CN100533850C - Counter electrode for photoelectric converter and photoelectric converter - Google Patents
Counter electrode for photoelectric converter and photoelectric converter Download PDFInfo
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- CN100533850C CN100533850C CN 200580043401 CN200580043401A CN100533850C CN 100533850 C CN100533850 C CN 100533850C CN 200580043401 CN200580043401 CN 200580043401 CN 200580043401 A CN200580043401 A CN 200580043401A CN 100533850 C CN100533850 C CN 100533850C
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Abstract
The present invention provides a counter electrode for a photoelectric conversion element, includes a window electrode having a transparent substrate and a semiconductor layer provided on a surface of the transparent substrate, a sensitizing dye being adsorbed on the semiconductor layer; a counter electrode having a substrate and a conductive film, provided on a surface of the substrate, that is arranged so as to face the semiconductor layer of the window electrode; and an electrolyte layer disposed at least in a portion between the window electrode and the counter electrode, wherein the counter electrode has carbon nanotubes provided on the substrate surface via the conductive film.
Description
Technical field
The present invention relates to be used for the structure to electrode of photo-electric conversion elements such as dye-sensitized solar cell.
The application advocates priority to Japanese Patent Application 2004-371703 number of application on December 22nd, 2004 and the Japanese Patent Application 2005-278096 of application on September 26th, 2005, and quotes its content at this.
Background technology
Under backgrounds such as environmental problem, resource problem, gazed at as the solar cell of clean energy resource.As solar cell, the battery that uses monocrystalline, polycrystalline or amorphous silicon is arranged.But there is the manufacturing cost height in silicon class solar cell in the past, and problem such as starving, thereby failing large tracts of land popularizes.
To this, the group that people such as the Graetzel of Switzerland form has proposed dye-sensitized solar cell.This battery is as cheap and can obtain the photo-electric conversion element of high conversion efficiency and receive publicity (for example: with reference to patent documentation 1, patent documentation 2, non-patent literature 1 etc.).
In general, dye-sensitized solar cell wet type solar cells such as (Dye Sensitized Solar Cell:DSC), for example, roughly be by active electrode, electrode and the electrolyte that contains redox couples such as iodine enclosed between these electrodes are constituted, wherein, active electrode is on a face of the transparent base that the materials such as glass good by light transmission constitutes, formed the electrode of perforated membrane, this perforated membrane is made of oxide semiconductor particulates (nano particle) such as titanium dioxide, has carried the light sensitizing coloring matter; To electrode is to be made of the conducting film on the face that is formed on the substrate that is made of insulating properties materials such as glass.
Patent documentation 1: No. 2664194 communique of Japan's special permission
Patent documentation 2: TOHKEMY 2001-160427 communique
Non-patent literature 1:M.Graetzel et al., Nature, 737, p.353,1991
Fig. 4 is the figure of an example that represents the structure of dye-sensitized solar cell in the past with schematic section.This dye-sensitized solar cell 50 is the main composition key element with first substrate 51, second substrate 55 and dielectric substrate 56, wherein, first substrate 51 is being formed with the porous semiconductor electrode that carried the light sensitizing coloring matter (below, be also referred to as dye-sensitized semi-conducting electrode or active electrode) 53 on the one face; Second substrate 55 is formed with conducting film 54; Dielectric substrate 56 is made of for example gel-like electrolyte of enclosing between first substrate 51 and second substrate 55.
As first substrate 51, adopted sheet material with light transmission, on the face of dye-sensitized semi-conducting electrode 53 sides of first substrate 51, dispose nesa coating 52 in order to make it have conductivity.Constitute window electrode 58 by first substrate 51, nesa coating 52 and dye-sensitized semi-conducting electrode 53.
On the other hand, as second substrate 55, the transparency carrier or the metal substrate of conductivity have been adopted, on the face of dielectric substrate 56 sides, in order to make it have conductivity, for example on transparent electrode base board or metallic plate, be provided with by evaporation or the formed conducting film 54 that constitutes by carbon and platinum of sputter with conductivity.Constitute electrode 59 by second substrate 55 and conducting film 54.
With dye-sensitized semi-conducting electrode 53 and conducting film 54 opposed modes, with the arranged spaced window electrode 58 of regulation with to electrode 59, and the encapsulant 57 that constitutes by thermoplastic resin of the periphery setting between two electrodes.Then, across sealing material 57, make window electrode 58 and electrode 59 is bonded, be assembled into battery thus, inlet 60 by electrolyte, filling electrolyte forms the dielectric substrate 56 that electric charge is transferred usefulness as electrolyte between two electrodes 58,59, and this electrolyte is to make iodine and iodide ion (I
-/ I
3-) wait the redox couple to be dissolved in the organic solvent such as acetonitrile and form.
In addition, known have: the structure etc. that has adopted the structure of the ionic liquid of fixedness, made aqueous electrolyte gelization be used as the structure of imitative solidifying body and adopted solid semiconductors such as p N-type semiconductor N with suitable gel.
Ionic liquid is also referred to as the normal temperature molten salt, and it is near the wide temperature range comprising room temperature, exist as stable liquid, only by with the salt that constitutes of the ion of electric charge of positive and negative.This ionic liquid does not have steam in fact because do not have the such volatilization of ordinary organic solvents, problem such as ignite, so the method that descends as the battery behavior that solves due to the volatilization receives publicity.
This kind dye-sensitized solar cell absorbs incident lights such as sunlight, and its oxide semiconductor particulate produces electromotive force because of light sensitizing coloring matter sensitizing at active electrode and between to electrode, thus, and as transform light energy being become the light conversion element of electric energy work.
In order to improve the generating efficiency of dye-sensitized solar cell, need further to accelerate electronics from electrode is moved to electrolytical.For common carbon film of use in the past and platinum film for electrode, movement of electrons speed is slower, has the leeway of bigger raising generating efficiency.
Summary of the invention
The present invention In view of the foregoing makes, and its purpose is further to accelerate electronics from electrode is moved to electrolytical.
In order to achieve the above object, first technical scheme of the present invention provides a kind of photo-electric conversion element and uses electrode, and this photo-electric conversion element comprises: the window electrode has transparency carrier and is arranged at above-mentioned transparency carrier surface, has carried the semiconductor layer of sensitizing coloring matter; To electrode, the conducting film that has substrate and be arranged at the aforesaid substrate surface and be oppositely arranged with the above-mentioned semiconductor layer of above-mentioned window electrode; And dielectric substrate, be disposed at above-mentioned window electrode and above-mentioned at least a portion between the electrode; Above-mentioned have the carbon nano-tube that is provided with across above-mentioned conducting film on the aforesaid substrate surface to electrode, and the brush and sac like that above-mentioned carbon nano-tube is fixed with the one end is formed on the above-mentioned conducting film.
In addition, in first technical scheme of the present invention, above-mentioned brush and sac like carbon nano-tube also can vertically be orientated with substrate surface.
In addition, in first technical scheme of the present invention, also can make above-mentioned brush and sac like carbon nano-tube each other be spaced apart 1～1000nm.
In addition, in first technical scheme of the present invention, constitute above-mentioned substrate to electrode, its face that is provided with above-mentioned conducting film and above-mentioned carbon nano-tube has also carried out oxidation processes.
In addition, second technical scheme of the present invention provides a kind of photo-electric conversion element, comprising: the window electrode has transparency carrier and is arranged at above-mentioned transparency carrier surface, has carried the semiconductor layer of sensitizing coloring matter; To electrode, have substrate and be arranged at the aforesaid substrate surface and the conducting film that is oppositely arranged with the above-mentioned semiconductor layer of above-mentioned window electrode and be arranged at the carbon nano-tube on aforesaid substrate surface across above-mentioned conducting film, the brush and sac like that above-mentioned carbon nano-tube is fixed with the one end is formed on the above-mentioned conducting film; And dielectric substrate, be disposed at above-mentioned window electrode and above-mentioned at least a portion between the electrode.
In second technical scheme of the present invention, above-mentioned semiconductor layer also can be oxide semiconductor porous.
By use above-mentioned such constitute to electrode, constitute photo-electric conversion element as described above, can improve electronic emission energy to electrode, electrolyte can enter between the carbon nano-tube, thereby obtains the effect identical with nano-composite gel electrolyte.
Promptly, for for the nano-composite gel electrolyte that has carried out gelation after having mixed electroconductive particles such as carbon fiber and carbon black in the ionic liquid, semiconductor particle or electroconductive particle can play the effect that electric charge moves, the conductivity of gel-like electrolyte constituent becomes well, can obtain the light transfer characteristic when having used aqueous electrolyte.
To this, in the present invention, because carbon nano-tube plays the effect that electric charge moves, and electrolyte enters between the carbon nano-tube, so in near the electrolyte the electrode, can obtain effect identical when having used nano-composite gel electrolyte, and the electronics translational speed improves, can obtain high-photoelectric transformation efficiency.
Description of drawings
Fig. 1 is the skeleton diagram of an example of the cross-sectional configuration of expression photo-electric conversion element of the present invention.
Fig. 2 conceptually amplifies the figure that represents the structure to electrode of the present invention with stereoscopic figure.
Fig. 3 is the figure of the expression cross-sectional configuration to electrode of the present invention.
Fig. 4 is the figure of an example that represents the cross-sectional configuration of photo-electric conversion element in the past.
Symbol description:
1... inlet, 10... photo-electric conversion element, 11... first substrate, 12... nesa coating, 13... carbon nano-tube, 21... second substrate, 22... nesa coating, 23... porous semiconductor film to electrode, 2... window electrode, 3... dielectric substrate, 4... encapsulant, 5... electrolyte
Embodiment
Below, use accompanying drawing, photo-electric conversion element of the present invention and photo-electric conversion element are used electrode is described.
Fig. 1 has represented an example of the structure of photo-electric conversion element of the present invention with skeleton diagram.
Photo-electric conversion element 10 of the present invention mainly be by be formed with carbon nano-tube 13 to electrode 1, be formed with the window electrode 2 of the porous semiconductor film 23 that has carried sensitizing coloring matter and the electrolyte 3 enclosed between them constitutes.
To electrode 1, across the nesa coating 12 that forms in order to make it have conductivity, be provided with the carbon nano-tube 13 of brush and sac like on the surface of the first transparent substrate 11.
On the other hand, window electrode 2 has used second substrate 21 with light transmission, and across being used to make its nesa coating with conductivity 22, is provided with the porous semiconductor film 23 that has carried sensitizing coloring matter.
In the carbon nano-tube 13 of the brush and sac like mode relative with the porous semiconductor film 23 that has carried sensitizing coloring matter, across predetermined distance configuration window electrode with to electrode, the encapsulant 4 that the periphery setting between two electrodes is made of thermoplastic resin also is bonded them and is assembled into battery.Then, by the inlet 5 of electrolyte, between two electrodes 1,2, filling electrolyte forms the dielectric substrate 3 that electric charge is transferred usefulness as electrolyte, and this electrolyte is to make by iodine and iodide ion (I
-/ I
3-) redox couple that constitutes is dissolved in the organic solvent acetonitrile and forms.
Fig. 2 conceptually amplifies with stereoscopic figure and has represented the structure to electrode 1 of the present invention.Fig. 3 schematically represents its cross-sectional configuration.As Fig. 2, shown in Figure 3, of the present invention to the surface of electrode 1 at first substrate 11 that constitutes by transparent glass etc., having formed by thickness h is the nesa coating 12 that the fluorine doped tin oxide (Fluorine-doped-Tin-Oxide:FTO) about 0.1 μ m constitutes, so that it has conductivity, and has carbon nano-tube 13 on the surface of nesa coating 12.The brush and sac like that carbon nano-tube 13 is fixed with the one end is formed on the nesa coating 12 of a face that is arranged at first substrate 11.Though the direction of growth of the carbon nano-tube 13 of brush and sac like is not limit, especially preferably to form with the rectangular substantially mode in the surface of nesa coating 12.
By constituting as described above electrode, electrolyte is filled between each carbon nano-tube 13, thereby can further improve the electrolytical conductivity of iodine.
The present invention has adopted carbon nano-tube to replace in the past carbon film and platinum film.
Carbon nano-tube has has made structure cylindraceous with graphite linings, is that diameter is, length is a few μ m about 0.7～50mm, has hollow structure and the very big material of aspect ratio.As the electrical properties of carbon nano-tube, depend on diameter and chirality and present from metal to semi-conductive character.In addition,, has bigger Young's modulus, even but and be to have the crooked also material of the characteristic of relieve stresses as engineering properties.And, owing to there is not free key, aspect chemical, be stable therefore, and, owing to only constitute, receive publicity as the material that is of value to environment by carbon atom.
Because therefore above such unique rerum natura can expect the following application of carbon nano-tube: be applied to electronic emission source and flat-panel monitor, be applied to the electrode material of nanoscale devices and lithium battery or be applied to the interpolation material etc. that detector probe, gaseous storage material, nanoscale developmental tube, resin are strengthened usefulness as electronic material as electron source.
Carbon nano-tube has the barrel-shaped structure that graphite linings forms drum or truncated cone shape.Specifically, it is the single-layer carbon nano-tube (SWCNT:single-wall carbonnanotubes) of one deck and multilayer carbon nanotube (MWCNT:multi-wall carbon nanotubes) that graphite linings is multilayer (more than 2 layers) etc. that graphite linings is arranged, its any one all can be used as of the present invention to electrode.
When being single-layer carbon nano-tube, its diameter is that about 0.5nm～10nm, length are about 10nm～1 μ m, and when being multilayer carbon nanotube, its diameter is that about 1nm～100nm, length are about 50nm～50 μ m.
The diameter d of the carbon nano-tube 13 of brush and sac like of the present invention shown in Figure 3 is preferably 5～75nm, and height H is about 0.1～500nm.In addition, the interval D of each carbon nano-tube 13 is preferably about 1～1000nm.
For carbon nano-tube, the shape that aspect ratio is bigger, its electronic emission performance height can be applied to the emitter in electronic emission source.Can think: for the front end from carbon nano-tube produces electronic emission, and it vertically is orientated, can improves the electronic emission ability.Therefore, when be applied to photo-electric conversion element to electrode the time, can realize photoelectric conversion efficiency good to electrode.
In addition, can think the brush and sac like carbon nano-tube is used for electrode, will make electrolyte be easy to enter between carbon nano-tube and the carbon nano-tube, can improve the electrolytical conductivity of iodine.
In the present invention, can obtain the effect identical with nano-composite gel electrolyte.Promptly, for for the nano-composite gel electrolyte that has carried out gelation after having mixed electroconductive particles such as carbon fiber and carbon black in the ionic liquid, semiconductor particle or electroconductive particle can play the effect that electric charge moves, the conductivity of gel-like electrolyte constituent becomes well, can obtain the light transfer characteristic when having used aqueous electrolyte.
To this, in the present invention, because carbon nano-tube plays the effect that electric charge moves, and electrolyte enters between the carbon nano-tube, so in near the electrolyte the electrode, can obtain effect identical when having used nano-composite gel electrolyte, the electronics translational speed improves, and can obtain high-photoelectric transformation efficiency.
Carbon nano-tube can adopt known chemical gas-phase method (CVD method) to make.For example, in TOHKEMY 2001-220674 communique, following content is disclosed, promptly, on silicon substrate, by metals such as sputter or evaporation nickel, cobalt, iron and after the film forming, in inert atmosphere, hydrogen atmosphere or vacuum, preferably with 500～900 ℃ temperature heating 1～60 minute, then, hydrocarbon gas such as acetylene, ethene or alcohol gas are used as unstrpped gas, after using general chemical gas-phase method (CVD method) to carry out film forming, growing diameter on silicon substrate is that 5～75nm, length are the carbon nano-tube of 0.1～500 μ m.
When adopting the CVD method to form the brush and sac like carbon nano-tube, can control the length and the thickness of brush and sac like carbon nano-tube by the control temperature and time.
About brush and sac like carbon nano-tube used in the present invention, preferred: diameter be 5～75nm, length be 0.1～500 μ m, carbon nano-tube each other be spaced apart 1～1000nm.After the diameter of brush and sac like carbon nano-tube had exceeded proper range, aspect ratio diminished, and electronic emission can reduce.After the length of brush and sac like carbon nano-tube has exceeded proper range, be difficult to vertically be orientated with substrate surface.In addition, when brush and sac like carbon nano-tube interval each other during, then be difficult to obtain the effect identical with nano-composite gel electrolyte greater than proper range.
About as first substrate 11 and second substrate 21 and the transparent base that uses, the substrate that employing is made of the material with light transmission, if glass, PETG (Polyethylene terephthalate), PEN (PolyethyleneNaphtahalate), Merlon, polyether sulfone (Polyether sulfone) etc. then can use any material usually as the employed material of the transparent base of solar cell.For transparent base, consider the patience of electrolyte is suitably selected from them.In addition, consider that preferred light transmission is measured substrate to the greatest extent, and then the preferred transmission rate is the substrate more than 90% from purposes.
Nesa coating the 12, the 22nd, in order to give transparency carrier 11,21 conductivity, and the film that on one face, forms.In the present invention, in order to realize significantly not damaging the structure of the transparency of transparency carrier, preferably clear conducting film the 12, the 22nd, the film that constitutes by conductive metal oxide.
As conductive metal oxide, for example can adopt tin-doped indium oxide (Indium Tin Oxide:ITO), fluorine doped tin oxide (Fluorine doped Tin Oxide:FTO), tin oxide (SnO
2) etc.From being easy to film forming and angle cheap for manufacturing cost, in them, preferred ITO, FTO.In addition, nesa coating 12,22 also can adopt the monofilm that only is made of ITO, perhaps the stacked film of stacked FTO on the ITO film.If use such nesa coating, then can constitute the nesa coating that uptake is few and conductance is high of the light of viewing area.
In to electrode 1, on the nesa coating 12 of first substrate 11 that has formed above-mentioned nesa coating 12, form above-mentioned brush and sac like carbon nano-tube.
In addition, in window electrode 2, on the nesa coating 22 of second substrate 21 that has formed above-mentioned nesa coating 22, form the porous semiconductor film 23 that has constituted, carried the light sensitizing coloring matter by oxide semiconductor particulates such as titanium oxide.
As the method that forms porous semiconductor film 23, for example, except being suitable for following method, promptly, as required in the dispersion liquid that the oxide semiconductor microparticulate that makes sale on the market forms in required dispersant, perhaps in the colloidal solution that available sol-gel process is adjusted, after having added required additive, pass through silk screen print method, ink jet printing method, rolling method, the scraper plate coating process, spin-coating method, the method that known method such as spraying process apply, also applicable following method, promptly, electrode base board be impregnated in colloidal solution and makes the oxide semiconductor particulate attached to the electrophoretic deposition on the electrode base board by electrophoresis; After blowing agent being mixed in colloidal solution or dispersion liquid and applying, carry out the method for porous by sintering; After having mixed polymer microballoon (polymer microbeads) and coating, remove this polymer microballoon by heat treated or chemical treatment and form the method etc. that porous is carried out in the space.
To sensitizing coloring matter by porous semiconductor film 23 carryings, there is not particular restriction, for example can be from having the ruthenium complex or the iron complex of the dentate that comprises bipyridine structure, three pyridine structures etc., the metal complex of porphyrin class or phthalocyanines, and in the organic pigment such as eosin, rhodamine, merocyanine, cumarin, according to the material of purposes and oxide semiconductor perforated membrane, suitably select to use.
About enclosing to the dielectric substrate 3 between electrode 1 and the window electrode 2, can use known dielectric substrate, for example, can list and electrolyte be contained be immersed in the interior and dielectric substrate of formation of oxide semiconductor porous layer 23.In addition, also can list after electrolyte being contained be immersed in the oxide semiconductor porous layer 23, use suitable gel to make this electrolyte gelation (accurate solidification) and form the dielectric substrate of one, perhaps the gelatinous electrolyte that contains oxide semiconductor particle and electroconductive particle of ionic liquid etc. with oxide semiconductor porous layer 23.
As above-mentioned electrolyte, can use the liquid that iodine, iodide ion, tert .-butylpyridine electrolyte ingredients such as (tertiary butylpyridine) is dissolved in ethylene carbonate (ethylene carbonate) or methoxyl group second cyanogen organic solvents such as (methoxyacetonitrile) and forms.
Employed gel as with this electrolyte gelation the time can list polyvinylidene fluoride (Poly Vinylidine DiFluoride), polyethylene oxide derivant (polyethylene oxide), amino acid derivativges etc.
In addition, as above-mentioned ionic liquid, do not have particular determination, can list at room temperature and to be liquid, the compound of the nitrogen-atoms that will have quaternized is as cation or anionic normal temperature molten salt.
As the cation of normal temperature molten salt, can list imidazoles (imidazolium) derivative, pyridine derivate, quaternary ammonium salt derivative etc.
As the anion of normal temperature molten salt, can list BF
4 -, PF
6 -, F (HF) n
-, bis trifluoromethyl sulfimide (N (CF
3SO
2)
2 -), iodide ion etc.
The photo-electric conversion element of the present invention of assembling above-mentioned each structural element as shown in Figure 1 and obtaining, because electronic emission can high brush and sac like carbon nano-tube be used for electrode, thus obtained electronics to electrode to electrolytical degree of excursion height, photo-electric conversion element that photoelectric conversion efficiency is high.
Embodiment
(embodiment 1～6)
Use following material, made and have the such photo-electric conversion element of Fig. 2, Fig. 3 the structure shown in Figure 1 of electrode.
(electrolyte)
As the electrolyte of embodiment 1, embodiment 3 and embodiment 4, modulated the electrolyte of forming by ionic liquid that contains iodine/iodide ion redox couple (1-methyl-3-methylimidazole-bis trifluoromethyl sulfimide) etc.
As the electrolyte of embodiment 2, embodiment 5 and embodiment 6, used by mixing the TiOx nano particle of 10wt%, and carried out centrifugation and the nano-composite gel electrolyte produced.
(window electrode)
Use the glass substrate of band FTO film as transparent electrode substrate, surface in the FTO of this transparent electrode plate film side, the coating average grain diameter is the slurries shape aqueous dispersion of the titanium oxide of 20nm, and dry back has formed the oxide semiconductor perforated membrane of thick 7 μ m 450 ℃ of following heat treated 1 hour.Then, make it in the ethanolic solution of bipyridyl ruthenium complex compound (N3 pigment), flood a night and make its carrying pigment, thereby make the exit window electrode.
(to electrode)
In embodiment 1 and embodiment 2, employing is with the common chemical gas-phase method (CVD) of acetylene gas as unstrpped gas, forming diameter on the glass substrate of band FTO film is that 10～50nm, length are the brush and sac like carbon nano-tube of 0.5～10 μ m, with it as to electrode.Carbon nano-tube is formed generally perpendicularly on substrate, each carbon nano-tube be spaced apart 10～50nm.
In embodiment 3 and embodiment 5, adopt the common chemical gas-phase method (CVD) of acetylene gas as unstrpped gas, forming diameter on the titanium plate is that 10～50nm, length are the brush and sac like carbon nano-tube of 0.5～10 μ m, with it as to electrode.Carbon nano-tube is formed generally perpendicularly on substrate, each carbon nano-tube be spaced apart 10～50nm.In this example, adopted the titanium plate of not implementing anodized as the titanium plate.
In embodiment 4 and embodiment 6, except adopted the titanium plate of having implemented anodized as the titanium plate, other are all produced electrode in the same manner with embodiment 3.
To six kinds of photo-electric conversion elements so producing, carried out the mensuration of light transfer characteristic.In table 1, represented photoelectric conversion efficiency together.The CNT of table 1 is meant above-mentioned brush and sac like carbon nano-tube.In addition, in the anodic oxidation hurdle of set titanium plate, the situation of this processing has been implemented in " having " expression in table 1, and the situation of this processing is not implemented in " nothing " expression, and "---" expression is not owing to use the titanium plate and incongruent situation.
Table 1
| To electrode structure | The anodic oxidation of titanium plate | Electrolytical kind | Conversion efficiency (%) | |
| |
CNT/FTO CNT/FTO CNT/ titanium plate CNT/ titanium plate CNT/ titanium plate CNT/ titanium plate | ------nothing has or not | Ionic liquid nano-composite gel ionic liquid ionic liquid nano-composite gel nano-composite gel | 6.5 6.5 6.6 6.8 6.4 6.6 |
| Comparative example 1 comparative example 2 comparative examples 3 | Platinum/FTO platinum/FTO platinum/titanium plate | ------do not have | Nano-composite gel ionic liquid ionic liquid | 5.9 5.1 5.1 |
(comparative example 1)
As electrolyte, used by mixing the TiOx nano particle of 10wt%, and carried out centrifugation and the nano-composite gel electrolyte produced.Employing utilizes sputtering method to form the glass substrate of the band FTO film of the electrode film that is made of platinum to electrode.The window electrode is identical with embodiment.
Use such material, produced the photo-electric conversion element of structure shown in Figure 4.
To the photo-electric conversion element of making like this, carried out the mensuration of light transfer characteristic.Its photoelectric conversion efficiency is illustrated in the table 1 in the lump.
(comparative example 2)
Electrolyte is same as the previously described embodiments, has used ionic liquid electrolyte.Identical to electrode with above-mentioned comparative example 1, adopt and utilize sputtering method to form the glass substrate of the band FTO film of the electrode film that constitutes by platinum.The window electrode is identical with embodiment.
Use such material, produced the photo-electric conversion element of structure shown in Figure 4.
To the photo-electric conversion element of so producing, carried out the mensuration of light transfer characteristic.Its photoelectric conversion efficiency is illustrated in the table 1 in the lump.
(comparative example 3)
Electrolyte is identical with the foregoing description 1, has used ionic liquid electrolyte.Identical to electrode with above-mentioned comparative example 1, adopt and utilize sputtering method to form the titanium-base of the electrode film that constitutes by platinum.The window electrode is identical with embodiment.But, in this example,, adopted the titanium plate of not implementing anodized as the titanium plate.
Use such material, produced the photo-electric conversion element of structure shown in Figure 4.
To the photo-electric conversion element that so makes, carried out the mensuration of light transfer characteristic.Its photoelectric conversion efficiency is illustrated in the table 1 in the lump.
From the result of table 1, can clearly draw:
(1) by employing used CNT replace in the past platinum to electrode, can make conversion efficiency improve 0.6～1.4%.Its effect and electrolytical kind irrelevant (embodiment 1 compares with comparative example 2, and embodiment 2 compares with comparative example 1).
(2) even use titanium plate replaces FTO in the past, also can obtain the effect of above-mentioned (1).This effect and electrolytical kind irrelevant (embodiment 1 and embodiment 3 compare, and embodiment 2 and embodiment 5 compare).
When (3) adopting the titanium plate,, can further increase conversion efficiency by implementing anodized.Its effect and electrolytical kind irrelevant (embodiment 3 and embodiment 4 compare, and embodiment 5 and embodiment 6 compare).
According to above result, can confirm: the photo-electric conversion element to electrode of carbon nano-tube that used of the present invention of having packed into has good photoelectric conversion efficiency.
In addition, when using the titanium plate and implementing anodized, preferably make the thickness of oxide layer of utilizing this processing formation below 500nm.If thicker than 500nm, then electric current is difficult for flowing to substrate (titanium plate) from the CNT that synthesizes on oxide layer, and is therefore improper.
More than, the preferred embodiments of the present invention have been described, but have the invention is not restricted to these embodiment.In the scope that does not break away from aim of the present invention, can carry out adding, omit, replacing and other changes of structure.The present invention can't help above-mentioned explanation and limits, and is limited only by the accompanying claims.
Claims (6)
1. a photo-electric conversion element is used electrode, and above-mentioned photo-electric conversion element comprises: the window electrode has transparency carrier and is arranged at above-mentioned transparency carrier surface, has carried the semiconductor layer of sensitizing coloring matter; To electrode, the conducting film that has substrate and be arranged at the aforesaid substrate surface and be oppositely arranged with the above-mentioned semiconductor layer of above-mentioned window electrode; And dielectric substrate, be disposed at above-mentioned window electrode and above-mentioned at least a portion between the electrode; It is characterized in that:
Above-mentioned have the carbon nano-tube that is provided with across above-mentioned conducting film on the aforesaid substrate surface to electrode,
The brush and sac like that above-mentioned carbon nano-tube is fixed with the one end is formed on the above-mentioned conducting film.
2. photo-electric conversion element according to claim 1 is used electrode, it is characterized in that: above-mentioned brush and sac like carbon nano-tube and substrate surface vertically are orientated.
3. photo-electric conversion element according to claim 1 is used electrode, it is characterized in that: above-mentioned brush and sac like carbon nano-tube each other be spaced apart 1～1000nm.
4. photo-electric conversion element according to claim 1 is used electrode, it is characterized in that: constitute above-mentioned substrate to electrode, its face that above-mentioned conducting film and above-mentioned carbon nano-tube are set has carried out oxidation processes.
5. a photo-electric conversion element is characterized in that, comprising:
The window electrode has transparency carrier and is arranged at the aforesaid substrate surface, has carried the semiconductor layer of sensitizing coloring matter;
To electrode, have substrate, be arranged at aforesaid substrate surface and the conducting film that is oppositely arranged with the above-mentioned semiconductor layer of above-mentioned window electrode and be arranged at the carbon nano-tube on aforesaid substrate surface across above-mentioned conducting film, the brush and sac like that above-mentioned carbon nano-tube is fixed with the one end is formed on the above-mentioned conducting film; And
Dielectric substrate is disposed at above-mentioned window electrode and above-mentioned at least a portion between the electrode.
6. photo-electric conversion element according to claim 5 is characterized in that: above-mentioned semiconductor layer is an oxide semiconductor porous.
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|---|---|---|---|
| JP2004371703 | 2004-12-22 | ||
| JP371703/2004 | 2004-12-22 | ||
| JP278096/2005 | 2005-09-26 |
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| CN100533850C true CN100533850C (en) | 2009-08-26 |
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|---|---|---|---|---|
| CN101262019B (en) * | 2008-03-26 | 2012-01-11 | 北京师范大学 | Photoelectrical chemical solar battery for silicon nano line |
| US8604332B2 (en) * | 2010-03-04 | 2013-12-10 | Guardian Industries Corp. | Electronic devices including transparent conductive coatings including carbon nanotubes and nanowire composites, and methods of making the same |
| CN101872842A (en) * | 2010-06-24 | 2010-10-27 | 电子科技大学 | Organic photoelectric device and preparation method thereof |
| KR101137378B1 (en) * | 2010-07-16 | 2012-04-20 | 삼성에스디아이 주식회사 | Dye-sensitized solar cell |
| JPWO2021085047A1 (en) * | 2019-10-31 | 2021-05-06 |
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