ", the explanation omission therefore will be here.In addition, as the metal oxide that constitutes the 2nd electrode pattern, preferably consider to constitute said the 1st electrode layer constituent work function etc. and suitably select.In addition, as the thickness of employed the 2nd electrode pattern among the present invention, though not special the qualification, be in the scope of 0.1～500nm specifically, wherein more preferably in the scope of 1nm～300nm.
(3) dye-sensitized solar cell is with the right formation method of base material
Below, describe with the right method of base material forming dye-sensitized solar cell.As forming dye-sensitized solar cell with the right method of base material; So long as can obtain the method for the good dye-sensitized solar cell of energy conversion efficiency; Just not special the qualification; Specifically, can according to respect to after the dielectric substrate handled of the filling stated form period of this operation of carrying out of operation, ground as follows is roughly distinguished.That is, situation of before said dielectric substrate forms operation, carrying out this operation and the situation of after said dielectric substrate forms operation, carrying out this operation are arranged.
When this operation was carried out before said dielectric substrate forms operation; Owing to also do not form dielectric substrate; Therefore between said folder interlayer and said the 2nd electrode pattern, in order to have the gap that forms dielectric substrate, it is right with base material to need to form dye-sensitized solar cell.Under this situation; As forming dye-sensitized solar cell with the right method of base material; So long as the dye-sensitized solar cell that can obtain to have possessed said gap is with the right method of base material, just not special the qualification, however for example can enumerate the method for using spacer etc.As said spacer block, for example can enumerate glass spacer, resin spacer or olefines perforated membrane etc.In addition, as said gap, so long as have the gap of the width that can form dielectric substrate, just not special the qualification, however in general be in the scope of 0.01～100 μ m, wherein more preferably in the scope of 0.1～50 μ m.
On the other hand, when this operation is carried out,, therefore do not need to be provided with as described above the gap after said dielectric substrate forms operation owing to be formed with dielectric substrate on the base material and on the folder interlayer.Under this situation; As forming dye-sensitized solar cell, so long as can obtain the method for required dye-sensitized solar cell, just not special the qualification with the right method of base material; Yet specifically, can enumerate the said method that electrode base material is fitted etc.
In addition; In this operation; Can be through using general sealant, form battery unit accordingly with the shape of folder interlayer that has been patterned and the 2nd electrode pattern etc., it is right with base material to be formed on the dye-sensitized solar cell that has possessed a plurality of battery units on the base material.
2. fill and handle
Below, filling processing of the present invention is described.Filling of the present invention is handled and is meant that dye-sensitized dose supports operation and form operation at said dye-sensitized dose dielectric substrate that carries out after supporting operation.Among the present invention; Through oxide semiconductor electrode is handled carrying out said filling with base material with laminated body, the oxide semiconductor electrode that has heat resistant substrate, oxide semiconductor electrode or dye-sensitized solar cell, make dye-sensitized solar cell.Below, dye-sensitized dose of handling as filling of the present invention supported operation and dielectric substrate form operation and describe.
(1) dye-sensitized dose supports operation
At first, dye-sensitized dose that said filling is handled supports operation and describes.Said dye-sensitized dose supports operation; Be to said oxide semiconductor electrode with laminated body, said have the oxide semiconductor electrode of heat resistant substrate, said oxide semiconductor electrode or said dye-sensitized solar cell with base material to what carry out, be to support dye-sensitized dose operation at the folder interlayer of these members and the pore surface of oxide semiconductor layer.
(a) dye-sensitized dose
In this operation employed dye-sensitized dose so long as because of rayed produces the material of electric charge, just not special the qualification, however specifically, can use organic pigment or metal complex dye.For example, can enumerate the pigment of acridine, azo class, indigo class, quinones, Coumarins, merocyanine class, phenyl xanthene (phenylxanthene) class as organic pigment.Wherein, preferred Coumarins.
In addition, as said metal complex dye, preferred ruthenium class pigment, preferred especially ruthenium two pyridine pigments and ruthenium three pyridine pigments as ruthenium complex.This be because; Though in oxide semiconductor layer; Basically can't absorb visible light (light of the wavelength about 400～800nm); But for example through supported ruthenium complex compound in oxide semiconductor layer, what for can absorb significantly and produce opto-electronic conversion to connecting visible light, thereby the light wavelength zone that can carry out opto-electronic conversion can be widened significantly.
(b) support dye-sensitized dose method
In this operation; As the method that supports dye-sensitized dose on the pore surface of said folder interlayer and said oxide semiconductor layer; Not special the qualification; For example can enumerate and in dye-sensitized dose solution, flood the member that makes it dry method behind said oxide semiconductor layer and the said folder interlayer, exposed the folder interlayer to not having heat resistant substrate, for example coating such as oxide semiconductor electrode has been dissolved dye-sensitized dose solution and has been made it the method etc. of drying.
(2) dielectric substrate forms operation
Below, the dielectric substrate formation operation that said filling is handled describes.It is between said the 2nd electrode pattern and said folder interlayer that said dielectric substrate forms operation, and the porous body pore of said oxide semiconductor layer and said folder interlayer is inner, forms the operation of the dielectric substrate that transmits the electric charge that produces because of rayed.
(a) dielectric substrate
The dielectric substrate that utilizes this operation to obtain is between the folder interlayer and the 2nd electrode pattern of dye-sensitized solar cell, the layer of the charge transport between carry out in said folder interlayer and said oxide semiconductor layer, being supported dye-sensitized dose and said the 2nd electrode pattern.Said dielectric substrate as a rule contains redox couple, as said redox couple, can use employed redox couple in general dye-sensitized solar cell.As concrete redox couple, can enumerate iodo-iodine compound, bromo-bromine compounds.In addition,, metal iodides such as LiI, NaI, KI, CaI etc. can be enumerated,, LiBr, NaBr, KBr, CaBr can be enumerated as said bromine compounds as said iodine compound 2Deng.
In addition, as the form of the dielectric substrate that utilizes this operation to obtain, so long as can carry out the form of charge transport, no matter just not special the qualification is solid, shaped, gel, liquid any form can.Specifically, can enumerate with said redox couple use polymeric solidization form, use the gelating agent gelation form, make it to be dissolved in the solvent and fluidization form etc.
And; Among the present invention; Because said folder interlayer and said oxide semiconductor layer are porous mass, therefore when use said gelation redox couple and said fluidization redox couple the time, the part of said redox couple is just mobile to porous mass inside.
As employed macromolecule in the said solidification, though not special the qualification, for example can enumerate CuI, polypyrrole, polythiophene etc.This kind macromolecule is owing to have conductivity, and cavity conveying property is high, therefore is suitable for being used.
In addition, as said gelating agent, though not special the qualification, for example when the electrolyte of acquisition physical gel, can enumerate polyacrylonitrile, polymethacrylates etc. as gelating agent.In addition, when obtaining the electrolyte of chemical gel, can enumerate esters of acrylic acid, methyl acrylic ester etc.And so-called physical gel is meant the gel because of near interaction gelation room temperature of physics, and so-called chemical gel is meant the gel of the chemical bond gelation that obtains because of cross-linking reaction etc.
In addition, as said solvent, though not special the qualification, for example can enumerate water, acetonitrile, methoxy propoxy nitrile etc.
In addition, utilize dielectric substrate that this operation obtains as required, can also contain additives such as crosslinking agent, Photoepolymerizationinitiater initiater, tackifier, normal temperature fuse salt.
In addition, as the thickness of the dielectric substrate that utilizes this operation to obtain, though not special the qualification, comprise that the thickness of folder interlayer and oxide semiconductor layer is preferably in the scope of 2 μ m～100 μ m, wherein more preferably in the scope of 2 μ m～50 μ m.This be because, therefore when less than said scope, then, might cause short circuit because the folder interlayer contacts with the 2nd electrode pattern easily, when surpassing said scope, then internal resistance becomes big, might cause the performance reduction.
(b) the formation method of dielectric substrate
Below, the method that forms dielectric substrate is described.As the method that forms said dielectric substrate; So long as can obtain the method for the good dye-sensitized solar cell of energy conversion efficiency; Just not special the qualification; Yet specifically, can be according to respect to as followsly roughly distinguishing the described period that electrode base material is formed this operation of carrying out of operation.That is, have in said situation of carrying out this operation before electrode base material is formed operation and in said situation of carrying out this operation after electrode base material is formed operation.
When this operation by said when carrying out before electrode base material is formed operation, because it is not right with base material also to form dye-sensitized solar cell, therefore at direct formation dielectric substrate just on the base material and on the folder interlayer.Thus, just need to form dielectric substrate with self-supporting property.As the method that forms this kind dielectric substrate; Though not special the qualification; Yet specifically; The dielectric substrate that can enumerate the constituent through will containing said dielectric substrate forms with coating liquid and is coated on base material and the folder interlayer, is meant to solidify to wait and the method (rubbing method) of formation dielectric substrate etc.In said rubbing method, mainly obtain the dielectric substrate of solid, shaped, under the situation of the dielectric substrate that obtains said solid, shaped, as a rule, said dielectric substrate forms and contains said redox couple, keeps its said macromolecule with coating liquid.
Coating process as said rubbing method; Not special the qualification; Can use known coating process; Specifically, can enumerate mould cladding process, intaglio plate cladding process, reverse intaglio plate cladding process, cylinder cladding process, reverse cylinder cladding process, excellent cladding process, scraper cladding process, knife coating, air-blade type cladding process, slit die cladding process, sliding die cladding process, immersion coating method, fine excellent cladding process, the fine excellent cladding process of reverse, stencil printing (rotation mode) etc.
In addition; In said rubbing method, contain under the situation of crosslinking agent, Photoepolymerizationinitiater initiater etc. with coating liquid in said dielectric substrate formation, be coated with said dielectric substrate formation with after applying liquid; Make it sclerosis through irradiation active ray etc., just can form the dielectric substrate of solid, shaped.
On the other hand, when carrying out before electrode base material is formed operation,, therefore in this gap, formed dielectric substrate said when this operation because it is right with base material to be formed with the dye-sensitized solar cell with given gap.Under this situation; As the method that forms dielectric substrate; Though not special the qualification; Yet specifically, can enumerate through the dielectric substrate that between base material and folder interlayer and the 2nd electrode pattern, injects the constituent that contains said dielectric substrate and form with applying liquid, and the method (injection method) of formation dielectric substrate etc.In said injection method, can form solid, shaped, gel, liquid dielectric substrate.
As the method for implanting in the said injection method, form with the method that applies liquid so long as can between base material and folder interlayer and the 2nd electrode pattern, inject dielectric substrate, just not special the qualification, however for example can use the method for utilizing capillarity to inject.
In addition; In said injection method; Contain under the situation of said gelating agent with coating liquid in said dielectric substrate formation; Form with applying after liquid injects at dielectric substrate, for example the gel through carrying out temperature adjustment, ultraviolet irradiation, electron ray irradiation etc., can form having two dimension or three-dimensional crosslinked configuration or the dielectric substrate of solid, shaped.
3. the 1st electrode pattern forms and handles
Below, the 1st electrode pattern of the present invention is formed processing describe.It is that the 1st electrode layer is processed pattern-like that the 1st electrode pattern of the present invention is handled, and forms the processing of the 1st electrode pattern.At this moment, the 1st electrode pattern quilt forms with the pattern of folder interlayer etc. accordingly, and is formed according to the mode with area bigger than the pattern of folder interlayer etc.Handle through carrying out the 1st electrode pattern; Just can form said battery unit clear, that constitute by the folder interlayer that has been patterned and oxide semiconductor layer and the 1st electrode pattern in said " the D. oxide semiconductor electrode is with the manufacturing approach of laminated body "; Can these battery unit parallel connections be improved output current, or connect and the raising output voltage.As the method for the 1st electrode layer being processed pattern-like; So long as can form the method for required battery; Just not special the qualification; Yet specifically, can enumerate laser scribing method, wet etching, peel off method, dry-etching method, mechanical marking method etc., wherein more preferably laser scribing method and mechanical marking method.In addition; As other the method for the 1st electrode layer being processed pattern-like; For example can enumerate between the 1st electrode layer and base material the method that illustrated adhesive linkage patterning in said " E. has the manufacturing approach of the oxide semiconductor electrode of heat resistant substrate " is used etc.Specifically, this adhesive linkage and said oxide semiconductor electrode that has been patterned is bonding with the 1st electrode layer of laminated body through on base material, forming said adhesive linkage with pattern-like, make the oxide semiconductor electrode that has heat resistant substrate.When on from then on planting the oxide semiconductor electrode have heat resistant substrate, heat resistant substrate being peeled off, the 1st electrode layer on oxide semiconductor electrode only residue have the part of the adhesive linkage that has been patterned, consequently, can obtain the 1st electrode pattern.At this moment, the area through making the adhesive linkage that has been patterned is bigger than the area of the corresponding folder interlayer that has been patterned, and just can form the oxide semiconductor electrode that has possessed the 1st electrode pattern that has than presss from both sides bigger area such as interlayer.
4. fill processing and the 1st electrode pattern and form the period of handling
Below, describe carrying out the period that said filling is handled and the formation of said the 1st electrode pattern is handled.Said filling is handled as stated; Be to have dye-sensitized dose to support the processing that operation and said dielectric substrate form operation, to oxide semiconductor electrode with laminated body, the oxide semiconductor electrode that has heat resistant substrate, oxide semiconductor electrode or dye-sensitized solar cell with base material to carrying out said 2 operations.Among the present invention, both can be with said 2 situation that operation is carried out continuously, also can be with said 2 situation that operation is carried out respectively.In addition, said the 1st electrode pattern forms to be handled as stated, is the processing that forms the 1st electrode layer along the pattern of folder interlayer etc., and oxide semiconductor electrode is carried out with laminated body or oxide semiconductor electrode.And, among the present invention, do not form when handling even do not carry out said the 1st electrode pattern, also can obtain dye-sensitized solar cell.
Below, supporting operation, said the 1st electrode pattern with said dye-sensitized dose of in said filling is handled, carrying out at first, to form the period of handling be benchmark, and the manufacturing approach of dye-sensitized solar cell of the present invention is carried out illustration.
(a) oxide semiconductor electrode is at first carried out dye-sensitized dose of situation that supports operation with laminated body
As oxide semiconductor electrode is at first carried out the manufacturing approach of the dye-sensitized solar cell of dye-sensitized dose of situation that supports operation with laminated body, can enumerate following (i) to (iv) method.
(i) said oxide semiconductor electrode is carried out said dye-sensitized dose with laminated body and support operation; Handle through said the 1st electrode pattern is formed then, said base material forms operation, said stripping process, said dielectric substrate form operation and saidly electrode base material is formed operation carry out in proper order with this, and forms the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell
(ii) said oxide semiconductor electrode is carried out said dye-sensitized dose with laminated body and support operation; Form and handle through said base material being formed operation, said stripping process, said the 1st electrode pattern then, said dielectric substrate forms operation and saidly electrode base material is formed operation carry out in proper order with this, and forms the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell
(iii) said oxide semiconductor electrode is carried out said dye-sensitized dose with laminated body and support operation; Handle through said the 1st electrode pattern is formed then, said base material forms operation, said stripping process, saidly electrode base material is formed operation and said dielectric substrate form operation and carry out in proper order with this, and forms the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell
(iv) said oxide semiconductor electrode is carried out said dye-sensitized dose with laminated body and support operation; Form and handle through said base material being formed operation, said stripping process, said the 1st electrode pattern then, saidly electrode base material is formed operation and said dielectric substrate form operation and carry out in proper order, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this
(b) oxide semiconductor electrode is at first carried out the 1st electrode pattern with laminated body and form situation about handling
As oxide semiconductor electrode is at first carried out the manufacturing approach of the dye-sensitized solar cell of the situation that the 1st electrode pattern form to handle with laminated body, can enumerate following (v) to the method for (xi).
(v) said oxide semiconductor electrode is carried out said the 1st electrode pattern with laminated body and form processing; Form operation, said stripping process, said dielectric substrate and form operation and saidly electrode base material is formed operation carry out in proper order through supporting operation, said base material then, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this with said dye-sensitized dose
(vi) said oxide semiconductor electrode is carried out said the 1st electrode pattern with laminated body and form processing; Support operation, said stripping process, said dielectric substrate and form operation and saidly electrode base material is formed operation carry out in proper order through said base material being formed operation, said dye-sensitized dose then, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this
(vii) said oxide semiconductor electrode is carried out said the 1st electrode pattern with laminated body and form processing; Then through said base material is formed operation, said stripping process, said dye-sensitized dose support operation, said dielectric substrate and form operation and saidly electrode base material is formed operation carry out in proper order with this, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell
(viii) said oxide semiconductor electrode is carried out said the 1st electrode pattern with laminated body and form processing; Form operation, said stripping process, saidly electrode base material is formed operation and said dielectric substrate form operation and carry out in proper order through supporting operation, said base material then, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this with said dye-sensitized dose
(ix) said oxide semiconductor electrode is carried out said the 1st electrode pattern with laminated body and form processing; Support operation, said stripping process, saidly electrode base material is formed operation and said dielectric substrate form operation and carry out in proper order through said base material being formed operation, said dye-sensitized dose then, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this
(x) said oxide semiconductor electrode is carried out said the 1st electrode pattern with laminated body and form processing; Then through said base material is formed operation, said stripping process, said dye-sensitized dose support operation, saidly electrode base material is formed operation and said dielectric substrate form operation and carry out in proper order with this, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell
(xi) said oxide semiconductor electrode is carried out said the 1st electrode pattern with laminated body and form processing; Then through said base material being formed operation, said stripping process, saidly electrode base material is formed operation, said dye-sensitized dose support operation and said dielectric substrate and form operation and carry out in proper order, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this
(c) oxide semiconductor electrode that has heat resistant substrate is at first carried out dye-sensitized dose of situation that supports operation
As the manufacturing approach of the dye-sensitized solar cell that the oxide semiconductor electrode that has heat resistant substrate is at first carried out dye-sensitized dose of situation that supports operation, can enumerate following (xii) method to (xiii).
(xii) oxide semiconductor electrode that has heat resistant substrate is carried out dye-sensitized dose and support operation; Form operation and saidly electrode base material is formed operation carry out in proper order through said stripping process, said the 1st electrode pattern being formed operation, said dielectric substrate then, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this
(xiii) oxide semiconductor electrode that has heat resistant substrate is carried out dye-sensitized dose and support operation; Then through said stripping process, said the 1st electrode pattern being formed operation, saidly electrode base material is formed operation and said dielectric substrate form operation and carry out in proper order, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this
(d) oxide semiconductor electrode is at first carried out dye-sensitized dose of situation that supports operation
As oxide semiconductor electrode is at first carried out the manufacturing approach of the dye-sensitized solar cell of dye-sensitized dose of situation that supports operation with laminated body, can enumerate following (xiv) method to (xv).
(xiv) said oxide semiconductor electrode is carried out dye-sensitized dose and support operation; Handle through said the 1st electrode pattern is formed then, said dielectric substrate forms operation and saidly electrode base material is formed operation carry out in proper order with this, and forms the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell
(xv) said oxide semiconductor electrode is carried out dye-sensitized dose and support operation; Handle through said the 1st electrode pattern is formed then, saidly electrode base material is formed operation and said dielectric substrate form operation and carry out in proper order, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this
(e) oxide semiconductor electrode is at first carried out the 1st electrode pattern and form situation about handling
As the manufacturing approach of the dye-sensitized solar cell that oxide semiconductor electrode is at first carried out the situation that the 1st electrode pattern form to handle, can enumerate following (xvi) method to (xvii).
(xvi) said oxide semiconductor electrode is carried out said the 1st electrode pattern and form processing; Form operation and saidly electrode base material is formed operation carry out in proper order through supporting operation, said dielectric substrate then, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell with this with said dye-sensitized dose
(xvii) said oxide semiconductor electrode is carried out said the 1st electrode pattern and form processing; Then through said dye-sensitized dose is supported operation, saidly electrode base material is formed operation and said dielectric substrate forms operation and carry out in proper order with this, and form the manufacturing approach of the dye-sensitized solar cell of dye-sensitized solar cell
In the present invention; In said (i)～(xvii); More preferably (vii), the manufacturing approach of the dye-sensitized solar cell shown in (x), (xi), (xiv), (xv), (xvii), the manufacturing approach of the dye-sensitized solar cell shown in preferred (xvii) especially.
5. dye-sensitized solar cell
Below, the dye-sensitized solar cell that utilizes the present invention to obtain is described.Utilize dye-sensitized solar cell that the present invention obtains for example shown in Figure 19 (d), have: the oxide semiconductor electrode of the oxide semiconductor layer 63 ' that on base material 65, possessed the 1st electrode pattern 64 ' successively, has been patterned and the folder interlayer 62 ' that has been patterned; With said folder interlayer 62 ' mutually in the face of and possessed the 2nd electrode pattern 66 and opposite electrode 67 to electrode base material; Be formed at the dielectric substrate 69 between said folder interlayer 62 ' and said the 2nd electrode pattern 66.Constitute for each of the dye-sensitized solar cell that utilizes the present invention to obtain and since with the part of said " C. dye-sensitized solar cell " in the content put down in writing identical, therefore the explanation is here omitted.
And, in dye-sensitized solar cell of the present invention, utilize by the electric charge that produces in dye-sensitized dose and obtain photoelectric current, in general, can enumerate electronics as the electric charge that from dye-sensitized dose, produces.Utilize the irradiation of light, support dye-sensitized dose of absorbing light in folder interlayer and oxide semiconductor layer and shift to excited state.Dye-sensitized dose that is in excited state produces electronics, and the electronics that is produced is handed to folder interlayer etc.Then, pass the lead that is connected with the 1st electrode layer, carried to opposite electrode.So just can obtain photoelectric current.At this moment, dye-sensitized dose because of shifting oxidized to folder interlayer etc. the electronics that is produced.In addition, the electronics that is produced will be as the I that is present in the redox couple in the dielectric substrate after opposite electrode moves -/ I 3Central I 3Reduction, and form I -In addition, I -Through with oxidation dye-sensitized dose of reduction can get back to ground state.
And the present invention is not limited to said execution mode.Said execution mode is exemplary, and which kind of situation no matter the scheme that has the identical in fact formation of the thought of the technology of being put down in writing in the scope with technical scheme of the present invention and serve the same role effect be, all is contained in the technical scope of the present invention.
Embodiment
Below, it is further bright specifically to use embodiment that the present invention is carried out.
(embodiment 1)
1. the formation of porous layer
(1) oxide semiconductor layer forms the formation with layer
Form with applying liquid as oxide semiconductor layer, use particle size to be about the titanium oxide pastel Ti-NanoxideD (Solaronix corporate system) of 13nm, after skill in using a kitchen knife in cookery coating is scraped in utilization, at room temperature place 20 minutes after, 100 ℃ dry 30 minutes down.
(2) burn till
Form with layer for said oxide semiconductor layer, use electronics Muffle furnace (デ Application ケ Application corporate system P90), under 500 ℃, 30 minutes, atmospheric pressure atmosphere, burn till.So just obtained being used as the porous layer that porous body forms.
2. the formation of the 1st electrode layer
Form as the 1st electrode layer and to use composition, prepared in ethanol, to have dissolved the composition of stannic chloride of inidum chloride, the 0.005mol/l of 0.1mol/l.Thereafter; To carry out the said heat resistant substrate that burns till is located on the hotplate (400 ℃); Make porous layer upwards, on this porous layer that has been heated, utilize ultrasonic sprayer to spray described the 1st electrode layer and form and use composition; Form the ITO film of 500nm, formed dye-sensitized solar cell and used base material as nesa coating.
3. adhesive linkage and base material gives
Next, as adhesive linkage, the thermoplastic resin membrane below having processed.Through to density 0.898g/m 3Straight chain shape low density polyethylene (LDPE) (LLDPE) 98 weight portions in, mixed ethylene methoxylsilane 2 weight portions, radical initiator 0.1 weight portion and carry out glycerol polymerization have obtained the silane modified polyethylene resin.In this resin, mix by oxidation inhibitor, ultra-violet absorber, Photostabilised dose of weather agent particle that constitutes,, obtained the thermoplastic resin membrane of 50 microns of thickness through having used melt extruding of T shape mould.
Then; As the corona treatment face of the PET film (E5100 125 μ m spin in Japan) of transparent resin film base material and the dye-sensitized solar cell that processes the front with the ITO face of base material between the thermoplastic resin membrane that processes of clamping front, utilize the cylinder laminating machine to fit down at 130 ℃.
4. heat resistant substrate peels off
Thereafter, through alkali-free glass substrate is peeled off, with porous layer and the 1st electrode layer to the transfer printing of base material side.
5. the pattern of porous layer is handled
Through porous layer pruned, formed the porous layer of 0.8mm thereafter.
6. dye-sensitized dose give
Through said porous layer impregnated in pre-prepd absorption with pigment solution (with the ruthenium complex (RuL of island KCC 2(NCS) 2) be dissolved in the absolute ethyl alcohol, make concentration reach 3 * 10 -4Mol/l), the dye-sensitized solar cell that has obtained in porous layer, having supported sensitizing coloring matter is used base material.
7. the making of dye-sensitized solar cell
Use the dye-sensitized solar cell of gained to use base material, made dye-sensitized solar cell as followsly.The dielectric substrate formation that forms dielectric substrate is adjusted with composition as followsly.With methoxyacetonitrile as solvent, with the liquid of the tert .-butylpyridine of the dimethyl propyl imidazoles iodide of the iodine of the lithium iodide that has dissolved concentration 0.1mol/l, concentration 0.05mol/l, concentration 0.3mol/l, concentration 0.5mol/l as electrolyte.
Utilize the sarin of thickness 20 μ m film adhered said electrode for dye-sensitized solar cell, opposed base material, flood dielectric substrate formation betwixt and made dye-sensitized solar cell with applying liquid.As opposed base material, used have the thickness of 150nm, and had on the opposed film substrate of ITO sputtering layer that sheet resistance is 7 Ω/ and utilize sputter to give the material of thickness for the platinum film of 50nm.
(evaluation)
For the dye-sensitized solar cell of made, the result that the method for stating after the utilization has been measured current-voltage characteristic is short circuit current 14.8mA/cm 2, open circuit voltage 683mV, conversion efficiency 6.1%.
(embodiment 2)
Except utilizing following method to form the porous layer, utilize and made dye-sensitized solar cell with embodiment 1 identical method.
< the formation method of porous layer (embodiment 2) >
(1) the folder interlayer forms the formation with layer
Form with applying liquid as the folder interlayer, through according to the TiO that makes primary particle size 20nm 2Particulate (Japanese ア エ ロ ジ Le corporate system P25) reaches the mode that 1 quality %, acrylic resin (105 ℃ of molecular weight 25000, glass transition temperatures) (rayon of Mitsubishi corporate system BR87) reach 10 quality %; After utilizing paint mixer (paintshaker) to make resin dissolves in methyl ethyl ketone and toluene, with TiO 2Microparticulate and made the folder interlayer and form with applying liquid.On the alkali-free glass substrate of preparing as resistant substrates (thickness 0.7mm), utilize wire bar to apply this folder interlayer and form with applying liquid, make it dry.
(2) oxide semiconductor layer forms the formation with layer
Form with applying liquid as oxide semiconductor layer, through according to the TiO that makes primary particle size 20nm 2Particulate (Japanese ア エ ロ ジ Le corporate system P25) reaches 37.5 quality %, acetylacetone,2,4-pentanedione and reaches the mode that 1.25 quality %, polyethylene glycol (mean molecule quantity 3000) reach 1.88 quality %; Use homogenizer to make it to dissolve and be scattered in water and the isopropyl alcohol, made oxide semiconductor layer and formed with applying liquid.Form and utilize scraper to be coated with oxide semiconductor layer on the heat resistant substrate with layer to form having formed said folder interlayer with after applying liquid, at room temperature placed 20 minutes after, 100 ℃ dry 30 minutes down.
(3) burn till
Said folder interlayer formed with layer and said oxide semiconductor layer form, use electronics Muffle furnace (デ Application ケ Application corporate system P90), under 500 ℃, 30 minutes, atmospheric pressure atmosphere, burn till with layer.So just obtained porous layer as porous body formation.
(evaluation)
For the dye-sensitized solar cell of made, the result that the method for stating after the utilization has been measured current-voltage characteristic is short circuit current 13.2mA/cm 2, open circuit voltage 680mV, conversion efficiency 5.5%.
(comparative example 1)
Except as adhesive linkage, use density to be 0.898g/m 3LLDPE, utilizing with embodiment 2 identical method used thicknesses is beyond the thermoplastic film of 50 μ m, the method that utilization and embodiment 2 are identical has been manufactured experimently dye-sensitized solar cell.
But in said " 4. heat resistant substrate peels off ", when alkali-free glass substrate was peeled off, it was bad to produce transfer printing property, can't make dye-sensitized solar cell.
(comparative example 2)
Except as adhesive linkage, the EVA (ethylene-vinyl acetate copolymer) (タ マ Port リ corporate system SB-10) that uses 50 micron thick utilizes the method identical with embodiment 2 in addition, has made dye-sensitized solar cell.
(evaluation)
For the dye-sensitized solar cell of made, the result that the method for stating after the utilization has been measured current-voltage characteristic is short circuit current 13.2mA/cm 2, open circuit voltage 678mV, conversion efficiency 5.4%.
(embodiment 3)
Form with applying liquid as the folder interlayer, through according to the TiO that makes primary particle size 20nm 2It is the mode that the acrylic resin (105 ℃ of molecular weight 25000, glass transition temperatures) (rayon of Mitsubishi corporate system BR87) of polymethyl methacrylate reaches 10 quality % that particulate (Japanese ア エ ロ ジ Le corporate system P25) reaches 1 quality %, principal component; Use homogenizer with after resin dissolves is in methyl ethyl ketone and toluene, with TiO 2Microparticulate and made the folder interlayer and form with applying liquid.Utilize wire bar to be coated on the alkali-free glass substrate of preparing as resistant substrates (thickness 0.7mm) this coating liquid, make it dry.Thereafter, through in the zone of 1cm * 1cm, carrying out mask process, use the methyl ethyl ketone dissolving to remove in the zone beyond the said zone, the folder interlayer that has obtained having the zone of 1cm * 1cm forms uses pattern.
Form with applying liquid as oxide semiconductor layer, through according to the TiO that makes primary particle size 20nm 2Particulate (Japanese ア エ ロ ジ Le corporate system P25) reaches 37.5 quality %, acetylacetone,2,4-pentanedione and reaches the mode that 1.25 quality %, polyethylene glycol (mean molecule quantity 3000) reach 1.88 quality %; Use homogenizer to make it to dissolve and be scattered in water and the isopropyl alcohol, made slip.On the said heat resistant substrate and after said folder interlayer utilizes scraper to be coated with said slip on forming with pattern, at room temperature placed 20 minutes after, dry 30 minutes down at 100 ℃., use electronics Muffle furnace (デ Application ケ Application corporate system P90), under 500 ℃, 30 minutes, atmospheric pressure atmosphere, burn till thereafter.Folder interlayer and oxide semiconductor layer have so just been obtained as porous body formation.
, as 1st electrode layer form with apply liquid, prepared in ethanol, to have dissolved the coating liquid of stannic chloride of inidum chloride, the 0.005mol/l of 0.1mol/l thereafter.Thereafter; Carry out said burning till, the heat resistant substrate that will possess folder interlayer and oxide semiconductor layer is located on the hotplate (400 ℃), makes oxide semiconductor film upwards; On this oxide semiconductor film that has been heated; Utilize ultrasonic sprayer to spray described the 1st electrode layer and form, form the ITO film of 500nm, obtained oxide semiconductor electrode and used laminated body as electrically conducting transparent with applying liquid.
Thereafter, use PET film (A5100,125 μ m spin in Japan) as base material, said base material is implemented mask process, the coated heat sealant (spin, and MD1985), through it is air-dry, formed the adhesive linkage in the zone with 2.5cm * 2.5cm by Japan.Being in said folder interlayer according to the zone that makes this adhesive linkage forms with the mode on the zone of pattern; Said adhesive linkage and said oxide semiconductor electrode are fitted down at 120 ℃ with the ito surface of laminated body, obtained having the oxide semiconductor electrode of heat resistant substrate.
, from the oxide semiconductor electrode that have heat resistant substrate heat resistant substrate peeled off, obtained having the oxide semiconductor electrode of oxide semiconductor layer of being patterned etc. thereafter.
Thereafter, as dye-sensitized dose with the ruthenium complex (RuL of island KCC 2(NCS) 2) be dissolved in the ethanol solution, make concentration reach 3 * 10 -4Mol/l makes absorption and uses pigment solution, makes it to support on oxide semiconductor layer etc. through dipping.
Use the oxide semiconductor electrode that so obtains, made dye-sensitized solar cell as followsly.At first, the dielectric substrate formation that forms dielectric substrate is adjusted with applying liquid as followsly.With methoxyacetonitrile as solvent, with the liquid of the tert .-butylpyridine of the dimethyl propyl imidazoles iodide of the iodine of the lithium iodide that has dissolved concentration 0.1mol/l, concentration 0.05mol/l, concentration 0.3mol/l, concentration 0.5mol/l as electrolyte.
With said oxide semiconductor electrode, utilize the sarin of thickness 20 μ m to fit to electrode base material, flooded dielectric substrate betwixt and formed with applying liquid, with it as element.As to electrode base material, used have the thickness of 150nm, and had on the opposed base material of ITO sputtering layer that sheet resistance is 7 Ω/ and utilize sputter to give the material of thickness for the platinum film of 50nm.
For the dye-sensitized solar cell of made, the method for stating after the utilization has been measured current-voltage characteristic.Its result is that as the battery behavior of monocell, short circuit current is 13.8mA/cm 2, open circuit voltage is that 680mV, conversion efficiency are 5.9%.
(embodiment 4)
To contain dispersion liquid (ST-K01 of the former industry of stone (strain) system) the 2 weight portions mixing of the titanium oxide microparticle of average grain diameter 7nm as isopropyl alcohol 3 weight portions of dispersant, as photochemical catalyst; After having stirred 10 minutes under 90 ℃, add perfluoro alkoxy silane as binding agent (MF-160E of ト one ケ system プ ロ ダ Network Star (strain) system) 0.14 weight portion again and further mix, stir., with isopropanol floride be interpreted as 4 times, obtained being used to obtain the coating fluid of wettability change layer thereafter.
On the alkali-free glass substrate of preparing as heat resistant substrate (thickness is 0.7mm), rotation applies said coating liquid, with gained film 150 ℃ dry 10 minutes down, obtained the wettability change layer of thickness 10nm.
, prepare be formed with the photomask (ultraviolet mask) of the tetragonal peristome that be 1cm * 1cm, it is disposed on the said wettability change layer thereafter.Then, use mercury vapor lamp as light source, at exposure intensity 70mW/cm 2, under 50 seconds the condition of irradiation time, with said wettability change layer exposure.Utilize and should make public, the top central given area of being made public of wettability change layer has been obtained the wettability change pattern by hydrophiling.The zone of the hydrophiling water that drips to being utilized optionally exposure is 8 ° after utilizing contact angle determination device (CA-Z of consonance interface science (strain) system) to measure its contact angle.On the other hand, the contact angle of the water of the non-exposure portion of wettability change layer is 142 °, the hydrophiling on the zone that can confirm to make public.
Form with applying liquid as the folder interlayer, through according to the TiO that makes primary particle size 20nm 2It is the mode that the acrylic resin (105 ℃ of molecular weight 25000, glass transition temperatures) (rayon of Mitsubishi corporate system BR87) of polymethyl methacrylate reaches 10 quality % that particulate (Japanese ア エ ロ ジ Le corporate system P25) reaches 1 quality %, principal component; After utilizing homogenizer to make resin dissolves in methyl ethyl ketone and toluene, with TiO 2Microparticulate and made the folder interlayer and form with applying liquid.Should apply liquid utilizes wire bar to be coated on the said wettability change layer.This film in fact only be formed at photocatalysis layer form with in the middle of layer top by hydrophiling the zone on, that is, only be formed in the exposure portion of 1cm * 1cm.The shape hold facility of filming is high, films not formed by the part of hydrophiling., wettability change layer and folder interlayer formed Zone Full with pattern, use mercury vapor lamp as light source, at exposure intensity 70mW/cm thereafter 2, make public under 50 seconds the condition of irradiation time.Through making public, be formed with the folder interlayer and form with the zone beyond the pattern by hydrophiling.Contact angle before and after the hydrophiling is respectively 143 °, 8 °.
With embodiment 1 described in identically made dye-sensitized solar cell thereafter.
To the dye-sensitized solar cell of made, the method for stating after the utilization has been measured current-voltage characteristic.
In addition, carried out performance evaluation with embodiment 1, its result is that as the battery behavior of single battery, short circuit current is 13.8mA/cm identically 2, open circuit voltage is that 680mV, conversion efficiency are 5.9%.
(evaluation method)
A. ageing stability evaluation
Dye-sensitized solar cell to made in embodiment 1, embodiment 2 and comparative example 2; After making through moment of 1 month measured current-voltage characteristic once more; Its result does; The sustainment rate of conversion efficiency is 95%, 96% among embodiment 1, the embodiment 2, and is respectively 82% sustainment rate in the comparative example 2, and the reduction of performance is fairly obvious.After the dye-sensitized solar cell of made carries out visualization in to the comparative example 2 of having observed the performance reduction, seen peeling off between PET base material and the 1st electrode layer.
B. the evaluation method of current-voltage characteristic
The evaluation of the element of made is following, with AM1.5, simulated solar irradiation (incident intensity 100mW/cm 2) as light source, make it to measure through utilizing ソ one ス メ ジ ヤ one ユ ニ Star ト (ケ one ス レ one 2400 types) to apply voltage from having the base material side incident of the porous layer that has adsorbed pigment.

Claims (8)

1. oxide semiconductor electrode; The adhesive linkage that has base material, is formed on the said base material and processes by thermoplastic resin, the 1st electrode layer that is formed on the said adhesive linkage and processes by metal oxide, be formed on said the 1st electrode layer and contain the porous layer of metal-oxide semiconductor (MOS) particulate; Wherein, Said porous layer by the oxide semiconductor layer that contacts with said the 1st electrode layer, be formed on the said oxide semiconductor layer and compare the higher folder interlayer of void content and constitute with said oxide semiconductor layer, said thermoplastic resin contains silane-modified resin.
2. oxide semiconductor electrode according to claim 1 is characterized in that said thermoplastic resin contains adhesive resin.
3. oxide semiconductor electrode according to claim 1 is characterized in that, said base material is the resin-made membrane base material.
4. oxide semiconductor electrode according to claim 1 is characterized in that, said porous layer contains and the identical metallic element of the metallic element that metal oxide had that constitutes said the 1st electrode layer.
5. oxide semiconductor electrode according to claim 1 is characterized in that, said porous layer is carried out pattern to be handled.
6. oxide semiconductor electrode according to claim 1 is characterized in that, the surface adsorption of contained metal-oxide semiconductor (MOS) particulate has the pigment sensitizer in said porous layer.
7. an oxide semiconductor electrode that has heat resistant substrate is characterized in that, on the porous layer that the described oxide semiconductor electrode of claim 1 is had, has heat resistant substrate.
8. dye-sensitized solar cell; It is characterized in that; In porous layer the surface adsorption of contained metal-oxide semiconductor (MOS) particulate dye-sensitized dose the described oxide semiconductor electrode of claim 1 with by what the 2nd electrode layer and opposed base material constituted electrode base material is configured to: folder is at a distance from containing the dielectric substrate of redox couple, and said porous layer and said the 2nd electrode layer are opposed.
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