CN103035410A

CN103035410A - Dye-sensitized photoelectric conversion device and manufacturing method thereof and metal oxide slurry

Info

Publication number: CN103035410A
Application number: CN2011103057173A
Authority: CN
Inventors: 李勇明; 高濂; 杨松旺
Original assignee: Shanghai Institute of Ceramics of CAS; Sony Corp
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2011-10-08
Filing date: 2011-10-08
Publication date: 2013-04-10
Anticipated expiration: 2031-10-08
Also published as: CN103035410B

Abstract

Provided is a manufacturing method capable of achieving production of an excellent and productive dye-sensitized photoelectric conversion device. The manufacturing method of the dye-sensitized photoelectric conversion device includes the following steps: preparing metal oxide slurry by spreading more than two kinds of metal oxide nano-particles, at least one kind of scattering particles and binders to dispersing agents, and forming multihole semiconductor layers by using the metal oxide slurry, wherein the more than two kinds of the metal oxide nano-particles respectively possess different particle size distributions.

Description

Dye sensitized optoelectronic converting device and manufacture method thereof, and metal oxide paste

Technical field

Present technique relates to dye sensitized optoelectronic converting device and manufacture method thereof, and metal oxide paste.Be specifically related to use metal oxide paste to form the manufacture method of the dye sensitized optoelectronic converting device of porous semiconductor layer.

Background technology

Solar energy resources is very abundant, is a kind of resource of tool exploitation possibility.Solar cell is the device that luminous energy directly is converted to electric energy by photoelectric effect or Photochemical effects.Solar cell uses sunlight as the energy, and is therefore little to environmental impact, has great prospect.

Solar cell can be categorized as silicon solar cell according to the material of its use, multi-element compounds thin-film solar cells, dye sensitized optoelectronic converting device, organic solar batteries etc.Wherein, dye sensitized optoelectronic converting device is a kind of battery that in recent years attracts most attention.

As dye sensitized optoelectronic converting device, the battery that is proposed by the researcher of Lausanne, SUI Polytechnics be widely known by the people (for example, with reference to non-patent literature 1).This battery is the porous semiconductor layer (TiO with the molecule sensitization ₂Layer, ZnO layer etc.) as the semiconductor solar cell of light anode, have all superiority such as low cost, simple in structure, easy manufacturing, suitable volume production.

As the manufacture method of porous semiconductor layer, proposing has the technology (for example, with reference to patent documentation 1, non-patent literature 2,3) of using metal oxide paste.

Technical literature formerly

Patent documentation

Patent documentation 1: Japanese documentation JP 2006-49311 communique

Non-patent literature

Non-patent literature 1:B.O ' Regan, M.

Nature, 353,737 (1991)

Non-patent literature 2:S.Ito et al, " Fabrication of Thin Film Dye Sensitized Solar Cells with Solar to Electric Power Conversion Efficiency over 10% ", Thin Solid Films 2008,516,4613-4619.

Non-patent literature 3:Z.S.Wang et al, " Significant Influence of TiO ₂Photoelectrode Morphology on the Energy Conversion Efficiency of N719 Dye-Sensitized Solar Cell, " Coord.Chem.Rev.2004,248,1381-1389.

Summary of the invention

The problem that invention will solve

But, in above-mentioned patent documentation 1, non-patent literature 2,3 in the technology of record, with titania slurry apply repeatedly, dry, cure thickness and the effect that can obtain expecting.For repeatedly apply in this wise, dry, cure, film forming is processed needs a large amount of time and the energy, so these technology are unpractical technology from the viewpoint of industrial production.

Therefore, the purpose of present technique provides and can realize excellent productive dye sensitized optoelectronic converting device and manufacture method thereof, and metal oxide paste.

For the means of dealing with problems

In order to address the above problem, the first technology is a kind of manufacture method of dye sensitized optoelectronic converting device, may further comprise the steps:

By being distributed to, two or more at least metal oxide nanoparticles, at least a above scattering particles and binding agent prepare metal oxide paste in the dispersant; And

Use metal oxide paste to form porous semiconductor layer;

Wherein, two or more at least metal oxide nanoparticles has respectively different particle diameter distributions.

The second technology is a kind of dye sensitized optoelectronic converting device, comprising: optoelectronic pole, to electrode and dielectric substrate, wherein,

Optoelectronic pole comprises conductive layer and porous semiconductor layer,

Porous semiconductor layer comprises two or more at least metal oxide nanoparticles and at least a above scattering particles,

At least two or more metal oxide nanoparticles has respectively different particle diameters and distributes.

The 3rd technology is a kind of metal oxide paste for dye sensitized optoelectronic converting device, comprises:

At least two or more metal oxide nanoparticles;

At least a above scattering particles;

Binding agent; And

Dispersant;

In present technique, be preferably as follows: two or more at least metal oxide nanoparticles and at least a above scattering particles that will have the different-grain diameter distribution are distributed in the dispersant that has dissolved binding agent equably, make the metal oxide paste with predetermined rheological properties.

In present technique, be preferably as follows: after the oxidate nano colloid with high crystalline was coated on conductive layer or the conductive substrate and cures the formation adhesion layer, the dispersion that applies a metal oxide paste on the surface of adhesion layer formed metal oxide electrode.

In present technique, be preferably as follows: will have the optoelectronic pole that uses the porous semiconductor layer that above-mentioned metal oxide paste forms, comprise TiO ₂(B) the gel-like electrolyte layer of type nano wire and have porous graphene layer electrode combination is used.

In present technique, formed porous semiconductor layer with comprising the metal oxide paste with two or more at least metal oxide nanoparticles that different-grain diameter distributes and at least a above scattering particles.In the porous semiconductor layer that forms using such metal oxide paste, because can take into account adsorbance and these two mutual conflicting functions of light scattering effect of dyestuff, therefore only apply once a kind of slurry, just can form the porous semiconductor layer with excellent conversion efficiency.So, can simplify the formation step of porous semiconductor layer.

The invention effect

As mentioned above, according to present technique, the formation step of porous semiconductor layer can be simplified, therefore excellent productivity can be realized.And can cut down manufacturing cost.

Description of drawings

Fig. 1 is the profile that a configuration example of the dye sensitized optoelectronic converting device that an execution mode of present technique relates to is shown;

Fig. 2 is the profile that amplifies the part that porous semiconductor layer is shown;

Fig. 3 A and Fig. 3 B are the photos of surperficial SEM of the porous oxidation titanium layer of embodiment 1;

Fig. 4 A and Fig. 4 B are the photos of section SEM of the light anode of embodiment 1; Fig. 4 C is the photo of section SEM of the light anode of comparative example 5.

Symbol description

1 smooth anode

2 pairs of electrodes

3 dielectric substrates

4 seals

10 light

11 transparent bases

12 transparency conducting layers

13 adhesion layers

14 porous semiconductor layers

21 relative base materials

22 first pairs of electrode layers

23 second pairs of electrode layers

31 first metal oxide nanoparticles

32 second metal oxide nanoparticles

33 scattering particles

Embodiment

The contrast accompanying drawing describes according to the execution mode of following order to present technique.

(1) formation of dye sensitized optoelectronic converting device

(2) metal oxide paste

(3) manufacture method of dye sensitized optoelectronic converting device

(1) formation of dye sensitized optoelectronic converting device

Fig. 1 is the profile that a configuration example of the dye sensitized optoelectronic converting device that an execution mode of present technique relates to is shown.As shown in Figure 1, this dye sensitized optoelectronic converting device (for example, DSSC) comprise light anode (optoelectronic pole) 1, dielectric substrate 3, to electrode 2, seal 4.Light anode 1 with to electrode 2 relative configurations, have electrolyte 3 therebetween.For example sealed by seal 4 by light anode 1 with to the peripheral part in electrode 2 folded zones.In this dye sensitized optoelectronic converting device, be the sensitive surface of accepting such as the light such as sunlight 10 such as the face of light anode-side.

(light anode)

Light anode 1 comprises: base material 11, the transparency conducting layer 12 that forms on the surface of base material 11 and the porous semiconductor layer 14 that forms on the surface of transparency conducting layer 12.As required, light anode 1 can also comprise adhesion layer 13 between transparency conducting layer 12 and porous semiconductor layer 14.By forming adhesion layer 13, can effectively suppress the generation of dark current and the again combination of electronics, and can improve the photoelectric conversion efficiency of battery.

(to electrode)

Electrode 2 is comprised: base material 21, form on the surface of base material 21 to electrode layer (first pair of electrode layer) 22 and form on the surface to electrode layer 22 to electrode layer (second pair of electrode layer) 23.

(base material)

Have the transparency as the base material 11 that is used for the light anode and get final product, without particular limitation of, can use various base materials, for example can use inorganic substrate or plastic basis material with transparency.In the middle of these base materials, if consider processability, light weight, then preferably use transparent plastic substrate.As the shape of substrate, can example such as film with transparency, thin plate, substrate etc.As the material of this base material, preferably to have the base material of good isolation, solvent resistance, weatherability etc. from the outside moisture of invading of dye sensitized optoelectronic converting device or gas etc.As the material of inorganic substrate, such as exemplifying out quartz, sapphire, glass etc.As the material of plastic basis material, for example can use known macromolecular material.As known macromolecular material, specifically, for example can exemplify out: triacetyl cellulose (TAC), polyester (TPEE), PETG (PET), PEN (PEN), polyimides (PI), polyamide (PA), aramid fiber, polyethylene (PE), polyacrylate, polyether sulfone, polysulfones, polypropylene (PP), the biacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), Merlon (PC), epoxy resin, carbamide resin, polyurethane resin, melamine, cyclic olefin polymer (COP) etc.In the material of the material of these inorganic substrates and plastic basis material, particularly preferably use the high base material of transmissivity in visible light zone, but be not limited thereto.

In addition, the thickness of base material 11 is especially restriction not, can freely select according to the inside of optical transmission rate, dye sensitized optoelectronic converting device and the isolation between the outside etc.Specifically, in the situation that use plastic basis material as base material 11, its thickness is from the preferred 38 μ m of productive angle～500 μ m, but without particular limitation of in this scope.Adopt will to the face of electrode side as situation about accepting such as the formation of the sensitive surface of the light such as sunlight 10 under, also can use opaque base material as base material 11.

As the base material 21 that is used for electrode, without particular limitation of in the base material with transparency, also can use opaque base material, such as using opaque or having the various base materials such as transparent inorganic substrate or plastic basis material.As the material of inorganic substrate or plastic basis material, for example can use equally as the material of above-mentioned base material 11 for the light anode and illustrative material, but can also use in addition the opaque base materials such as metal base.As metal base, such as using the conductive substrates such as Titanium, aluminium, copper, nickel, stainless steel.

(transparency conducting layer)

Material as transparency conducting layer 12 for example can exemplify out: tin oxide; The tin oxide of fluorine, antimony or phosphorus has mixed; The indium oxide of tin, fluorine or tin and fluorine has mixed; Antimony oxide; The titanium oxide of niobium has mixed; Zinc oxide; The zinc oxide of aluminium has mixed; Noble metal; Carbon nano-tube; Graphene; Conductivity carbon dust etc.

The visible light transmissivity of base material 11 and transparency conducting layer 12 is more high better, preferably more than 50%, more preferably more than 90%.In the situation that the visible light transmissivity is lower than 50%, the impact of the photoelectric conversion efficiency of battery there is the tendency of apparition.

The resistance of transparency conducting layer 12 is the smaller the better, preferably is suppressed to generally speaking 100 Ω/cm ²Below.Resistance at transparency conducting layer 12 surpasses 100 Ω/cm ²Situation under, the impact of the photoelectric conversion efficiency of battery is had the tendency of apparition.

Adhesion layer 13 forms as required.By forming adhesion layer 13, can effectively suppress the generation of dark current and the again combination of electronics, and can improve the photoelectric conversion efficiency of battery.

Adhesion layer 13 for example contains and comprises metal oxide as the metal oxide nanoparticles of main component.Metal oxide nanoparticles is the semi-conductive crystallinity nano particle of N-shaped preferably.Metal oxide in the metal oxide nanoparticles for example preferably contains from titanium oxide (TiO ₂), tin oxide (SnO ₂), niobium oxide (Nb ₂O ₅), zinc oxide (ZnO), tungsten oxide (WO ₃), indium oxide (In ₂O ₃), cupric oxide (Cu ₂O), chromium oxide (CrO ₃), strontium titanates (SrTiO ₃) and lead stannate (ZnSnO ₃) etc. at least a N-shaped semiconductor selected, particularly preferably contain the N-shaped semiconductor of titanium oxide.The crystallinity metal oxide nano colloid that is distributed in the dispersant in use forms in the situation of adhesion layer, and preferably using particle diameter is the crystallinity metal oxide nanoparticles of 20～30nm.By using such nano particle, can guarantee the effect of adhesion layer 13.

Adhesion layer 13 is for example formed by crystallinity metal oxide nano colloid.Adhesion layer 13 is not have to add to be used to form the room forming agent of porous and the metal oxide layer of porosity, it is characterized in that and transparency conducting layer 12 fluid-tight engagement, effectively reduces the dark current of battery.

The thickness of adhesion layer 13 is preferably 10～1000nm, more preferably in the scope of 50～500nm.If the not enough 10nm of the thickness of adhesion layer 13 is then insufficient to dark current and the inhibition of again being combined of electronics of porous semiconductor layer 14 between transparency conducting layer 12.If the thickness of adhesion layer 13 surpasses 1000nm, then porosity descends, and absorption and the electrolytical conductibility of restriction dyestuff may cause the photoelectric conversion efficiency of battery to descend.

The pore volume of adhesion layer 13 is preferably 0.01～0.40cm ³/ g is more preferably at 0.05～0.30cm ³In/g the scope.If pore volume surpasses 0.40cm ³/ g, then electrolyte easily contacts with transparency conducting layer 12, and is insufficient to the inhibition of the again combination of dark current and electronics.On the other hand, though can form the adhesion layer 13 of high compactness by methods such as sputters, if compactness is too high, the not enough 0.01cm of pore volume ³/ g, the mobility that then may hinder electronics, perhaps may cause and the porous semiconductor layer 14 that forms afterwards between adhesiveness descend.In addition, also may between adhesion layer 13 and porous semiconductor layer 14, produce the crack, cause the decrease in efficiency of battery.In addition, add the adhesion layer 13 that water decomposition forms because crystallinity is low by the presoma that will contain metal oxide, the mobility that may hinder electronics descends to the inhibition of the again combination of electronics.

The central value of the room diameter of adhesion layer 13 is preferably 1～20nm, more preferably in 2～10nm scope.If the not enough 1nm of the central value of the room diameter of adhesion layer 13, then interelectrode resistance increases, and the transmission that is unfavorable for electronics and the tendency of collection are arranged.On the other hand, if the room diameter of adhesion layer 13 surpasses 20nm, then electrolyte contacts with transparency conducting layer 12 and precipitates, exist dark current and electronics again in conjunction with the tendency of apparition.

(porous semiconductor layer)

Porous semiconductor layer 14 comprise two or more at least crystallinity metal oxide nanoparticles and at least a more than have the light scattering function scattering particles, preferably disperse equably these crystallinity metal oxide nanoparticles and scattering particles.At least two or more metal oxide nanoparticles preferably has respectively different particle diameters and distributes.

Fig. 2 is the profile of an example that the formation of porous semiconductor layer is shown.As shown in Figure 2, porous semiconductor layer 14 for example comprises the first metal oxide nanoparticles 31 that has the first particle diameter and distribute, the second metal oxide nanoparticles 32 with the distribution of the second particle diameter and the optical scatter 33 with light scattering function.For example in 20～80nm scope, the average grain diameter of the second metal oxide nanoparticles 32 is for example in 7～20nm scope for the average grain diameter of the first metal oxide nanoparticles 31.In addition, in Fig. 2, omitted the diagram of dyestuff.Here, the average grain diameter of the first metal oxide nanoparticles is following tries to achieve.Cut out the section of porous semiconductor layer 14 by FIB (Focused Ion Beam, focused ion beam) processing, by this section of tem observation, obtain the TEM photo.Then, from this TEM photo, select first metal oxide nanoparticles, measure the particle diameter of the Breadth Maximum of this particulate.100 particulates selecting at random from the TEM photo are carried out described mensuration, merely measured value is averaged (arithmetic average), obtain the average grain diameter of the first metal oxide nanoparticles.The average grain diameter of the second metal oxide nanoparticles is also by trying to achieve with the same method of the average grain diameter of above-mentioned the first metal oxide nanoparticles.

(to electrode layer)

As to

electrode layer

22,23 material, as long as have the reduction catalysts function, without particular limitation of, such as using the precious metal materials such as platinum, ruthenium, rhodium, also can be on the surface of conductive substrate evaporation or electroplated electrode material form.As to

electrode layer

22,23 electrode material, for example can exemplify out tin oxide, the tin oxide of mixed fluorine, antimony or phosphorus, the indium oxide of mixed tin, fluorine or tin and fluorine, antimony oxide, the mixed titanium oxide of niobium, zinc oxide, the zinc oxide of the aluminium that mixed, noble metal, carbon nano-tube, Graphene, conductivity carbon dust etc.In order to obtain desirable reduction catalysts effect, preferably electrode layer 23 is had loose structure, electrode layer 22 is had continuous structure.Identical material can be used to

electrode layer

22,23, also different materials can be used.In addition, also can use the combination of two or more materials.Can similarly be transparency electrode with transparency conducting layer 12 to electrode layer 22.That is, can use the material same with transparency conducting layer 12 to the material of electrode layer 22.

(dyestuff)

Dye Adsorption is at porous semiconductor layer 14.In the situation that also have adhesion layer 13 between transparency conducting layer 12 and the porous semiconductor layer 14, also can make Dye Adsorption to adhesion layer 13.

As the dyestuff of photosensitizer so long as excite and produce photoelectronic material and get final product by absorbing at least a light in visible light, infrared light, near infrared light and the ultraviolet light, without particular limitation of, can use organic dyestuff, metal complex, natural dye, quantum dot etc.As dyestuff, particularly such as enumerating: the basic-dyeable fibres such as anthocyan dyestuff, phenosafraine, methylenum careuleum, fat such as oxa anthracenes dyestuff, merocyanine, Sai Enning indigo plant, krypton cyanines such as rhodamine B, rose-red, eosin.And, can enumerate azo dyes, phthalocyanine compound, ruthenium bipyridyl complexes, terpyridyl ruthenium complex, the sour cyanines in side, polycyclic quinone dyestuff etc.As quantum dot, specifically such as the quantum dot that can enumerate CdS, CdSe, PbS, PbSe etc.Preferred ruthenium bipyridyl complexes wherein is because the output capacity of its quantum is high and good stability.Also can mix and use two or more in the above-mentioned dyestuff.Dyestuff is not limited to above-mentioned example.

(dielectric substrate)

As dielectric substrate 3, for example can use the mixture of the salt with electro-chemical activity and at least a compound that forms oxidation-reduction pair.Specifically, for example, can use iodine (I ₂) with mixture, the bromine (Br of metal iodide or organic iodide ₂) with the metal complexs such as mixture, fewrricyanic acid halide, fewrricyanic acid halide, ferrocene or ferricinum ion of metal bromide or organic bromide, poly-sulphur sodium, alkyl hydrosulfide or alkyl disulfide sulfides, hydroquinones, quinone etc.Lithium, sodium, potassium, magnesium, calcium, caesium etc. are preferably used as the cation of above-mentioned metallic compound, and in addition, tetra-allkylammonium class, pyridines or imidazoles grade in an imperial examination quaternary ammonium compound are preferably used as the cation of above-mentioned organic compound.But present technique is not limited to these examples.In addition, also can be with two kinds in the above material or two or more mixing as electrolyte.Wherein, the electrolyte that particularly preferably iodine and lithium iodide, sodium iodide or iodate imidazoles grade in an imperial examination quaternary ammonium compound is mixed with each other and forms.Preferred 0.05～the 5mol/L of the concentration of electrolytic salt is more preferably in the scope of 0.2～3mol/L.Single iodine or the concentration of bromine are preferably in 0.0005～1mol/L scope, more preferably in the scope of 0.001～0.3mol/L.In addition, by in electrolyte, adding take 4-tert .-butylpyridine etc. as main aminated compounds as additive, can improve the open circuit voltage of battery.

In electrolyte 3, also can use existing solvent.Particularly, can enumerate water, alcohols, ether oligomer, carboxylate, phosphate, acid amides, nitromethane, hydrocarbon, halogenated hydrocarbon, methylformamide, methyl-sulfoxide, sulfolane 66 sulfides, 1-METHYLPYRROLIDONE, NVP, 1,3-dimethyl-imidazolinone, 3-methyl oxazolidinone, ethylene carbonate ester, methyl cyanide, gamma-butyrolacton etc.But present technique is not limited to these examples, also the solvent of two or more mixing in the above-mentioned solvent can be used as electrolytical solvent in addition.

In addition, also can be with electrolyte dissolution in ionic liquid.Ionic liquid refers to the salt that dissolves at normal temperatures have high ion concentration, and the mobility of ion be large to have high ionic conductivity, therefore can use as electrolytical matrix.As ionic liquid, for example can use the ionic liquid of tetraalkyl class, imidazoles, pyridines quaternary ammonium salt, particularly, such as using 2-methyl isophthalic acid-pyrrolin, 1-methylpyrazole, 1-ethyl carbazole etc.But present technique is not limited to these examples, in addition also can be with two kinds in these ionic liquids or two or more mixed liquid as solvent.

For leak of liquid and the electrolytical volatilization that reduces electrooptical device, as required can be with above-mentioned electrolyte composition producing high-molecular or gelation.Such as gelling agent, polymer, cross-linking monomer etc. being dissolved in the electrolyte composition, also the nanoparticulate dispersed of inorganic, metal oxide can be formed gel-like electrolyte in electrolyte composition, further can also add as required ionic conductivity and promote material.Gel-like electrolyte is also referred to as accurate solid electrolyte.Promote material as ionic conductivity, for example can use nanotube, the nanofiber of titanium oxide, TiO from titanium oxide ₂The material of more than one that (B) select in the group of type nano wire, carbon nano-tube and Graphene etc.Because these particulates have the conductive structure of one dimension or two dimension, therefore can be in the three-dimensional conductive mesh of crosslinked rear formation.Therefore, promote ionic conductivity, can further improve photoelectric conversion efficiency.

About the ratio of gel-type vehicle and electrolyte composition, when the ratio of electrolyte composition was high, ionic conductivity uprised, the mechanical strength step-down.On the contrary, if the amount of electrolyte composition is very few, mechanical strength increases, and ionic conductivity descends but then.The ratio of the electrolyte composition in the gel-like electrolyte is preferably in 50～99% scopes, more preferably in 80～97% scopes.Become in the gelatinous situation at electrolyte composition, its viscosity is preferably more than 1000cp, more preferably in 5000～20000cp scope.

In addition, above-mentioned electrolyte and plasticizer are dissolved in the polymer together, when the plasticizer volatilization is removed, can access the dye sensitized optoelectronic converting device of complete solid.

In addition, also can use solid electrolyte as the electrolyte in the present technique.As solid electrolyte, for example except CuI, CuBr, outside the inorganic matters such as CuSCN, can also enumerate: polyaniline, polypyrrole, polythiophene, the arylamine zoarium of birdsing of the same feather flock together, acrylic compounds, methacrylic, the perhaps condensate of acrylic based and methacrylic, polyvinylcarbazole, the triphenyl diamine condensate, the low molecular gel of Valine derivative, the glycolmethacrylate oligomer, poly-(o-aminoanisole), epoxychloropropane-ethenyl copolymer, 2,2 ', 7,7 '-four (N, N-two-p-methoxyphenyl-amine)-9, the two fluorenes (MeOTAD) of 9 '-volution, persulfonic acid resin etc. has the fluorine family ion exchange resin of proton-conducting, perfluoro-hydrocarbon copolymer, the hydrocarbon perfluorinated sulfonic acid, polyethylene glycol oxide, pass through Br ^-, BF ^4-, N ^-(SO ₂CF ₃) ₂Form in conjunction with and add to the condensate of polymerization in vinyl monomer, the PMMA monomer etc. with glyoxaline cation.

(2) metal oxide paste

The metal oxide paste that an execution mode of present technique relates to is the slurry that is used to form the porous semiconductor layer 14 of dye sensitized optoelectronic converting device, comprises two or more at least crystallinity metal oxide nanoparticles, at least a above scattering particles with light scattering function, organic binder bond and dispersant.For example, two or more at least crystallinity metal oxide nanoparticles and at least a above scattering particles are distributed in the dispersant with predetermined content (concentration) equably via organic binder bond, are modulated into the metal oxide paste with predetermined viscosity.This metal oxide paste has the feature that solid content is high, rheological behavior is good.The porous semiconductor layer 14 that is formed by this metal oxide paste has been realized the balance of the optimum of the absorption of dyestuff and these two conflicting functions of light scattering.Thereby, can once be formed for a kind of slurry coating the porous semiconductor layer 14 of dye sensitized optoelectronic converting device, can significantly simplify film forming and process, and can significantly cut down manufacturing cost.

(metal oxide nanoparticles)

At least two or more metal oxide nanoparticles has respectively different-grain diameter and distributes.For example, two or more at least metal oxide nanoparticles comprises the first large metal oxide nanoparticles of particle diameter and the second little metal oxide nanoparticles of particle diameter.As the shape of metal oxide nanoparticles, such as using more than one the shape of from the group of spherical, bar-shaped, wire, tree shape, fibrous and tubulose etc., selecting.

In the situation of the metal oxide nanoparticles that uses two or more 3D shapes, its average grain diameter is preferably in 7～80nm scope, more preferably in 10～50nm scope.Have in use in the situation of the metal oxide that two kinds of particle diameters distribute, preferably have the average grain diameter of the first metal oxide nanoparticles that a kind of particle diameter distributes in the scope of 20～80nm, have the average grain diameter of the second metal oxide nanoparticles that another kind of particle diameter distributes in the scope of 7～20nm.If the not enough 20nm of the average grain diameter of the first metal oxide nanoparticles, the aperture of the porous semiconductor layer 14 that then forms is little, and the mobile tendency that becomes difficulty of electrolyte is arranged.If the average grain diameter of the first metal oxide nanoparticles surpasses 80nm, the surface area of the porous semiconductor layer 14 that then forms descends, the tendency that has the adsorbance of dyestuff to tail off.On the other hand, if the not enough 7nm of the average grain diameter of the second metal oxide nanoparticles, then the degree of crystallinity of nano particle is low, the again large tendency of possibility change of combination of photoelectron is arranged, if the average grain diameter of the second metal oxide nanoparticles surpasses 20nm, the surface area of the porous semiconductor layer 14 that then forms descends, the tendency that has the adsorbance of dyestuff to tail off.The mass ratio of the first metal oxide nanoparticles and the second metal oxide nanoparticles (the first metal oxide nanoparticles/the second metal oxide nanoparticles) is preferably in 0.5～20.0 scope.If mass ratio less than 0.5, the aperture of the porous semiconductor layer 14 that then forms diminishes, and the mobile tendency that becomes difficulty of electrolyte is arranged.If mass ratio surpasses 20.0, the surface area of the porous semiconductor layer 14 that then forms descends, the tendency that has the adsorbance of dyestuff to tail off.

Except the metal oxide nanoparticles of 3D shape, can also use the metal oxide nanoparticles of one dimension shape or two-dimensional shapes, also can being used in combination the metal oxide nanoparticles of one dimension shape, two-dimensional shapes and 3D shape.In the situation of the metal oxide nanoparticles that uses two-dimensional shapes, preferred average thickness is in 5～50nm scope, and average area is at 50nm ²～5.0 * 10 ⁷Nm ²In the scope, more preferably average thickness is in 7～40nm scope, and average area is at 50nm ²～5.0 * 10 ⁷Nm ²In the scope.In the situation of metal oxide nanoparticles as metal oxide nanoparticles of the bar-shaped or wire of using the one dimension shape, its average grain diameter is preferably in 5～40nm scope, more preferably in 7～30nm scope, its average length is preferably in 50～5000nm scope, more preferably in 60～2000nm scope.In the situation of nanotube-shaped titanium oxide as metal oxide nanoparticles of using the one dimension shape, its external diameter is preferably in 5～40nm scope, more preferably in 7～30nm scope, its internal diameter is preferably in 2～20nm scope, more preferably in 5～10nm scope, its wall thickness is preferably in 1～10nm scope.

If the average grain diameter of the metal oxide nanoparticles of one dimension shape is too small, although crystallinity is lower, specific area after the film forming is large, the adsorbance of dyestuff is large, but pore volume and the aperture of the porous semiconductor layer 14 that forms are little, have the tendency that the electrolytical movement with predetermined viscosity is had a negative impact.In addition, along with thickness increases, crystal boundary rolls up, and the internal resistance of battery increases thus, has the tendency that photoelectric conversion efficiency descends.On the other hand, if the average grain diameter of the metal oxide nanoparticles of one dimension shape is excessive, then the specific area of porous semiconductor layer 14 reduces, pore volume and aperture reduce, adsorbance as the dyestuff of emulsion descends thus, the photoelectric current of battery descends, and has the tendency that can not obtain high photoelectric conversion efficiency.

Here, the average grain diameter of metal oxide nanoparticles is following tries to achieve.At first, observe metal oxide nanoparticles by infiltration type electron microscope (TEM), obtain the TEM photo.Then, from this TEM photo, select a metal oxide nanoparticles, measure the widest particle diameter of this particulate.100 particulates selecting at random from the TEM photo are carried out this mensuration, merely measured value is averaged (arithmetic average), obtain average grain diameter.The average grain diameter of the average grain diameter of the first metal oxide nanoparticles and the second metal oxide nanoparticles is also all by trying to achieve with the same method of the average grain diameter of above-mentioned metal oxide nanoparticles.

The content of the metal oxide nanoparticles in the metal oxide paste is preferably in 1.0～35.0 quality % scopes, more preferably in 5.0～30.0 quality % scopes.If contain quantity not sufficient 1.0 quality %, then when masking for the step that reaches necessary thickness becomes many, and have the tendency that film easily forms the crack.On the other hand, if content surpasses 35.0 quality %, then the mobile variation of slurry has the tendency of masking decline.

(scattering particles)

One or more that select the group of the hollow structure that scattering particles such as the hollow condensate that can use condensate from sub-micron or micron-sized titanium oxide microparticle, nano particle, nano particle and the room forming agent by polystyrene spheres etc. form etc.The average grain diameter of scattering particles is preferably in 100～3000nm scope, more preferably in 100～800nm scope, further preferably in 200～400nm scope.If the average grain diameter of scattering particles is too small, then has the tendency of the function reduction of scattered light.On the other hand, if the average grain diameter of scattering particles is excessive, then the specific area of porous semiconductor layer 14 reduces, and the adsorbance of dyestuff descends, and therefore has the tendency that photoelectric current descends.And if the average grain diameter of scattering particles is excessive, then the optical transmission distance shortens, and has the tendency of the utilization ratio decline of light.Here, the average grain diameter of scattering particles is by trying to achieve with the same method of the average grain diameter of above-mentioned metal oxide nanoparticles.In the situation that polystyrene spheres is used as the room forming agent, when the burning polystyrene spheres, form the room of corresponding particle diameter, this room has effective light scattering effect.In addition, for the electrolytical movement in the porous semiconductor layer 14, the room structure is more favourable than scattering particles.

The content of the scattering particles in the metal oxide paste is preferably in 1.0～20.0 quality % scopes, more preferably in the scope of 2.0～10.0 quality %.If contain quantity not sufficient 1.0 quality %, the tendency that then has light scattering effect to descend.On the other hand, if content surpasses 20.0 quality %, the surface area of the porous semiconductor layer 14 that then forms descends, the tendency that has the adsorbance of dyestuff to tail off.With respect to metal oxide nanoparticles 100 mass fractions, scattering particles are preferably 10～50 mass fractions, more preferably 20～40 mass fractions.If the amount of scattering particles is few, the light scattering effect of the porous semiconductor layer 14 that then forms is insufficient, and is same with single nano-particle layer, hinders the crystal boundary wall of the movement of electronics to become many, and the again combination of electronics easily occurs, and has the tendency that photoelectric conversion efficiency descends.On the other hand, if the amount of scattering particles is too much, and the amount of nano particle is very few, and then the adsorbance as the dyestuff of emulsion descends, and has the tendency that photoelectric conversion efficiency descends.The mass ratio of metal oxide nanoparticles and scattering particles (metal oxide nanoparticles/scattering particles) is preferably in 2.0～10.0 scopes.If mass ratio less than 2.0, the surface area of the porous semiconductor layer 14 that then forms descends, the tendency that has the adsorbance of dyestuff to tail off.On the other hand, if mass ratio surpasses 10.0, the tendency that then has light scattering effect to descend.

In the situation that small polystyrene spheres is used as the room forming agent, the particle diameter of small polystyrene spheres is preferably in 100～500nm scope, more preferably in 200～400nm scope.The content of polystyrene is preferably in the scope of 20～80 quality % of the content of metal oxide nanoparticles, more preferably in the scope of 30～50 quality % of the content of metal oxide nanoparticles.

Metal oxide nanoparticles in the metal oxide paste and the total content of scattering particles are preferably in 5.0～40.0 quality % scopes, more preferably in 10.0～35.0 quality % scopes.If above-mentioned total content less than 5 quality % then after metal oxide paste coating, have the tendency of the pantostrat that is difficult to form predetermined thickness.On the other hand, if above-mentioned total content surpasses 40 quality %, then the screening characteristics of metal oxide paste descends, and the tendency of film forming difficulty is arranged.

Metal oxide nanoparticles and scattering particles preferably comprise metal oxide as main component.Metal oxide preferably comprises at least a N-shaped semiconductor of selecting from the group of titanium oxide, tin oxide, zinc oxide, niobium oxide, tungsten oxide, indium oxide, cupric oxide, chromium oxide, strontium titanates and zinc.

Preferably with the crystallinity metal oxide as metal oxide nanoparticles and scattering particles.More particularly, preferably with crystalline titanium oxide as metal oxide nanoparticles and scattering particles, for example preferably use anatase type titanium oxide, plate titanium type titanium oxide, Titanium Dioxide Rutile Top grade, TiO ₂(B) titanium oxide of type crystal structure etc. particularly preferably uses the anatase type titanium oxide of high crystalline.

Metal oxide nanoparticles in the present technique and the manufacture method of scattering particles, as long as can form the crystallinity metal oxide microparticle of above-mentioned particle diameter, without particular limitation of.The form of raw material both can be the powder of drying regime, also can be to be dispersed in colloid in the dispersant etc.

(dispersant)

As the dispersant of metal oxide paste, such as using more than one that from the group of water, alcohols, ketone, glycols, terpin class, ethers and amino-compound class etc., select.

Specifically, alcohols can be enumerated methyl alcohol, ethanol, isopropyl alcohol, butanols etc.Ketone can be enumerated acetone etc.Glycols can be enumerated ethylene glycol, propylene glycol etc.The terpin class can be enumerated terpinol, dihydroterpineol, terpinolene etc.Ethers can be enumerated butyl carbitol etc.The amino-compound class can be enumerated formamide etc.

Dispersant as the metal oxide paste that is used for silk screen printing preferably uses the high boiling solvents such as terpinol, butyl carbitol.In situation about need to not cure with the temperature more than 200 ℃, preferably make the low boiling alcohols such as water, methyl alcohol, ethanol, isopropyl alcohol, n-butanol as the dispersant of metal oxide paste.

(binding agent)

Metal oxide paste can comprise binding agent as required.For example, as binding agent, can use more than one that from the group of ethyl cellulose, methylcellulose, carboxymethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, acrylic resin, ketone resins and melmac etc., select.By in metal oxide paste, comprising binding agent, can improve the viscosity of metal oxide paste.Thereby plating oxide slurry equably in the processing of silk screen printing etc. can form clearly porous semiconductor layer 14 of surface smoothing, boundary line, and can access pore volume and the aperture of expectation.

Although the content of the binding agent in the metal oxide paste is according to the kind of binding agent and difference, preferably in 1.0～40.0 quality % scopes, more preferably in 4.0～10.0 quality % scopes.If binding agent contain quantity not sufficient 1.0 quality %, the tendency that then has the effect of binding agent to descend.On the other hand, if the content of binding agent surpasses 40.0 quality %, then the viscosity of metal oxide paste is too high, has the tendency of the intensity decline of the screening characteristics decline of metal oxide paste, the surperficial roughening that applies difficult, layer, formed porous semiconductor layer 14.

Binding agent preferably comprises viscosity different two kinds of ethyl celluloses or a kind of ethyl cellulose.By comprising two kinds or a kind of ethyl cellulose as binding agent, can control the flowability of slurry.In the situation that binding agent comprises two kinds of ethyl celluloses, two kinds of ethyl celluloses be preferably viscosity in the high viscosity ethyl cellulose more than the 30cp and below the 70cp and viscosity at the low viscosity ethyl cellulose more than the 5cp and below the 15cp.By using the different ethyl cellulose of this viscosity, can control the flowability of slurry.In the situation that binding agent comprises a kind of ethyl cellulose, this ethyl cellulose is preferably viscosity at the ethyl cellulose more than the 30cp and below the 100cp.By using the ethyl cellulose of this viscosity, can simplify the manufacturing step of slurry.

In the situation that use ethyl cellulose as binding agent, viscosity is that the mass ratio (low viscosity ethyl cellulose/high viscosity ethyl cellulose) of the high viscosity ethyl cellulose of 30～50cp and the low viscosity ethyl cellulose that viscosity is 5～15cp is preferably 50/50～70/30.If mass ratio less than 50/50, then the flowability of slurry is too strong, has the tendency on the surface that can not control porous semiconductor layer 14 etc.On the other hand, if mass ratio surpasses 70/30, then the flowability of slurry is too poor, has the tendency of masking difficult.Here, viscosity number is as solvent and measuring from the solution that is 10 quality % at 25 ℃ of lower solid constituent concentrations with toluene.

As the manufacture method of metal oxide paste, can adopt the whole bag of tricks that two or more at least metal oxide nanoparticles and at least a above scattering particles can be distributed to equably in the dispersant that has dissolved binding agent.For example, with metal oxide microparticle (for example, powdery or colloidal dispersions), binding agent, dispersant etc. are dispersed in advance such as evenly mixing (mechanical agitation, high shear force disperse or ultrasonic wave dispersion etc.) in the low boiling solution such as ethanol and fully afterwards, remove the low boiling point solvents such as ethanol by the rotary evaporation method, form the metal oxide paste of expectation, by mixing, pulverizing, aggegations such as three-high mills (triple roll mill), can modulate mixed uniformly metal oxide paste afterwards.In addition, also can directly metal oxide microparticle be distributed in the dispersant that has dissolved binding agent, can evenly mix and modulate the metal oxide paste of expectation by powerful machinery (ball mill, colloidal mill, taper grinding machine or revolution rotation mixer).The method is suitable for the industrialization volume production of metal oxide paste.

(3) manufacture method of dye sensitized optoelectronic converting device

An example of the manufacture method of the dye sensitized optoelectronic converting device that then, an execution mode of present technique is related to describes.

(formation of transparency conducting layer)

At first, form transparency conducting layer 12 on the surface of base material 11.Formation method as transparency conducting layer 12, for example can enumerate pyrolysismethod, spray pyrolysis, ultrasonic atomization pyrolysismethod, magnetron sputtering method, chemical vapour deposition technique (CVD), plasma enhanced chemical vapor deposition method (PECVD), the masking techniques such as plasma physical vapor deposition method (PEPVD), chemical vapor deposition.

(formation of adhesion layer)

Then, form adhesion layer 13 on the surface of transparency conducting layer 12 as required.Specifically, the colloid that for example will contain the metal oxide nanoparticles of high crystalline is coated on the surface of transparency conducting layer 12, carries out drying and cures under predetermined temperature.Thus, can form that adhesiveness with transparency conducting layer 12 is good, uniform film thickness, not have crannied adhesion layer 13.As coating method, can use more than one that from the group of spin-coating method, rolling method, adherography, electrophoresis, dip coating and spraying process etc., select, from the angle of industrial production, preferred adherography.

Be used to form the concentration of the metal oxide nanoparticles in the colloid (solution) of adhesion layer 13 preferably in 2～20 quality % scopes, more preferably in 5～15 quality % scopes.If the concentration deficiency of colloid 2 quality % then possibly can't form the thickness of expectation or continuous metal oxide layer.Therefore, must repeatedly apply and drying steps, and also might produce the crack on the dry film.On the other hand, if the concentration of colloid surpasses 20 quality %, the masking step becomes uncontrollable, has the tendency that can not obtain uniform film.

If dry can then can adopt existing method removing dispersant in the colloid, being to carry out under the temperature of the solution commonly used such as water or ethanol, also can adopt natural drying.Usually get final product about 0.1～2 hour with 60～150 ℃ of dryings.

Although only process by drying and can make its sclerosis, by under predetermined temperature, curing processing, can access more preferably adhesiving effect as required.

In curing processing, also can be preferably with 200～550 ℃, more preferably with 300～500 ℃ of annealing in process of carrying out about 0.1～5 hour.

(formation of porous semiconductor layer)

Then, form porous semiconductor layer 14 at transparency conducting layer 12 or on the surface of the adhesion layer 13 that forms as required.Specifically, for example metal oxide paste is coated on the surface of transparency conducting layer 12 or adhesion layer 13, through super-dry and curing, forms the porous metal oxide layer, be porous semiconductor layer 14.The thickness of porous semiconductor layer 14 is preferably in 0.1～50 μ m scope.Optimal thickness is according to other inscapes of the dyestuff that uses etc., battery and difference.

The metal oxide paste that present embodiment relates to is characterised in that not to be needed repeatedly to apply, and just can form the thickness of expectation by primary coating.The coating method of metal oxide paste is especially restriction not, can use existing known method, such as using silk screen print method, volume to volume print process (roll to roll), hectographic printing method, woodburytype, toppan printing, rolling method, scraper coating process (scratch coating), spin-coating method, infusion process, spraying process, gravure coating method etc.If dry can carrying out under the temperature that can remove dispersant then can be used existing method, also can be natural drying.Usually get final product in the drying of carrying out about 0.2～2 hour under 50～200 ℃.Cure preferably 250～650 ℃, more preferably under 350～550 ℃, carry out curing in 0.1～5 hour processing, both can in atmosphere, carry out, also can in oxygen or other oxidizing atmospheres, carry out.

In the situation that use silk screen printing to process, if select the silk screen of suitable mesh, and adjust printing parameter, then just can form the porous oxidation titanium layer of expectation thickness by one-step print.

(Dye Adsorption)

Then, for example make Dye Adsorption in porous semiconductor layer 14.The method of absorbing dye without particular limitation of, but for example can following absorbing dye.At first, dyestuff is dissolved in the solvent modulation solution.For dissolving dye, can heat as required, add the filtration of cosolvent and insoluble composition.Solvent preferably uses the solubilized dyestuff and can reconcile solvent to the Dye Adsorption of porous semiconductor layer 14, for example can use separately or mix use following two or more: alcohols, nitryl class, halogenated hydrocarbon, nitromethane, ethers, dimethyl sulfoxide (DMSO), furans are (for example, oxolane), 1-METHYLPYRROLIDONE, 1,3-dimethyl-imidazolinone, 3-methyl oxazolidinone, toluene, amide-type, ester class, carbonate, ketone, hydro carbons, water etc., but be not limited to this.

Then, such as by infusion process, spraying process etc., make the solvent adsorption of having dissolved dyestuff behind porous semiconductor layer 14, carry out drying.In addition, also the solution of dyestuff can be coated to porous semiconductor layer 14 in heat cycles, and make thus Dye Adsorption to porous semiconductor layer 14.The adsorption time of dyestuff can be selected according to the concentration of absorbing process or dye solution, for example by using the dye solution of high concentration, the adsorption time of dyestuff can be shortened to about several minutes.For example, dyestuff being dissolved in solution in the high boiling solvent can directly drip to porous semiconductor layer 14 and carry out Dye Adsorption.In addition, in the high situation of the acidity of dyestuff, can add deoxycholic acid or its analog and relax association and aggegation between the dyestuff.

After Dye Adsorption, also can process by amine the inner surface of porous semiconductor layer 14, remove the dyestuff of superfluous ground (multilayer) absorption.On the other hand, make pyridine, 4-tert .-butylpyridine, the amines such as polyvinylpyridine are adsorbed in the surface that dyestuff does not have the metal-oxide semiconductor (MOS) of absorption, can reduce photoelectronic again combination.In addition, in the situation that use liquid amine as these amines, can directly use, use after also can being dissolved into organic solvent.

(electrolytical filling)

Then, for example behind the UV cured type adhesive that the edge part of electrode 2 is formed by silk screen printing as sealant 4, paste light anode 1 via this UV cured type adhesive.At this moment, light anode 1 with to electrode 2 with predetermined space, for example with 1～100 μ m, preferably configure so that the interval of 1～50 μ m is relative.Thus, by light anode 1, electrode 2 and sealant 3 formed the space that will fill dielectric substrate 3.Then, for example from being pre-formed the inlet on the electrode 2 is being injected electrolyte to this space, dielectric substrate 3 is being filled in the space.Stop up this inlet thereafter.Thus, manufacturing is as the dye sensitized optoelectronic converting device of target.

According to an execution mode of present technique, can use a kind of metal oxide paste (semiconductor slurry) to form the porous semiconductor layer 14 of expectation thickness by primary coating, therefore can simplify significantly film forming and process.In addition, because the porous semiconductor layer 14 that forms by metal oxide paste has Dye Adsorption amount and light scattering effect both sides concurrently, therefore can realize the dye sensitized optoelectronic converting device of high-photoelectric transformation efficiency.In addition, use Graphene as in the situation to electrode 22,23 material replacing noble metal platinum, can reduce significantly the cost of battery manufacture material.In addition, can carry out battery production at production line by the dipping technique of the original creation in short several minutes, finished, can further cut down the battery manufacture cost.In addition, using TiO ₂(B) nano wire of type is made in the situation of gel-like electrolyte, can improve the stability of battery, and can raise the efficiency.Thereby present technique not only can improve the performance of battery, and can cut down significantly its manufacturing cost, and therefore industrial effect is excellent.

In addition, forming in the situation of metal oxide layer as adhesion layer 13 of high crystalline between transparency conducting layer 12 and the porous semiconductor layer 14, can further improve the photoelectric conversion efficiency of dye sensitized optoelectronic converting device.

Embodiment

Specify by the following examples present technique, but present technique is not limited to these embodiment.

In following embodiment and comparative example, following the trying to achieve of average grain diameter of each titanium oxide microparticle (large grain diameter nano particle, small particle diameter nano particle, scattering particles).At first, observe titanium oxide microparticle by infiltration type electron microscope (TEM), obtain the TEM photo.Then, from this TEM photo, select a titanium oxide microparticle, measure the widest particle diameter of this particulate.100 particulates selecting at random from the TEM photo are carried out this mensuration, to measured value being averaged (arithmetic average), obtain average grain diameter merely.

(embodiment 1)

(formation of titanium oxide adhesion layer)

The aqueous solution of crystallinity nano particle that will contain the titanium oxide of 20 quality % is coated to FTO (the fluorine doping SnO of transparent conductive base ₂) on the layer, carry out natural dryingly, then in 510 ℃ Muffle furnace (muffle furnace), cured 30 minutes, form the titanium oxide adhesion layer of thickness 200nm.

(modulation of titania slurry: from the aqueous solution modulation slurry of Titanium dioxide nanoparticle)

At first, be that the aqueous solution (content of Titanium dioxide nanoparticle the is 20 quality %) 15g of the Titanium dioxide nanoparticle of 29nm carries out 10 minutes centrifugal treating with 5000 rev/mins rotating speed to average grain diameter, give up the top clarified solution, and use ethanol to carry out 3 times and clean.Then, be that the TiOx nano powder 0.6g of 10nm and titanium dioxide powder 1.0g that average grain diameter is 250nm are distributed in the ethanol of 200mL with average grain diameter, it is the ethyl cellulose 0.8g of 30～70cp and the ethanolic solution 18g of the ethyl cellulose 1.0g that viscosity is 5～15cp (content of ethyl cellulose is 10 quality %) that viscosity has been dissolved in interpolation, has further added terpinol 13.6g.Then, mechanical agitation 4 hours, carry out shear rate and be 10000 rev/mins high shear treatment 15 minutes, carry out 15 minutes dispersion by the ultrasonic wave that is output as 400W, then remove ethanol by the rotary evaporation method, soft-agglomerated in the sediment that obtains pulverized by three-high mill, modulated homodisperse titania slurry.The content of each composition in the titania slurry that modulates is shown in the table 1.

(formation of porous oxidation titanium layer)

At first, use the as described above titania slurry of modulation, the titanium oxide adhesion layer is carried out a silk screen printing.At this moment, select suitable silk screen (for example ST165) to modulate the thickness of filming.Then, dry 15 minutes of the thermometal plates by 100 ℃ cured in 510 ℃ Muffle furnace 30 minutes afterwards, and having formed thickness is the porous oxidation titanium layer of 12 μ m.Made thus the light anode.Below, will suitably be called titanium oxide layer by the layer that titanium oxide adhesion layer and porous oxidation titanium layer form.

Surface and the section of the porous oxidation titanium layer of making have as described above been observed by scanning electron microscope (SEM:Scanning Electron Microscope).The results are shown in Fig. 3 A, Fig. 3 B, Fig. 4 A, Fig. 4 B.In addition, measure the most probable aperture of porous oxidation titanium layer by nitrogen adsorption/desorption method, further obtained the BET specific area of porous oxidation titanium layer.The results are shown in the table 1.

In addition, the following intermembranous adhesiveness of estimating the light anode.At first, on the surface of porous oxidation titanium layer, draw 6 piece parallel lines of cut with the interval of 1mm in length and breadth with knife, formed 50 foursquare unit.Then, square shaped cells is sticked adhesive tape, then peeled off adhesive tape.And obtain the number of the unit residual peeling off that adhesive tape rear oxidation titanium layer is not stripped from, and based on this unit number, minute 4 grade evaluations the adhesiveness between titanium oxide layer and the FTO transparency conducting layer.Its result is shown in the table 1.Below show the metewand of 4 grades.

◎: 50 of residual unit number

Zero: 45～49 of residual unit number

△: 43～44 of residual unit number

*: residual unit number is below 42

Then, the titanium oxide layer that obtains is put into 60 ℃ the aqueous solution of the titanium tetrachloride that contains 0.05mol/L and placed 30 minutes, water and absolute ethyl alcohol are cleaned respectively, then cure 30 minutes with 510 ℃, have formed the titanium oxide layer of processing through titanium tetrachloride.Afterwards, by the titanium oxide layer irradiating ultraviolet light of ultraviolet lamp to processing, utilize the photocatalysis of the titanium oxide that produces owing to UV-irradiation, decompose and removed the organic impurities that remains in the titanium oxide layer.

(absorption of dyestuff)

At first, refining (purity＞95%) dyestuff Z991 (cis-two (different thiocyanate closes) (2,2 '-bipyridyl-4,4 '-dicarboxylic acid radical closes) (4,4 '-two (4-(4-nonyl sulfur phenenyl) sulfur phenenyl) ruthenium (II) ((cis-Bis (isothiocyanato) (2,2 '-bipyridyl-4,4 '-dicarboxylato) (4,4 '-di (4-(4-nonyl thiophenyl) thiophenyl)-2 '-bipyridyl) ruthenium (II))).Then, the dyestuff of refining is dissolved in the methyl-sulfoxide (DMSO), is modulated into the solution that concentration is 10mmol/L, and add the deoxycholic acid (DCA, 10mmol/L) as coadsorbent, this solution is dripped on the porous oxidation titanium layer, carried out the absorption of dyestuff.This processing has been carried out 5 minutes.Afterwards, use methyl-sulfoxide and methyl cyanide, then the titanium oxide layer of dyestuff of having cleaned Adsorption on Surface successively in the dark carries out natural dryingly, has obtained having adsorbed the light anode of dyestuff.

(to the manufacturing of electrode)

At first, by (7000 rev/mins of spin-coating methods, 30 seconds) dispersion liquid that will contain Graphene (graphene) aqueous solution of 1 quality % deposits on the ITO layer of the glass substrate of cleaning fully, forms one deck porous graphene layer (100nm is thick), formed thus porous catalyst layer.Afterwards, obtained electrode through the normal temperature drying.

(electrolytical manufacturing)

At first, will mix with 85: 15 volume ratio as methyl cyanide and the nitropentane of solvent, be modulated into mixed solvent.Then, in the mixed solvent that modulates, dissolve 1 of 1mol/L, 3-dimethyl-3-imidazoles iodide (1,3-Dimethyl-3-imidazolium iodide), behind the guanidine thiocyanate (guanidinium thiocyanate) of the 4-tert .-butylpyridine (4-tert-butylpyridine) of the lithium iodide of the iodine of 0.03mol/L, 0.05mol/L, 1mol/L and 0.1mol/L, become electrolyte through abundant hybrid modulation.

Then, use the TiO of gelation ₂(B) as the additive of electrolyte, such as modulated gelatinous electrolyte.At first, add the mass ratio of anatase type titanium oxide nanometer powder take 1% to concentration in the sodium hydrate aqueous solution of 15mol/L, modulate dispersion liquid through mixing 1 hour.Then, the dispersion liquid that modulates transferred in 180 ℃ the autoclave with teflon lined, the heat treatment that water has been carried out 72 hours modulates the titanate of one-dimentional structure.Afterwards, stir on one side, use the aqueous hydrochloric acid solution pickling two hours of 0.05mol/L on one side, through filtering and water-washing step, in 400 ℃ Muffle furnace, cured 4 hours, obtained TiO ₂(B) nano wire.Then, with the TiO that obtains ₂(B) nano wire adds in the above-mentioned electrolyte with the ratio of 10 quality %, processes by the ultrasonic wave that carried out 1 hour and has carried out sufficient mixing, dispersion.Thus, obtained gel-like electrolyte.

(assembling)

At first, use scraper as described above the gel-like electrolyte that obtains to be coated on the porous oxidation titanium layer that has adsorbed dyestuff, formed gelatinous dielectric substrate.

Then, with the light anode with configure electrode is relative, the gel-like electrolyte layer is positioned between the two, be that the ultraviolet hardening resin of the insulation filling agent of 30 μ m is coated to the side and has sealed dielectric substrate with having mixed particle diameter, then respectively electrode is drawn by lead-in wire, made dye sensitized optoelectronic converting device.

Embodiment 2

Except the modulation step of titania slurry, obtained similarly to Example 1 dye sensitized optoelectronic converting device.The modulation step of the titania slurry of the present embodiment below is shown.

(modulation of titania slurry: from Powder Oxidation titanium nano particle modulation slurry)

At first, be that the titanium dioxide powder 1.0g that TiOx nano powder (P25) 3g of 21nm, TiOx nano powder 0.6g that average grain diameter is 10nm and average grain diameter are 250nm is distributed in the ethanol of 200mL with average grain diameter.Then, it is the ethyl cellulose 0.8g of 30～70cp and the ethanolic solution 18g of the ethyl cellulose 1.0g that viscosity is 5～15cp (content of ethyl cellulose is 10 quality %) that viscosity has been dissolved in interpolation, has further added terpineol 13.6g.Then, mechanical agitation 4 hours, the shear rate of carrying out 15 minutes is 10000 rev/mins high shear treatment, undertaken by the ultrasonic wave of exporting 400 watts after 15 minutes the dispersion, remove ethanol by the rotary evaporation method, pulverize by three-high mill soft-agglomerated in the sediment that obtains, modulated homodisperse titania slurry.The content of each composition in the titania slurry that modulates is shown in the table 1.

(embodiment 3)

(modulation of titania slurry: can quantity-produced by the combination of solid-liquid mixing and colloid mill and cone mill process)

At first, be that the ethyl cellulose 800g of 30～70cp and ethyl cellulose 1.0kg that viscosity is 5～15cp add fully dissolving in the terpinol of 13.6kg to viscosity.Then, be after titanium dioxide powder 1.0kg solid-liquid that TiOx nano powder (P25) 3.0kg of 21nm, TiOx nano powder 600g that average grain diameter is 10nm and average grain diameter are 250nm mixes with this solution, average grain diameter, carry out 20 minutes high shear treatment by colloidal mill and taper grinding machine.Then, pulverize by three-high mill soft-agglomerated in the sediment that obtains, modulated homodisperse titania slurry.The content of each composition in the titania slurry that modulates is shown in the table 1.

(embodiment 4)

(modulation of titania slurry: use single ethyl cellulose and by ball mill can quantity-produced processing)

At first, be that the ethyl cellulose 1.8kg of 40～100cp adds fully dissolving in the terpineol of 13.6kg to viscosity.Then, be that titanium dioxide powder 1.0kg that TiOx nano powder (P25) 3.0kg of 21nm, TiOx nano powder 600.0g that average grain diameter is 10nm and average grain diameter are 250nm uses ball mill (zirconia ball, zirconia tank) to mix 12 hours with 100 rev/mins rotating speed with this solution, average grain diameter, modulated homodisperse titania slurry.The content of each composition in the titania slurry that modulates is shown in the table 1.

(comparative example 1)

Except the modulation step of titania slurry, obtained similarly to Example 1 dye sensitized optoelectronic converting device.The modulation step of the titania slurry of this comparative example below is shown.

(the modulation of titania slurry: the situation of not adding the second metal oxide nanoparticles)

At first, be that TiOx nano powder (P25) 3.6g of 21nm and titanium dioxide powder 1g that average grain diameter is 250nm are distributed in the ethanol of 200mL with average grain diameter.Then, it is the ethyl cellulose 0.8g of 30～70cp and the ethanolic solution of the ethyl cellulose 1.0g that viscosity is 5～15cp (content of ethyl cellulose is 10 quality %) that viscosity has been dissolved in interpolation, has further added terpineol 13.6g.Then, mechanical agitation 4 hours, carry out shear rate and be 10000 rev/mins high shear treatment 15 minutes, carry out 15 minutes dispersion by the ultrasonic wave that is output as 400 watts, remove ethanol by the rotary evaporation method afterwards, pulverize by three-high mill soft-agglomerated in the sediment that obtains, modulated homodisperse titania slurry.The content of each composition in the titania slurry that modulates is shown in the table 1.

(comparative example 2)

(the modulation of titania slurry: the situation of not adding the second metal oxide nanoparticles and scattering particles)

At first, after TiOx nano powder (P25) 4.6g that with average grain diameter is 21nm is distributed to the ethanol of 200mL, it is the ethyl cellulose 0.8g of 30～70cp and the ethanolic solution 18g of the ethyl cellulose 1.0g that viscosity is 5～15cp (content of ethyl cellulose is 10 quality %) that viscosity has been dissolved in interpolation, has further added terpineol 13.6g.Then, mechanical agitation 4 hours, the shear rate of carrying out 15 minutes is 10000 rev/mins high shear treatment, carry out 15 minutes dispersion by the ultrasonic wave of exporting 400 watts, remove ethanol by the rotary evaporation method afterwards, pulverize by three-high mill soft-agglomerated in the sediment that obtains, modulated homodisperse titania slurry.The content of each composition in the titania slurry that modulates is shown in the table 1.

(comparative example 3)

Except the formation step of the modulation step of titania slurry and porous oxidation titanium layer, obtained similarly to Example 1 dye sensitized optoelectronic converting device.The modulation step of titania slurry of this comparative example and the formation step of porous oxidation titanium layer below are shown.

(modulation of titania slurry A)

At first, after TiOx nano powder (P25) 4.6g that with average grain diameter is 21nm is distributed to the ethanol of 200mL, it is the ethyl cellulose 0.8g of 30～70cp and the ethanolic solution 18g of the ethyl cellulose 1.0g that viscosity is 5～15cp (content of ethyl cellulose is 10 quality %) that viscosity has been dissolved in interpolation, has further added terpineol 13.6g.Then, mechanical agitation 4 hours is carried out shear rate and is 10000 rev/mins high shear treatment 15 minutes, carries out 15 minutes dispersion by the ultrasonic wave that is output as 400 watts, has removed ethanol by the rotary evaporation method afterwards.Then, pulverize by three-high mill soft-agglomerated in the sediment that obtains, modulated homodisperse titania slurry A.The content of each composition among the titania slurry A that modulates is shown in the table 1.

(modulation of titania slurry B)

At first, be after TiOx nano powder (P25) 3.6g of 21nm and titanium dioxide powder 1.0g that average grain diameter is 250nm are distributed to the ethanol of 200mL with average grain diameter, adding viscosity is the ethyl cellulose 0.8g of 30～70cp and the ethyl cellulose 1.0g that viscosity is 5～15cp, has further added terpineol 13.6g.Then, mechanical agitation 4 hours is carried out shear rate and is 10000 rev/mins high shear treatment 15 minutes, carries out 15 minutes dispersion by the ultrasonic wave that is output as 400 watts, has removed ethanol by the rotary evaporation method afterwards.Then, pulverize by three-high mill soft-agglomerated in the sediment that obtains, modulated homodisperse titania slurry B.The content of each composition among the titania slurry B that modulates is shown in the table 1.

(formation of porous oxidation titanium layer: use two kinds of titania slurry film forming)

At first, use titania slurry A to carry out silk screen printing on the surface of adhesion layer, form the layer of titania slurry A, after carrying out drying under 100 ℃, further carry out the layer that silk screen printing forms titania slurry B, after carrying out drying under 100 ℃, again carry out the layer that silk screen printing forms titania slurry B.Titania slurry A layer and the two-layer titania slurry B layer of one deck have been formed as described above.At this moment, the thickness that uses appropriate silk screen modulation to film.Then, dry 15 minutes of the thermometal plates by 100 ℃ cured in 510 ℃ Muffle furnace 30 minutes afterwards, had formed to have the porous oxidation titanium layer that thickness is the double-layer structure of 12 μ m.

Then, the porous oxidation titanium layer that obtains is positioned in 60 ℃ the aqueous solution of the titanium tetrachloride that contains 0.05mol/L 30 minutes, clean by water and absolute ethyl alcohol respectively, under 510 ℃, cured 30 minutes afterwards, obtained the porous oxidation titanium layer of processing through titanium tetrachloride.Afterwards, by the treated porous oxidation titanium layer of ultraviolet lamp irradiation, utilize the photocatalysis of the titanium oxide that produces owing to UV-irradiation, decompose and removed residual organic impurities in the porous oxidation titanium layer.

(embodiment 5)

Except the formation step of omission titanium oxide adhesion layer, directly forming the porous oxidation titanium layer on the surface of transparent conductive base FTO layer, obtained similarly to Example 1 dye sensitized optoelectronic converting device.Observe the section of the porous oxidation titanium layer that passes through dye sensitized optoelectronic converting device obtained above by scanning electron microscope.Its result is shown in Fig. 4 C.

(embodiment 6)

Except the formation step of titanium oxide adhesion layer, obtained similarly to Example 1 dye sensitized optoelectronic converting device.The formation step of the titanium oxide adhesion layer of the present embodiment below is shown.

(formation of titanium oxide adhesion layer)

At first, FTO glass after cleaning is positioned on 450 ℃ the thermometal plate, use the aqueous isopropanol of the ethyl diacetateization two n-butoxy titaniums (titanium di-isopropoxide bis (acetylacetonate)) of 0.2mol/L, applied for 1 second by spraying process to FTO glass.Then, the thermometal plate temperature is brought up to 500 ℃ and then annealed 30 minutes, formed thickness and be about the compactness titanium oxide layer of 100nm as adhesion layer.

(embodiment 7)

Except the manufacturing step to electrode, obtained similarly to Example 1 dye sensitized optoelectronic converting device.The manufacturing step to electrode of the present embodiment below is shown.

(to the manufacturing step of electrode)

By sputtering method, having piled up thickness at glass substrate successively is the metallic chromium layer of 50nm and the noble metal platinum layer that thickness is 100nm.Afterwards, further spray chloroplatinic aqueous isopropanol, and under 380 ℃ temperature, cure 15 minutes, formed take the porous noble metal platinum as catalyst to electrode layer.Obtained electrode thus.

(embodiment 8)

Except to the manufacturing step of electrode, electrolytical manufacturing step and the installation step, obtained similarly to Example 1 dye sensitized optoelectronic converting device.Below, the manufacturing step to electrode of the present embodiment, electrolytical manufacturing step and installation step are shown.

(to the manufacturing of electrode)

Formed electrode at first, similarly to Example 1.Then, be the hole section that is used for filling electrolyte of 0.5mm electrode having been formed diameter.

(electrolytical manufacturing)

At first, will mix with 85: 15 volume ratio as methyl cyanide and the nitropentane of solvent, be modulated into mixed solvent.Then, in the mixed solvent that modulates, dissolve 1 of 1mol/L, 3-dimethyl-3-imidazoles iodide (1,3-Dimethyl-3-imidazolium iodide), the iodine of 0.03mol/L, the lithium iodide of 0.05mol/L, the 4-tert .-butylpyridine (4-tert-butylpyridine) of 1mol/L and the guanidine thiocyanate (guanidinium thiocyanate) of 0.1mol/L, become electrolyte through abundant hybrid modulation.

(assembling)

At first, with light anode and opposite each other to electrode, having mixed particle diameter in side coating is that the ultraviolet hardening resin of the insulation filling agent of 30 μ m seals.Then, under reduced pressure, from being pre-formed above-mentioned electrolyte is being injected to the gap between two electrodes in the hole section on the electrode, then using the length of side is that 5 millimeters carrying is with sheets of glass and utilize UV-cured dose of closed hole section.Then, electrode is drawn by lead-in wire respectively.Thus, obtained between electrode layer, having electrolyte as electrolytical dye sensitized optoelectronic converting device.

(evaluation)

The following embodiment 1～8 that makes as described above, the dye sensitized optoelectronic converting device of comparative example 1～3 estimated.That is, by the solar simulator (AM1.5,100mW/cm2) that has used the standard type hernia lamp, measured open circuit voltage Voc, short-circuit current density Jsc, fill factor FF and the efficiency eta of dye sensitized optoelectronic converting device.Its result is shown in the table 1.

[table 1]

Above, the execution mode of present technique is specified, but present technique is not limited to above-mentioned execution mode, can carry out various distortion based on the technological thought of present technique.

For example, the formation of enumerating in the above-mentioned execution mode, method, step, shape, material and numerical value etc. only are examples, also can use as required different therewith formations, method, step, shape, material and numerical value etc.

In addition, the formation of above-mentioned execution mode, method, step, shape, material and numerical value etc. can mutually combinations in the scope of the purport that does not break away from present technique.

In addition, present technique can also adopt following formation.

(1) a kind of manufacture method of dye sensitized optoelectronic converting device may further comprise the steps:

Use described metal oxide paste to form porous semiconductor layer;

Wherein, described two or more at least metal oxide nanoparticles has respectively different particle diameter distributions.

(2) such as the manufacture method of (1) described dye sensitized optoelectronic converting device, wherein,

Described two or more at least metal oxide nanoparticles comprises at least: the second metal oxide nanoparticles in the first metal oxide nanoparticles in the scope of average grain diameter more than 20nm and below the 80nm and the scope of average grain diameter more than 7nm and below the 20nm.

(3) such as the manufacture method of (2) described dye sensitized optoelectronic converting device, wherein,

The content of the metal oxide nanoparticles in the described metal oxide paste is more than 1.0 quality % and in the scope below the 35.0 quality %,

The mass ratio of described the first metal oxide nanoparticles and described the second metal oxide nanoparticles (the first metal oxide nanoparticles/the second metal oxide nanoparticles) in the scope more than 0.5 and below 20.0,

The content of the described scattering particles in the described metal oxide paste is more than 1.0 quality % and in the scope below the 20.0 quality %,

The mass ratio of described metal oxide nanoparticles and scattering particles (metal oxide nanoparticles/scattering particles) in the scope more than 2.0 and below 10.0,

Described metal oxide nanoparticles in the described metal oxide paste and the total content of described scattering particles are more than the 5.0 quality % and below the 40.0 quality %.

(4) such as the manufacture method of each described dye sensitized optoelectronic converting device in (1)～(3), wherein,

Described at least a above scattering particles are that average grain diameter is submicron order or micron-sized at least a above scattering particles.

(5) such as the manufacture method of (4) described dye sensitized optoelectronic converting device, wherein,

The average grain diameter of described scattering particles is more than the 100nm and below the 3000nm.

(6) such as the manufacture method of each described dye sensitized optoelectronic converting device in (1)～(5), wherein,

In the formation step of described porous semiconductor layer, by coating, cure described metal oxide paste and form described porous semiconductor layer.

(7) such as the manufacture method of each described dye sensitized optoelectronic converting device in (1)～(6),

Described dispersant comprises terpinol,

Described binding agent comprises two kinds of ethyl celluloses or a kind of ethyl cellulose of different viscosities,

The content of the described binding agent in the described metal oxide paste is more than 1.0 quality % and in the scope below the 40.0 quality %.

(8) such as the manufacture method of (7) described dye sensitized optoelectronic converting device, wherein,

Described two kinds of ethyl celluloses are viscosity in the high viscosity ethyl cellulose more than the 30cp and below the 70cp and viscosity at the low viscosity ethyl cellulose more than the 5cp and below the 15cp,

The mass ratio of described high viscosity ethyl cellulose and described low viscosity ethyl cellulose (low viscosity ethyl cellulose/high viscosity ethyl cellulose) in the scope more than 50/50 and below 70/30,

Described a kind of ethyl cellulose is that viscosity is at the ethyl cellulose more than the 30cp and below the 100cp.

(9) such as the manufacture method of each described dye sensitized optoelectronic converting device in (1)～(8), wherein,

Described metal oxide nanoparticles and described scattering particles comprise metal oxide as main component,

Described metal oxide is to comprise more than one the N-shaped semiconductor of selecting from the group of titanium oxide, tin oxide, niobium oxide, zinc oxide, tungsten oxide, indium oxide, cupric oxide, chromium oxide, strontium titanates and lead stannate.

(10) such as the manufacture method of each described dye sensitized optoelectronic converting device in (1)～(9), wherein, after described metal oxide paste manufacturing step, and before the formation step of described porous semiconductor layer, also comprise by at the surface of conductive layer coating high crystalline metal oxide nano colloid and cure to form the step of adhesion layer.

(11) such as the manufacture method of (10) described dye sensitized optoelectronic converting device, wherein, in the scope of the thickness of described adhesion layer more than 10nm and below the 1000nm,

The pore volume of described adhesion layer is at 0.01cm ³Above and the 0.40cm of/g ³In the scope below the/g,

In the scope of central value more than 1nm and below the 20nm of the room diameter of described adhesion layer.

(12) such as the manufacture method of (10) described dye sensitized optoelectronic converting device, wherein,

Described metal oxide nano colloid comprises the metal oxide nanoparticles take metal oxide as main component,

(13) such as the manufacture method of each described dye sensitized optoelectronic converting device in (1)～(12), further comprising the steps of:

By with TiO ₂(B) the type nano wire adds in the electrolyte and gelation forms gel-like electrolyte; And

Form the dielectric substrate that comprises described gel-like electrolyte at described porous semiconductor layer and between to electrode.

(14) such as the manufacture method of each described dye sensitized optoelectronic converting device in (1)～(13), wherein, further comprising the steps of: as the surface by graphene solution being coated to conductive layer, to make Graphene be deposited on the surface of conductive layer and form the porous graphene layer and form electrode.

(15) a kind of dye sensitized optoelectronic converting device comprises: optoelectronic pole, to electrode and dielectric substrate, wherein,

Described optoelectronic pole comprises conductive layer and porous semiconductor layer,

Described porous semiconductor layer comprises two or more at least metal oxide nanoparticles and at least a above scattering particles,

Described two or more at least metal oxide nanoparticles has respectively different particle diameters and distributes.

(16) a kind of metal oxide paste for dye sensitized optoelectronic converting device comprises:

At least two or more metal oxide nanoparticles;

At least a above scattering particles;

Binding agent; And

Dispersant;

Claims

1. the manufacture method of a dye sensitized optoelectronic converting device may further comprise the steps:

Use described metal oxide paste to form porous semiconductor layer;

2. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 1, wherein,

3. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 2, wherein,

The content of metal oxide nanoparticles in described metal oxide paste is more than 1.0 quality % and in the scope below the 35.0 quality %,

The content of described scattering particles in described metal oxide paste is more than 1.0 quality % and in the scope below the 20.0 quality %,

Described metal oxide nanoparticles and the total content of described scattering particles in described metal oxide paste are more than the 5.0 quality % and below the 40.0 quality %.

4. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 1, wherein,

5. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 4, wherein,

6. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 1, wherein,

7. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 1, wherein,

Described dispersant comprises terpinol,

The content of described binding agent in described metal oxide paste is more than 1.0 quality % and in the scope below the 40.0 quality %.

8. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 7, wherein,

9. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 1, wherein,

10. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 1, wherein, after described metal oxide paste manufacturing step, and before the formation step of described porous semiconductor layer, also comprise by at the surface of conductive layer coating high crystalline metal oxide nano colloid and cure to form the step of adhesion layer.

11. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 10, wherein, in the scope of the thickness of described adhesion layer more than 10nm and below the 1000nm,

12. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 10, wherein,

13. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 1 is further comprising the steps of:

14. the manufacture method of dye sensitized optoelectronic converting device as claimed in claim 1 is further comprising the steps of: the surface by graphene solution being coated to conductive layer, make Graphene be deposited on the surface of conductive layer and form the porous graphene layer and form electrode.

15. a dye sensitized optoelectronic converting device comprises: optoelectronic pole, to electrode and dielectric substrate, wherein,

16. a metal oxide paste that is used for dye sensitized optoelectronic converting device comprises:

At least two or more metal oxide nanoparticles;

At least a above scattering particles;

Binding agent; And

Dispersant;