JP2010153231A - Coating material for forming porus metal oxide semiconductor film, and photoelectric cell - Google Patents
Coating material for forming porus metal oxide semiconductor film, and photoelectric cell Download PDFInfo
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- JP2010153231A JP2010153231A JP2008330818A JP2008330818A JP2010153231A JP 2010153231 A JP2010153231 A JP 2010153231A JP 2008330818 A JP2008330818 A JP 2008330818A JP 2008330818 A JP2008330818 A JP 2008330818A JP 2010153231 A JP2010153231 A JP 2010153231A
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- Prior art keywords
- metal oxide
- semiconductor film
- oxide semiconductor
- porous metal
- forming
- Prior art date
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- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 194
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 192
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- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
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- BTIJJDXEELBZFS-QDUVMHSLSA-K hemin Chemical compound CC1=C(CCC(O)=O)C(C=C2C(CCC(O)=O)=C(C)\C(N2[Fe](Cl)N23)=C\4)=N\C1=C/C2=C(C)C(C=C)=C3\C=C/1C(C)=C(C=C)C/4=N\1 BTIJJDXEELBZFS-QDUVMHSLSA-K 0.000 description 1
- 229940025294 hemin Drugs 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- SJHHDDDGXWOYOE-UHFFFAOYSA-N oxytitamium phthalocyanine Chemical compound [Ti+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 SJHHDDDGXWOYOE-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
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- 239000011232 storage material Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000001018 xanthene dye Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
Description
本発明は、新規多孔質金属酸化物半導体膜形成用塗料および該塗料を用いて形成された多孔質金属酸化物半導体膜を有する光電気セルとに関する。 The present invention relates to a novel coating material for forming a porous metal oxide semiconductor film and a photoelectric cell having a porous metal oxide semiconductor film formed using the coating material.
高バンドギャップを有する金属酸化物半導体材料が光電変換材料、光触媒材料等の他光センサーや蓄電材料（バッテリー）等に用いられている。
このうち、光電変換材料は光エネルギーを電気エネルギーとして連続して取り出せる材料であり、電極間の電気化学反応を利用して光エネルギーを電気エネルギーに変換する材料である。このような光電変換材料に光を照射すると、一方の電極側で電子が発生し、対電極に移動し、対電極に移動した電子は、電解質中をイオンとして移動して一方の電極に戻る。このエネルギー変換は連続であるため、たとえば、太陽電池などに利用されている。
Metal oxide semiconductor materials having a high band gap are used for other optical sensors such as photoelectric conversion materials and photocatalyst materials, and power storage materials (batteries).
Among these, the photoelectric conversion material is a material that can continuously extract light energy as electric energy, and is a material that converts light energy into electric energy using an electrochemical reaction between electrodes. When such a photoelectric conversion material is irradiated with light, electrons are generated on one electrode side, move to the counter electrode, and the electrons moved to the counter electrode move as ions in the electrolyte and return to the one electrode. Since this energy conversion is continuous, it is used, for example, for solar cells.
一般的な太陽電池は、先ず透明性導電膜を形成したガラス板などの支持体上に光電変換材料用半導体の膜を形成して電極とし、次に、対電極として別の透明性導電膜を形成したガラス板などの支持体を備え、これらの電極間に電解質を封入して構成されている。 In general solar cells, a semiconductor film for a photoelectric conversion material is first formed on a support such as a glass plate on which a transparent conductive film is formed, and then another transparent conductive film is used as a counter electrode. A support such as a formed glass plate is provided, and an electrolyte is sealed between these electrodes.
光電変換材料用半導体膜に吸着した光増感材に例えば太陽光を照射すると、光増感材は可視領域の光を吸収して励起する。この励起によって発生する電子は半導体に移動し、次いで、透明導電性ガラス電極に移動し、２つの電極を接続する導線を通って対電極に移動し、対電極に移動した電子は電解質中の酸化還元系を還元する。一方、半導体に電子を移動させた光増感材は、酸化体の状態になっているが、この酸化体は電解質中の酸化還元系によって還元され、元の状態に戻る。このようにして電子が連続的に流れ、光電変換材料は太陽電池として機能する。 For example, when the photosensitizer adsorbed on the semiconductor film for photoelectric conversion material is irradiated with sunlight, the photosensitizer absorbs light in the visible region and is excited. The electrons generated by this excitation move to the semiconductor, then move to the transparent conductive glass electrode, move to the counter electrode through the conducting wire connecting the two electrodes, and the electrons transferred to the counter electrode are oxidized in the electrolyte. Reduce the reduction system. On the other hand, the photosensitizer that has moved electrons to the semiconductor is in an oxidant state, but this oxidant is reduced by the redox system in the electrolyte and returns to its original state. In this way, electrons flow continuously, and the photoelectric conversion material functions as a solar cell.
この光電変換材料としては、半導体膜表面に可視光領域に吸収を持つ分光増感色素を吸着させたものが用いられている。たとえば、特開平１−２２０３８０号公報（特許文献１）には、金属酸化物半導体膜の表面に、ルテニウム錯体などの遷移金属錯体からなる分光増感色素層を有する太陽電池が記載されている。また、特表平５−５０４０２３号公報（特許文献２）には、金属イオンでドープした酸化チタン半導体層の表面に、ルテニウム錯体などの遷移金属錯体からなる分光増感色素層を有する太陽電池が記載されている。 As this photoelectric conversion material, a material obtained by adsorbing a spectral sensitizing dye having absorption in a visible light region on the surface of a semiconductor film is used. For example, Japanese Patent Application Laid-Open No. 1-220380 (Patent Document 1) describes a solar cell having a spectral sensitizing dye layer made of a transition metal complex such as a ruthenium complex on the surface of a metal oxide semiconductor film. Japanese Patent Application Laid-Open No. 5-504023 (Patent Document 2) discloses a solar cell having a spectral sensitizing dye layer made of a transition metal complex such as a ruthenium complex on the surface of a titanium oxide semiconductor layer doped with metal ions. Are listed.
このような半導体膜の形成は、チタニアゾル等の微細粒子からなる塗料を電極基板上に塗布し、乾燥し、ついで、焼成する工程を繰り返して行い多孔質の厚膜を形成する方法が一般的である。
光増感材の吸着量の高く、光電変換効率を高めようとすると、比較的微粒の金属酸化物粒子を用いることが望まれるが、しかしながら、微細粒子を用いると、細孔径および細孔容積が小さくなり、さらに焼結しやすくなるため、得られる半導体膜の細孔径および細孔容積が小さくなってしまい、このため電解質の拡散が不充分となるため光電変換効率が不満足なものであった。 In order to increase the adsorption amount of the photosensitizer and increase the photoelectric conversion efficiency, it is desirable to use relatively fine metal oxide particles. However, when fine particles are used, the pore diameter and the pore volume are reduced. Since it becomes smaller and becomes easier to sinter, the pore diameter and pore volume of the obtained semiconductor film become smaller, and thus the diffusion of the electrolyte becomes insufficient, so that the photoelectric conversion efficiency is unsatisfactory.
一方、細孔径、細孔容積を大きくするために粒子径の大きな微粒子を用いると光増感材の吸着量が低下し、光電変換効率が低下する問題があった。また、粒子径が大きすぎると半導体膜の強度が低下したり、クラックが入り易くなる等の問題があった。 On the other hand, when fine particles having a large particle diameter are used to increase the pore diameter and pore volume, there is a problem that the amount of adsorption of the photosensitizer decreases and the photoelectric conversion efficiency decreases. Further, when the particle diameter is too large, there are problems such as the strength of the semiconductor film being lowered and cracks being easily generated.
このため、微細な粒子を使用しても多孔性を有する半導体膜を形成することが望まれていた。 For this reason, it has been desired to form a porous semiconductor film even if fine particles are used.
上記問題点に鑑み本発明者等は鋭意検討した結果、溶媒として水と有機溶媒との混合溶媒を用い、ミクロエマルジョンを形成させた多孔質金属酸化物半導体膜形成用塗料を用いると、ミクロエマルジョンによって、粒子を均一に分散できるだけではなく、膜の細孔径および細孔容積を大きくでき、しかも強度を低下させないことを見出して本発明を完成するに至った。 As a result of diligent investigations in view of the above problems, the present inventors have used a mixed solvent of water and an organic solvent as a solvent, and when using a coating for forming a porous metal oxide semiconductor film in which a microemulsion is formed, a microemulsion As a result, it was found that not only the particles can be uniformly dispersed, but also the pore diameter and pore volume of the membrane can be increased and the strength is not lowered, and the present invention has been completed.
本発明の構成は以下の通りである。
[1] 平均粒子径が５〜３００ｎｍの範囲にある金属酸化物微粒子金属酸化物微粒子と、水および有機溶媒の混合溶媒とからなり、
該混合溶媒がエマルジョンを形成している多孔質金属酸化物半導体膜形成用塗料。
[2]前記混合溶媒中の水の含有量が０．５〜６．５重量％の範囲にあるか、あるいは有機
溶媒の含有量が０．５〜６．５重量％の範囲にある[1]の多孔質金属酸化物半導体膜形成
用塗料。
[3]前記有機溶媒が水と相溶性のないアルコール類、ケトン類、グリコール類、エーテル
類から選ばれる１種以上である[1]または[2]の多孔質金属酸化物半導体膜形成用塗料。
[4]エマルジョン安定化剤として界面活性剤を含み、混合溶媒中の該界面活性剤の含有量
が０．５〜５．０重量％の範囲にある[1]〜[3]の多孔質金属酸化物半導体膜形成用塗料。[5]前記金属酸化物粒子が、酸化チタン、酸化ランタン、酸化ジルコニウム、酸化ニオビ
ウム、酸化タングステン、酸化ストロンチウム、酸化亜鉛、酸化スズ、酸化インジウムからなる群から選ばれる１種以上である[1]〜[4]の多孔質金属酸化物半導体膜形成用塗料。[6]前記金属酸化物粒子が結晶性酸化チタンである[5]の多孔質金属酸化物半導体膜形成用塗料。
[7]さらに増粘剤を含み、該増粘剤の含有量が０．１〜１５重量％の範囲にある[1]〜[6]
の多孔質金属酸化物半導体膜形成用塗料。
[8]表面に電極層(1)を有し、かつ該電極層(1)表面に光増感材を吸着した多孔質金属酸化
物半導体膜(1)が形成されてなる基板(1)と、
表面に電極層(2)を有する基板(2)とが、
前記電極層(1)および電極層(2)が対向するように配置してなり、
多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質層を設けてなる光電気セルにおいて、
多孔質金属酸化物半導体膜(1)が、[1]〜[7]の多孔質金属酸化物半導体膜形成用塗料を
用いて形成されてなることを特徴とする光電気セル。
[9]多孔質金属酸化物半導体膜(1)の細孔容積が０．３０〜０．６０ｍｌ／ｇの範囲にあり、平均細孔径が１０〜５０ｎｍの範囲にある[8]の光電気セルの製造方法。
[10]前記電極層(1)と多孔質金属酸化物半導体膜(1)との間にペルオキソチタン酸に由来する酸化チタン薄膜(1)を設けてなる[8]または[9]の光電気セル。
[11]前記酸化チタン薄膜(1)の膜厚が１０〜７０ｎｍの範囲にあり、細孔容積が０．０１
〜０．２０ｍｌ／ｇの範囲にあり、平均細孔径が０．５〜５．０ｎｍの範囲にある[8]〜[10]の光電気セル。
The configuration of the present invention is as follows.
[1] A metal oxide fine particle having an average particle diameter in the range of 5 to 300 nm, a metal oxide fine particle, and a mixed solvent of water and an organic solvent,
A coating material for forming a porous metal oxide semiconductor film, wherein the mixed solvent forms an emulsion.
[2] The water content in the mixed solvent is in the range of 0.5 to 6.5% by weight, or the organic solvent content is in the range of 0.5 to 6.5% by weight. ] For forming a porous metal oxide semiconductor film.
[3] The coating material for forming a porous metal oxide semiconductor film according to [1] or [2], wherein the organic solvent is at least one selected from alcohols, ketones, glycols and ethers that are incompatible with water .
[4] A porous metal according to [1] to [3], which contains a surfactant as an emulsion stabilizer, and the content of the surfactant in the mixed solvent is in the range of 0.5 to 5.0% by weight. A coating for forming an oxide semiconductor film. [5] The metal oxide particles are at least one selected from the group consisting of titanium oxide, lanthanum oxide, zirconium oxide, niobium oxide, tungsten oxide, strontium oxide, zinc oxide, tin oxide, and indium oxide. [4] A coating material for forming a porous metal oxide semiconductor film. [6] The coating material for forming a porous metal oxide semiconductor film according to [5], wherein the metal oxide particles are crystalline titanium oxide.
[7] A thickener is further included, and the content of the thickener is in the range of 0.1 to 15% by weight [1] to [6]
A coating material for forming a porous metal oxide semiconductor film.
[8] A substrate (1) having an electrode layer (1) on the surface and a porous metal oxide semiconductor film (1) having a photosensitizer adsorbed on the surface of the electrode layer (1). ,
A substrate (2) having an electrode layer (2) on the surface,
The electrode layer (1) and the electrode layer (2) are arranged so as to face each other,
In the photoelectric cell comprising an electrolyte layer between the porous metal oxide semiconductor film (1) and the electrode layer (2),
A photoelectric cell, wherein the porous metal oxide semiconductor film (1) is formed using the porous metal oxide semiconductor film-forming paint described in [1] to [7].
[9] The photoelectric cell according to [8], wherein the porous metal oxide semiconductor film (1) has a pore volume in the range of 0.30 to 0.60 ml / g and an average pore diameter in the range of 10 to 50 nm. Manufacturing method.
[10] The photoelectricity according to [8] or [9], wherein a titanium oxide thin film (1) derived from peroxotitanic acid is provided between the electrode layer (1) and the porous metal oxide semiconductor film (1). cell.
[11] The thickness of the titanium oxide thin film (1) is in the range of 10 to 70 nm, and the pore volume is 0.01
The photoelectric cell according to [8] to [10], which is in a range of ˜0.20 ml / g and an average pore diameter is in a range of 0.5 to 5.0 nm.
本発明によれば、多孔質金属酸化物半導体膜形成用塗料中の水および有機溶媒の混合溶
媒がエマルジョンを形成している。このエマルジョンが、塗料を塗布した後、乾燥、過熱時に蒸散し、細孔を生じる。このように細孔が形成されていれば、光増感材の吸着量の高い比較的微粒の金属酸化物粒子を用いても電解質の拡散に有効な平均細孔径を有し、且つ細孔容積の大きな多孔質金属酸化物半導体膜を形成することができる。これにより、充分にバックカレントを抑制することができ、光電変換効率に優れた光電気セルを提供することができる。
According to the present invention, the mixed solvent of water and the organic solvent in the coating material for forming a porous metal oxide semiconductor film forms an emulsion. This emulsion evaporates when it is dried and overheated after applying the paint, producing pores. If pores are formed in this way, even if relatively fine metal oxide particles having a high adsorption amount of the photosensitizer are used, they have an average pore diameter effective for electrolyte diffusion and have a pore volume. Large porous metal oxide semiconductor films can be formed. Thereby, the back current can be sufficiently suppressed, and a photoelectric cell excellent in photoelectric conversion efficiency can be provided.
以下、まず、本発明に係る多孔質金属酸化物半導体膜形成用塗料について説明する。
［多孔質金属酸化物半導体膜形成用塗料］
本発明に係る多孔質金属酸化物半導体膜形成用塗料は、金属酸化物微粒子と水および有機溶媒の混合溶媒とからなり、該混合溶媒がエマルジョンを形成していることを特徴としている。
Hereinafter, first, the porous metal oxide semiconductor film-forming paint according to the present invention will be described.
[Porous metal oxide semiconductor film forming coating]
The coating material for forming a porous metal oxide semiconductor film according to the present invention comprises metal oxide fine particles and a mixed solvent of water and an organic solvent, and the mixed solvent forms an emulsion.
金属酸化物微粒子
本発明に用いる金属酸化物粒子としては、光電気セル用金属酸化物半導体膜に用いることのできる従来公知の金属酸化物粒子を用いることができる。
Metal Oxide Fine Particles As the metal oxide particles used in the present invention, conventionally known metal oxide particles that can be used for metal oxide semiconductor films for photoelectric cells can be used.
具体的には酸化チタン、酸化ランタン、酸化ジルコニウム、酸化ニオビウム、酸化タングステン、酸化ストロンチウム、酸化亜鉛、酸化スズ、酸化インジウムの１種または２種以上の金属酸化物粒子が好ましい。 Specifically, one or more metal oxide particles of titanium oxide, lanthanum oxide, zirconium oxide, niobium oxide, tungsten oxide, strontium oxide, zinc oxide, tin oxide, and indium oxide are preferable.
中でもアナタース型酸化チタン、ルチル型酸化チタン、ブルッカイト型酸化チタン等の結晶性の酸化チタンが好ましく、中でもアナタース型酸化チタンは所望の粒子径の粒子が得やすく、光電変換効率も高いので好適に用いることができる。 Of these, crystalline titanium oxides such as anatase-type titanium oxide, rutile-type titanium oxide, and brookite-type titanium oxide are preferable. Among them, anatase-type titanium oxide is preferable because it can easily obtain particles having a desired particle size and has high photoelectric conversion efficiency. be able to.
金属酸化物粒子の平均粒子径は、５〜３００ｎｍ、さらには１０〜２００ｎｍの範囲にあることが好ましい。
この範囲あれば、膜強度も高く、また、光増感剤の吸着量も大きいので、光電変換効率を高くすることができる。
The average particle diameter of the metal oxide particles is preferably in the range of 5 to 300 nm, more preferably 10 to 200 nm.
Within this range, the film strength is high and the amount of adsorption of the photosensitizer is large, so that the photoelectric conversion efficiency can be increased.
金属酸化物粒子の前記下限未満のものは得ることが困難であり、得られたとしても塗料中で凝集したり、結晶性が低いために電子移動が困難であったりするため光電変換効率が不充分になったり、半導体膜の強度が不充分となることがある。金属酸化物粒子の平均粒子径が大きすぎると、得られる半導体膜の酸化チタン粒子の結合（接合ともいう）小さくなるとともに、加熱処理時の結合が低く不充分となり、強度が不充分となることがあり、また、光増感材の吸着量が低下するために光電変換効率が低下する傾向がある。 It is difficult to obtain a metal oxide particle having a particle size lower than the lower limit, and even if it is obtained, it is agglomerated in the paint or electron transfer is difficult due to low crystallinity, resulting in poor photoelectric conversion efficiency. In some cases, the semiconductor film becomes insufficient or the strength of the semiconductor film becomes insufficient. If the average particle diameter of the metal oxide particles is too large, the bond (also referred to as bonding) of the titanium oxide particles in the resulting semiconductor film becomes small, the bond during heat treatment becomes low and insufficient, and the strength becomes insufficient. In addition, the photoelectric conversion efficiency tends to decrease because the adsorption amount of the photosensitizer decreases.
溶媒
本発明に係る多孔質金属酸化物半導体膜形成用塗料の溶媒には水および有機溶媒の混合溶媒を用いる。
Solvent A mixed solvent of water and an organic solvent is used as a solvent of the coating material for forming a porous metal oxide semiconductor film according to the present invention.
有機溶媒としては水と相溶性のないアルコール類、ケトン類、グリコール類、エーテル類から選ばれる１種以上であることが好ましい。
アルコールとしては沸点がブタノール以上のものが好ましく、ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール、テルピネオール、ジヒドロターピネオール等のアルコール類；ヘキシレングリコール等のグリコール類；ジエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソプルピルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエ
チルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ブチルカルビトール、ブチルカルビトールアセテート等のエーテル類；酢酸プルピル、酢酸イソブチル、酢酸ブチル、酢酸イソペンチル、酢酸ペンチル、酢酸３−メトキシブチル、酢酸２−エチルブチル、酢酸シクロヘキシル、エチレングリコールモノアセタート等のエステル類；メチルイソブチルケトン、ブチルメチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ジプロピルケトン、メチルペンチルケトン、ジイソブチルケトン、イソホロン、アセチルアセトン、アセト酢酸エステル等のケトン類等が挙げられる。
The organic solvent is preferably at least one selected from alcohols, ketones, glycols and ethers that are incompatible with water.
Alcohols having a boiling point higher than butanol are preferred, but alcohols such as butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, terpineol, dihydroterpineol; glycols such as hexylene glycol; diethyl ether, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butyl carbitol, butyl carbitol acetate, etc. Ethers; propyl acetate, isobutyl acetate, Esters such as butyl acid, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate; methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, Examples include ketones such as methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, and acetoacetate.
なかでも、テルピネオール、ヒジドロターピネオール、ブチルカルビトール等は蒸気圧が低く、高沸点であるため、スクリーン印刷用の塗料として好ましい。
水と有機溶媒の混合溶媒は塗料中でエマルジョンを形成している。
Among these, terpineol, hydridoterpineol, butyl carbitol and the like are preferable as paints for screen printing because of their low vapor pressure and high boiling point.
A mixed solvent of water and an organic solvent forms an emulsion in the paint.
エマルジョンにはオイル中に水滴が分散したＷ／Ｏ型エマルジョンと水中に油滴が分散したＯ／Ｗ型エマルジョンがあり、本発明ではいずれも用いることができる。
Ｗ／Ｏ型エマルジョンの場合、混合溶媒中の水の含有量は０．５〜６．５重量％、さらには１〜５重量％の範囲にあることが好ましい。この範囲にあると、エマルジョンが安定に存在でき、また、半導体膜の細孔径や細孔容積を大きくすることが可能となる。なお混合溶媒中の水含有量が少なすぎるとエマルジョンの効果が得られにくく、すなわち、金属酸化物微粒子の粒子径が小さくても細孔容積および／または平均細孔径の大きな多孔質金属酸化物半導体膜が得られない場合がある。混合溶媒中の水含有量が大きすぎても（ただし、Ｏ／Ｗ型エマルジョンの場合を除く）、エマルジョン中の水分量が多く、乾燥時の蒸発に伴い収縮がおこり、多孔質金属酸化物半導体膜の強度が不充分となる場合がある。
Emulsions include a W / O type emulsion in which water droplets are dispersed in oil and an O / W type emulsion in which oil droplets are dispersed in water, and any of them can be used in the present invention.
In the case of the W / O type emulsion, the content of water in the mixed solvent is preferably in the range of 0.5 to 6.5% by weight, more preferably 1 to 5% by weight. Within this range, the emulsion can exist stably, and the pore diameter and pore volume of the semiconductor film can be increased. If the water content in the mixed solvent is too small, the effect of the emulsion is difficult to obtain, that is, a porous metal oxide semiconductor having a large pore volume and / or average pore diameter even if the particle diameter of the metal oxide fine particles is small. A film may not be obtained. Even if the water content in the mixed solvent is too large (except in the case of O / W type emulsion), the water content in the emulsion is large, and shrinkage occurs due to evaporation during drying. The film strength may be insufficient.
また、Ｏ／Ｗ型エマルジョンの場合、混合溶媒中の有機溶媒の含有量は０．５〜６．５重量％、さらには１〜５重量％の範囲にあることが好ましい。この範囲にあると、エマルジョンが安定に存在でき、また、半導体膜の細孔径や細孔容積を大きくすることが可能となる。混合溶媒中の有機溶媒の含有量が少ないとエマルジョンの効果が得られにくく、すなわち、金属酸化物微粒子の粒子径が小さくても細孔容積および／または平均細孔径の大きな多孔質金属酸化物半導体膜が得られない場合がある。有機溶媒の含有量が多すぎると、エマルジョン中の有機溶媒の比率が高いため、乾燥時に急激な蒸発等が起こり、この場合も多孔質金属酸化物半導体膜の強度が不充分となる場合がある。 In the case of an O / W emulsion, the content of the organic solvent in the mixed solvent is preferably in the range of 0.5 to 6.5% by weight, more preferably 1 to 5% by weight. Within this range, the emulsion can exist stably, and the pore diameter and pore volume of the semiconductor film can be increased. If the content of the organic solvent in the mixed solvent is small, the effect of the emulsion is difficult to obtain, that is, a porous metal oxide semiconductor having a large pore volume and / or a large average pore diameter even if the particle size of the metal oxide fine particles is small A film may not be obtained. If the content of the organic solvent is too high, the ratio of the organic solvent in the emulsion is high, so that rapid evaporation occurs during drying, and in this case, the strength of the porous metal oxide semiconductor film may be insufficient. .
エマルジョンは、その大きさが５〜５０ｎｍ、さらには８〜３０ｎｍの範囲にあるミクロエマルジョンであることが好ましい。この範囲にあると、エマルジョンを使用する効果が高く、多孔質金属酸化物半導体膜の平均細孔径を大きくしたり、細孔容積を大きくでき、電解質の拡散、色素吸着等に有効な細孔を形成できる。エマルジョンの大きさが小さすぎると、本発明のエマルジョンを形成する効果、即ち得られる多孔質金属酸化物半導体膜の平均細孔径を大きくする効果が得られず、電解質の拡散、色素吸着等に有効な細孔径の細孔を形成することができないために、光電変換効率の向上が不充分となる場合がある。エマルジョンの大きさが大きすぎると、得られる多孔質金属酸化物半導体膜の細孔径が大きくなり過ぎ、半導体膜の強度が低下したり、クラックが発生する場合がある。 The emulsion is preferably a microemulsion having a size in the range of 5 to 50 nm, more preferably 8 to 30 nm. Within this range, the effect of using the emulsion is high, the average pore diameter of the porous metal oxide semiconductor film can be increased, the pore volume can be increased, and pores effective for electrolyte diffusion, dye adsorption, etc. Can be formed. If the size of the emulsion is too small, the effect of forming the emulsion of the present invention, that is, the effect of increasing the average pore size of the resulting porous metal oxide semiconductor film cannot be obtained, and it is effective for electrolyte diffusion, dye adsorption, etc. Since pores with a small pore size cannot be formed, the photoelectric conversion efficiency may be insufficiently improved. When the size of the emulsion is too large, the pore diameter of the resulting porous metal oxide semiconductor film becomes too large, and the strength of the semiconductor film may be reduced or cracks may occur.
このようなエマルジョンの大きさは動的光散乱法により測定することができる。なお、多孔質金属酸化物半導体膜形成用塗料中のエマルジョンの大きさは測定することが困難であるので、通常は、上記金属酸化物粒子と混合する前のエマルジョンの大きさを測定する。 The size of such an emulsion can be measured by a dynamic light scattering method. In addition, since it is difficult to measure the size of the emulsion in the coating material for forming the porous metal oxide semiconductor film, the size of the emulsion before mixing with the metal oxide particles is usually measured.
本発明では、細孔径を大きくするには、エマルジョンの大きさを大きくすればよく、細孔容積を多くするには、有機溶媒リッチのエマルジョンでは水含有量、水リッチのエマル
ジョンでは有機溶媒含有量を多くすればよい。
In the present invention, in order to increase the pore size, the size of the emulsion may be increased. To increase the pore volume, the water content in the organic solvent-rich emulsion and the organic solvent content in the water-rich emulsion. You should increase more.
本発明の多孔質金属酸化物半導体膜形成用塗料にはエマルジョン安定化剤として界面活性剤を含むことが好ましい。
この時の界面活性剤としては、親水性基および疎水性基を有する界面活性剤を用いる。
The paint for forming a porous metal oxide semiconductor film of the present invention preferably contains a surfactant as an emulsion stabilizer.
As the surfactant at this time, a surfactant having a hydrophilic group and a hydrophobic group is used.
例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、脂肪酸ポリグリセリンエステル、脂肪酸ショ糖エステル、脂肪酸アルカノールアミド、アルキルアミンオキサイド、アルキルアミドアミンオキサイド等が挙げられる。 For example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid polyglycerin ester, fatty acid sucrose ester, fatty acid alkanolamide, alkylamine oxide, alkylamidoamine oxide and the like can be mentioned.
界面活性剤の含有量は、混合溶媒中に５重量％以下、さらには０．５〜４重量％の範囲にあることが好ましい。この範囲で使用すると、エマルジョンが安定化しており、所望の細孔容積や平均細孔径を達成できる上、界面活性剤が細孔形成を阻害することもない。 The content of the surfactant is preferably 5% by weight or less, more preferably in the range of 0.5 to 4% by weight in the mixed solvent. When used in this range, the emulsion is stabilized, the desired pore volume and average pore diameter can be achieved, and the surfactant does not inhibit pore formation.
界面活性剤の含有量が少なすぎると、十分なエマルジョンが形成できない場合や、できたとしても不安定で、得られる多孔質金属酸化物半導体膜にクラック等が発生する場合がある。 If the content of the surfactant is too small, a sufficient emulsion cannot be formed, or even if it is possible, the resulting porous metal oxide semiconductor film may be cracked.
界面活性剤の含有量が５重量％を越えると、界面活性剤の量が多すぎ、エマルジョンによる細孔容積および平均細孔径の制御が困難となる。
さらに、本発明の多孔質金属酸化物半導体膜形成用塗料には増粘剤を含むことが好ましい。
When the content of the surfactant exceeds 5% by weight, the amount of the surfactant is too large, and it becomes difficult to control the pore volume and the average pore diameter by the emulsion.
Furthermore, it is preferable that the coating material for forming a porous metal oxide semiconductor film of the present invention contains a thickener.
増粘剤としては、ポリエチレンオキサイド、ポリアセチレン、ポリビニルピロリドン、ポリピロール、ヒドロキシプロピルセルロース、ポリアクリル酸、エチルセルロース、メチルセルロース、カルボキシメチルメチルセルロース、ポリビニルアルコール、アクリル樹脂、ケトン樹脂、メラミン樹脂等が挙げられる。このような増粘剤が多孔質金属酸化物半導体膜形成用塗料中に含まれていると、塗料の粘度が高くなり、これにより均一に塗布することができる。
塗料中の増粘剤の含有量は増粘剤の種類によっても異なるが１５重量％以下、さらには０．１〜１０重量％の範囲にあることが好ましい。
Examples of the thickener include polyethylene oxide, polyacetylene, polyvinyl pyrrolidone, polypyrrole, hydroxypropyl cellulose, polyacrylic acid, ethyl cellulose, methyl cellulose, carboxymethyl methyl cellulose, polyvinyl alcohol, acrylic resin, ketone resin, and melamine resin. When such a thickening agent is contained in the coating material for forming a porous metal oxide semiconductor film, the viscosity of the coating material is increased, whereby uniform application can be achieved.
The content of the thickener in the paint varies depending on the type of the thickener, but is preferably 15% by weight or less, and more preferably in the range of 0.1 to 10% by weight.
増粘剤が少ないと、前記増粘効果が不充分であり、増粘剤が多すぎると、乾燥―焼成後に増粘剤が半導体膜内に残存し、電子の移動を妨げるなどの理由より、充分な光電変換効率の向上効果が得られないことがある。 If the amount of the thickener is small, the thickening effect is insufficient, and if the amount of the thickener is too large, the thickener remains in the semiconductor film after drying-firing, and the movement of electrons is hindered. A sufficient effect of improving photoelectric conversion efficiency may not be obtained.
エマルジョンの作製方法としては、特に制限されないが、所定範囲となるように、水と有機溶媒とを混合し、攪拌（機械的に混合）するなどの方法を採用できる。
塗料の調製
多孔質金属酸化物半導体膜形成用塗料は、前記各原料を所定量配合し、機械的に混合することによって調製することができる。
The method for producing the emulsion is not particularly limited, and a method of mixing water and an organic solvent and stirring (mechanically mixing) so as to be within a predetermined range can be employed.
Preparation of paint The paint for forming a porous metal oxide semiconductor film can be prepared by blending a predetermined amount of each of the raw materials and mechanically mixing them.
粒子とエマルジョンとの混合条件は使用する各原料の種類、配合量、塗料の濃度等によって異なるが、前記エマルジョンを形成し、得られる半導体膜の平均細孔径、細孔容積が前記範囲となるように行う。 The mixing conditions of the particles and the emulsion vary depending on the types of raw materials to be used, the blending amount, the concentration of the paint, etc., but the average pore diameter and pore volume of the semiconductor film obtained by forming the emulsion are within the above ranges. To do.
混合方法としては、ボールミル、ペイントシェイカー、ロールミル、３本ロール、自転公転ミキサー等の装置を用い、混合条件としては塗料中へマイクロエマルジョンを含む溶媒が良く分散できる条件で実施すればよい。 As a mixing method, an apparatus such as a ball mill, a paint shaker, a roll mill, a triple roll, a rotation and revolution mixer or the like may be used, and the mixing may be performed under conditions that allow the solvent containing the microemulsion to be well dispersed in the paint.
なお、本発明では、水と有機溶媒を所定比で混合し、好ましくは界面活性剤を添加し、機械的に混合して予めエマルジョンを調製したもの金属酸化物粒子分散液等と混合し、さらに機械的に混合することが好ましい。この場合、均一な大きさのエマルジョンが形成されるためか、得られる多孔質金属酸化物半導体膜の細孔径分布が均一になり、電解質の拡散に有効で、かつ、色素吸着等に有効な細孔径の細孔が形成される傾向がある。 In the present invention, water and an organic solvent are mixed at a predetermined ratio, preferably a surfactant is added, and mechanically mixed to prepare an emulsion in advance and mixed with a metal oxide particle dispersion or the like. It is preferable to mix mechanically. In this case, because the emulsion of uniform size is formed, the pore size distribution of the obtained porous metal oxide semiconductor film becomes uniform, which is effective for electrolyte diffusion and effective for dye adsorption and the like. There is a tendency that pores having a pore diameter are formed.
多孔質金属酸化物半導体膜形成用塗料中の金属酸化物粒子の濃度は固形分として５〜３５重量％、さらには７〜２０重量％の範囲にあることが好ましい。
前記固形分濃度が薄すぎると、所望の厚さの多孔質金属酸化物半導体膜を形成できない場合があり、繰り返し半導体膜形成操作が必要となることがある。固形分濃度が高すぎると、分散液の粘度が高くなりすぎて、得られる多孔質金属酸化物半導体膜の緻密度が低下し、半導体膜の強度、耐摩耗性が不充分となることがある。
The concentration of the metal oxide particles in the coating material for forming a porous metal oxide semiconductor film is preferably in the range of 5 to 35% by weight, more preferably 7 to 20% by weight as the solid content.
If the solid content concentration is too low, a porous metal oxide semiconductor film having a desired thickness may not be formed, and a semiconductor film forming operation may be required repeatedly. If the solid content concentration is too high, the viscosity of the dispersion becomes too high, the density of the resulting porous metal oxide semiconductor film may decrease, and the strength and wear resistance of the semiconductor film may be insufficient. .
このような塗料は、光電気セルの多孔質半導体膜形成用に使用される。
つぎに、本発明に係る光電気セルについて説明する。
［光電気セル］
本発明に係る光電気セルは、表面に電極層(1)を有し、かつ該電極層(1)表面に光増感材を吸着した多孔質金属酸化物半導体膜(1)が形成されてなる基板(1)と、
表面に電極層(2)を有する基板(2)とが、
前記電極層(1)および電極層(2)が対向するように配置してなり、
多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質層を設けてなる光電気セルにおいて、
多孔質金属酸化物半導体膜(1)が、前記多孔質金属酸化物半導体膜形成用塗料を用いて
形成されたことを特徴としている。
Such a paint is used for forming a porous semiconductor film of a photoelectric cell.
Next, the photoelectric cell according to the present invention will be described.
[Photoelectric cell]
The photoelectric cell according to the present invention has an electrode layer (1) on the surface and a porous metal oxide semiconductor film (1) adsorbing a photosensitizer on the surface of the electrode layer (1). A substrate (1)
A substrate (2) having an electrode layer (2) on the surface,
The electrode layer (1) and the electrode layer (2) are arranged so as to face each other,
In the photoelectric cell comprising an electrolyte layer between the porous metal oxide semiconductor film (1) and the electrode layer (2),
The porous metal oxide semiconductor film (1) is formed by using the porous metal oxide semiconductor film-forming coating material.
本発明に係る光電気セルとしては、たとえば、図１に示すものが挙げられる。
図１は、本発明の光電気セルの１例を示す概略断面図であり、表面に電極層(1)を有し
、必用に応じて該電極層(1)上に酸化チタン薄膜(1)を有し、電極層(1)上、あるいは酸化
チタン薄膜(1)上に光増感材を吸着した多孔質金属酸化物半導体膜(1)が形成されてなる基板(1)と、表面に電極層(2)を有する基板(2)とが、前記電極層(1)および電極層(2)が対向
するように配置してなり、多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質が封入されている。
Examples of the photoelectric cell according to the present invention include those shown in FIG.
FIG. 1 is a schematic cross-sectional view showing an example of the photoelectric cell of the present invention, which has an electrode layer (1) on the surface and, if necessary, a titanium oxide thin film (1) on the electrode layer (1). A substrate (1) having a porous metal oxide semiconductor film (1) formed by adsorbing a photosensitizer on an electrode layer (1) or a titanium oxide thin film (1), and a surface thereof. The substrate (2) having the electrode layer (2) is disposed so that the electrode layer (1) and the electrode layer (2) face each other, and the porous metal oxide semiconductor film (1) and the electrode layer ( An electrolyte is enclosed between 2).
図１中、１は電極層(1)、２は半導体膜(1)、３は電極層(2)、４は電解質層(2)、５は基板(1)、６は基板(2)、７は酸化チタン薄膜(1)を示す。
なお、本発明に係る光電気セルは図示した光電気セルに限定されるものではなく、半導体膜を２層以上有し、この間に別の電極層および電解質層を設けた光電気セルであってもよい。
In FIG. 1, 1 is an electrode layer (1), 2 is a semiconductor film (1), 3 is an electrode layer (2), 4 is an electrolyte layer (2), 5 is a substrate (1), 6 is a substrate (2), Reference numeral 7 denotes a titanium oxide thin film (1).
The photoelectric cell according to the present invention is not limited to the photoelectric cell shown in the figure, and is a photoelectric cell having two or more semiconductor films and another electrode layer and an electrolyte layer provided therebetween. Also good.
基板
一方の基板としてはガラス基板、ＰＥＴ等の樹脂フィルム基板等の透明でかつ絶縁性を有する基板を用いることができる。
As the substrate on one side, a transparent and insulating substrate such as a glass substrate or a resin film substrate such as PET can be used.
他の一方の基板としては使用に耐える強度を有していれば特に制限はなく、ガラス基板、ＰＥＴ等の樹脂フィルム基板等の絶縁性基板の他に、金属チタン、金属アルミニウム、金属銅、金属ニッケルなどの導電性基板を使用することができる。 The other substrate is not particularly limited as long as it has enough strength to withstand use, and in addition to an insulating substrate such as a glass substrate or a resin film substrate such as PET, metal titanium, metal aluminum, metal copper, metal A conductive substrate such as nickel can be used.
本発明では、電極層(1)を形成する基板として、少なくとも一方の基板に樹脂フィルム
を用いることができる。
基板が樹脂フィルムであると、ガラス基盤を用いる場合より、基材自体が安価であることに加え、連続生産が可能であることから経済性に優れており、さらに、軽量の太陽電池がとなり、持運びが容易となるため、モバイル用等に適している。
In the present invention, as the substrate on which the electrode layer (1) is formed, a resin film can be used for at least one of the substrates.
When the substrate is a resin film, in addition to using a glass substrate, in addition to the base material itself being inexpensive, continuous production is possible and it is excellent in economic efficiency. Since it is easy to carry, it is suitable for mobile use.
樹脂フィルムとしては、ＰＥＮフィルム、ＰＥＴフィルム等従来公知の樹脂フィルムが挙げられる。また、基板は少なくとも一方が透明であればよい。
電極層
基板(1)表面に形成された電極層(1)としては、酸化錫、Ｓｂ、ＦまたはＰがドーピングされた酸化錫、Ｓｎおよび／またはＦがドーピングされた酸化インジウム、酸化アンチモン、酸化亜鉛、貴金属等などの従来公知の電極を使用することができる。
Examples of the resin film include conventionally known resin films such as a PEN film and a PET film. Further, it is sufficient that at least one of the substrates is transparent.
The electrode layer (1) formed on the surface of the electrode layer substrate (1) includes tin oxide, tin oxide doped with Sb, F or P, indium oxide doped with Sn and / or F, antimony oxide, oxidation Conventionally known electrodes such as zinc and noble metals can be used.
このような電極層(1)は、熱分解法、ＣＶＤ法などの従来公知の方法により形成するこ
とができる。
また、他の一方の基板(2)表面に形成された電極層(2)としては、還元触媒能を有するものであれば特に制限されるものでなく、白金、ロジウム、ルテニウム金属、ルテニウム酸化物等の電極材料、酸化錫、Ｓｂ、ＦまたはＰがドーピングされた酸化錫、Ｓｎおよび／またはＦがドーピングされた酸化インジウム、酸化アンチモンなどの導電性材料の表面に前記電極材料をメッキあるいは蒸着した電極、カーボン電極など従来公知の電極を用いることができる。
Such an electrode layer (1) can be formed by a conventionally known method such as a thermal decomposition method or a CVD method.
In addition, the electrode layer (2) formed on the surface of the other substrate (2) is not particularly limited as long as it has a reduction catalytic ability, and is composed of platinum, rhodium, ruthenium metal, ruthenium oxide. The electrode material was plated or deposited on the surface of a conductive material such as tin oxide, tin oxide doped with Sb, F or P, indium oxide doped with Sn and / or F, or antimony oxide. Conventionally known electrodes such as electrodes and carbon electrodes can be used.
このような電極層(2)は、基板(2)上に前記電極を直接コーティング、メッキあるいは蒸着させて、導電性材料を熱分解法、ＣＤＶ法等の従来公知の方法により導電層を形成した後、該導電層上に前記電極材料をメッキあるいは蒸着するなど従来公知の方法により形成することができる。 Such an electrode layer (2) was formed by directly coating, plating or vapor-depositing the electrode on the substrate (2), and forming a conductive layer by a conventionally known method such as a thermal decomposition method or a CDV method. Thereafter, the electrode material can be formed on the conductive layer by a conventionally known method such as plating or vapor deposition.
なお、基板(2)は、基板(1)と同様に透明基板であってもよく、また電極層(2)は、電極
層(1)と同様に透明電極であってもよい。さらに、基板(2)は基板(1)と同じものであって
もよく、電極層(2)は電極層(1)と同じものであってもよい。
The substrate (2) may be a transparent substrate similarly to the substrate (1), and the electrode layer (2) may be a transparent electrode similarly to the electrode layer (1). Furthermore, the substrate (2) may be the same as the substrate (1), and the electrode layer (2) may be the same as the electrode layer (1).
透明基板(1)と透明電極層(1)の可視光透過率は高い方が好ましく、具体的には５０％以上、特に好ましくは９０％以上であることが望ましい。可視光透過率が５０％未満の場合は光電変換効率が低くなることがある。 The visible light transmittance of the transparent substrate (1) and the transparent electrode layer (1) is preferably higher, specifically 50% or more, particularly preferably 90% or more. When the visible light transmittance is less than 50%, the photoelectric conversion efficiency may be lowered.
電極層(1)および電極層(2)の抵抗値は、各々１００Ω／ｃｍ2以下であることが好まし
い。電極層の抵抗値が１００Ω／ｃｍ2を超えて高くなると光電変換効率が低くなること
がある。
The resistance values of the electrode layer (1) and the electrode layer (2) are each preferably 100 Ω / cm 2 or less. The photoelectric conversion efficiency when the resistance value of the electrode layer is increased beyond 100 [Omega / cm 2 may decrease.
酸化チタン薄膜
本発明において、必要に応じて電極層(1)上に酸化チタン薄膜(1)を形成することができ、この酸化チタン薄膜(1)は増粘剤を含むペルオキシチタン酸水溶液を用いて形成された
ものであり、緻密な膜である。
Titanium oxide thin film In the present invention, a titanium oxide thin film (1) can be formed on the electrode layer (1) as necessary, and this titanium oxide thin film (1) uses a peroxy titanic acid aqueous solution containing a thickener. This is a dense film.
酸化チタン薄膜(1)は膜厚が１０〜７０ｎｍ、さらには２０〜４０ｎｍの範囲にあるこ
とが好ましい。酸化チタン薄膜(1)の膜厚が薄いと、酸化チタン膜(1)による暗電流の抑制、電子の再結合の抑制が不充分となる。酸化チタン薄膜(1)の膜厚が厚すぎると、エネル
ギー障壁が大きくなりすぎて電子の移動が抑制され、逆に光電変換効率が低下することがある。
The titanium oxide thin film (1) preferably has a thickness of 10 to 70 nm, more preferably 20 to 40 nm. If the thickness of the titanium oxide thin film (1) is small, the suppression of dark current and the suppression of electron recombination by the titanium oxide film (1) are insufficient. If the film thickness of the titanium oxide thin film (1) is too thick, the energy barrier becomes too large to suppress the movement of electrons, and conversely, the photoelectric conversion efficiency may decrease.
また、酸化チタン薄膜(1)は細孔容積が０．０１〜０．２０ｍｌ／ｇ、さらには０．０
２〜０．１５ｍｌ／ｇの範囲にあることが好ましい。細孔容積が前記上限よりも多いと、
緻密性が低下してしまい、電解液と電極との接触が起こり、電子の逆流、電子の再結合の抑制効果が不充分となることがある。なお、スパッタリングなどの方法でも、緻密な酸化チタン薄膜を得ることは可能であるが、緻密すぎて電子の移動を阻害したり、後に形成する多孔質金属酸化物半導体膜との密着性が不充分となることがある。
Further, the titanium oxide thin film (1) has a pore volume of 0.01 to 0.20 ml / g, more preferably 0.0.
It is preferably in the range of 2 to 0.15 ml / g. When the pore volume is larger than the upper limit,
Density may decrease, and contact between the electrolyte and the electrode may occur, and the effect of suppressing the backflow of electrons and the recombination of electrons may be insufficient. It is possible to obtain a dense titanium oxide thin film even by a method such as sputtering, but it is too dense to inhibit the movement of electrons or has insufficient adhesion to a porous metal oxide semiconductor film to be formed later. It may become.
酸化チタン薄膜(1)は平均細孔径が０．５〜５．０ｎｍ、さらには１．０〜３．５ｎｍ
の範囲にあることが好ましい。酸化チタン薄膜(1)の平均細孔径が前記上限よりも大きい
ものは、電解液と電極との接触が起こり、電子の逆流、電子の再結合の抑制効果が不充分となることがある。
The titanium oxide thin film (1) has an average pore diameter of 0.5 to 5.0 nm, more preferably 1.0 to 3.5 nm.
It is preferable that it exists in the range. When the average pore size of the titanium oxide thin film (1) is larger than the above upper limit, contact between the electrolytic solution and the electrode may occur, and the effect of suppressing the backflow of electrons and recombination of electrons may be insufficient.
このような酸化チタン薄膜(1)は、電極層(1)上に増粘剤を含むペルオキシチタン酸水溶液を、(A)スピンコート法、(B)ディップコート法、(C)フレキソ印刷法、(D)ロールコーター法、(E)電気泳動法から選ばれる１種以上の方法で塗布し、従来公知の方法で乾燥し、
硬化させることにより形成することができる。
Such a titanium oxide thin film (1) is a peroxytitanic acid aqueous solution containing a thickener on the electrode layer (1), (A) spin coating method, (B) dip coating method, (C) flexographic printing method, It is applied by one or more methods selected from (D) roll coater method and (E) electrophoresis method, and dried by a conventionally known method.
It can be formed by curing.
酸化チタン薄膜(1)の形成に用いるペルオキシチタン酸水溶液の濃度はＴiＯ2として０
．１〜２．０重量％、さらには０．３〜１．０重量％の範囲にあることが好ましい。ペルオキシチタン酸水溶液の濃度が薄いと、所望の膜厚の酸化チタン薄膜(1)が得られないこ
とがあり、繰返し塗布、乾燥を行う必要が生じる。ペルオキシチタン酸水溶液の濃度が薄いと、乾燥時にクラックが生じたり、緻密な膜を形成できないことがあり、暗電流の抑制、電子の再結合の抑制効果が得られないことがある。
The concentration of the peroxytitanic acid aqueous solution used for forming the titanium oxide thin film (1) is 0 as TiO 2.
. It is preferably in the range of 1 to 2.0% by weight, more preferably 0.3 to 1.0% by weight. If the concentration of the peroxytitanic acid aqueous solution is low, the titanium oxide thin film (1) having a desired film thickness may not be obtained, and it is necessary to repeatedly apply and dry the titanium oxide thin film (1). If the concentration of the peroxytitanic acid aqueous solution is low, cracks may occur during drying or a dense film may not be formed, and the effects of suppressing dark current and suppressing recombination of electrons may not be obtained.
ここで、ペルオキシチタン酸とは過酸化水和チタンをいい、たとえば、チタン化合物の水溶液、または水和酸化チタンのゾルまたはゲルに過酸化水素を加えて加熱することによって調製することができる。具体的には、まず、チタン化合物を加水分解してオルソチタン酸のゾルまたはゲルを調製する。 Here, peroxytitanic acid refers to hydrated titanium peroxide, and can be prepared, for example, by adding hydrogen peroxide to an aqueous solution of a titanium compound, or a sol or gel of hydrated titanium oxide and heating. Specifically, first, a titanium compound is hydrolyzed to prepare a sol or gel of orthotitanic acid.
オルソチタン酸のゲルは、チタン化合物として塩化チタン、硫酸チタン、硫酸チタニルなどのチタン塩を使用し、この水溶液にアルカリを加えて中和し、洗浄することによって得ることができる。また、オルソチタン酸のゾルは、チタン塩の水溶液をイオン交換樹脂に通して陰イオンを除去するか、あるいはチタンテトラメトキシド、チタンテトラエトキシド、チタンテトライソプロポキシドなどのチタンアルコキシドの水および／または有機溶媒に酸またはアルカリを加えて加水分解することによって得ることができる。 The orthotitanic acid gel can be obtained by using a titanium salt such as titanium chloride, titanium sulfate, or titanyl sulfate as a titanium compound, neutralizing the aqueous solution by adding an alkali, and washing. In addition, the sol of orthotitanic acid is used to remove anions by passing an aqueous solution of a titanium salt through an ion exchange resin, or water of titanium alkoxide such as titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide and the like. It can be obtained by adding an acid or alkali to an organic solvent and hydrolyzing it.
中和あるいは加水分解する際のチタン化合物の溶液のｐＨは７〜１３の範囲にあることが好ましい。チタン化合物溶液のｐＨが上記範囲にあるとオルソチタン酸のゲルまたはゾルの微細な粒子が得られ、後述する過酸化水素との反応が容易となる。 The pH of the titanium compound solution during neutralization or hydrolysis is preferably in the range of 7-13. When the pH of the titanium compound solution is in the above range, fine particles of orthotitanic acid gel or sol are obtained, and the reaction with hydrogen peroxide described later becomes easy.
さらに、中和あるいは加水分解する際の温度は０〜６０℃の範囲にあることが好ましく、特に好ましい範囲は０〜５０℃の範囲である。中和あるいは加水分解する際の温度が上記範囲にあるとオルソチタン酸のゲルまたはゾルの微細な粒子が得られ、後述する過酸化水素との反応が容易となる。得られたゲルまたはゾル中のオルソチタン酸粒子は、非晶質であることが好ましい。 Furthermore, the temperature at the time of neutralization or hydrolysis is preferably in the range of 0 to 60 ° C, and particularly preferably in the range of 0 to 50 ° C. When the temperature at the time of neutralization or hydrolysis is within the above range, fine particles of orthotitanic acid gel or sol are obtained, and the reaction with hydrogen peroxide described later becomes easy. The orthotitanic acid particles in the obtained gel or sol are preferably amorphous.
次に、オルソチタン酸のゲルまたはゾルあるいはこれらの混合物に、過酸化水素を添加してオルソチタン酸を溶解してペルオキシチタン酸水溶液を調製する。
ペルオキシチタン酸水溶液を調製するに際しては、オルソチタン酸のゲルまたはゾルあるいはこれらの混合物を、必要に応じて約５０℃以上に加熱したり、攪拌したりすることが好ましい。また、この際、オルソチタン酸の濃度が高くなるすぎると、その溶解に長時間を必要とし、さらに未溶解のゲルが沈殿したり、あるいは得られるペルオキシチタン酸
水溶液が粘調になることがある。このため、ＴiＯ2濃度としては、約１０重量％以下であることが好ましく、さらに約５重量％以下であることが望ましい。
Next, hydrogen peroxide is added to the orthotitanic acid gel or sol or a mixture thereof to dissolve the orthotitanic acid to prepare a peroxytitanic acid aqueous solution.
In preparing the peroxytitanic acid aqueous solution, it is preferable to heat or stir the orthotitanic acid gel or sol or a mixture thereof to about 50 ° C. or higher as necessary. At this time, if the concentration of orthotitanic acid is too high, it takes a long time to dissolve the solution, and an undissolved gel may precipitate, or the resulting peroxytitanic acid aqueous solution may become viscous. . For this reason, the TiO 2 concentration is preferably about 10% by weight or less, and more preferably about 5% by weight or less.
添加する過酸化水素の量は、Ｈ2Ｏ2／ＴiＯ2(オルソチタン酸はＴiＯ2に換算)重量比で１以上であれば、オルソチタン酸を完全に溶解することができる。Ｈ2Ｏ2／ＴiＯ2重量比が１未満であると、オルソチタン酸が完全には溶解せず、未反応のゲルまたはゾルが残存することがある。また、Ｈ2Ｏ2／ＴiＯ2重量比は大きいほど、オルソチタン酸の溶解速度は大きく反応時間は短時間で終了するが、あまり過剰に過酸化水素を用いても、未反応の過酸化水素が系内に残存するだけであり、経済的でない。このような量で過酸化水素を用いると、オルソチタン酸は０.５〜２０時間程度で溶解する。本発明に用いるペルオキシ
チタン酸水溶液は溶解後、５０〜９０℃で熟成することが好ましい。この熟成を行うと実質的に非晶質であるがアナターゼ類似のＸ線回折パターンを示し、平均粒子径が１０〜５０ｎｍの範囲にある粒子が生成し、前記細孔容積および平均細孔径を有する酸化チタン薄膜を再現性よく得ることができる。
If the amount of hydrogen peroxide to be added is 1 or more in terms of the weight ratio of H 2 O 2 / TiO 2 (ortho titanic acid is converted to TiO 2 ), the ortho titanic acid can be completely dissolved. If the H 2 O 2 / TiO 2 weight ratio is less than 1, orthotitanic acid may not be completely dissolved, and an unreacted gel or sol may remain. In addition, as the H 2 O 2 / TiO 2 weight ratio is larger, the dissolution rate of orthotitanic acid is larger and the reaction time is completed in a shorter time. Remains in the system and is not economical. When hydrogen peroxide is used in such an amount, orthotitanic acid dissolves in about 0.5 to 20 hours. The aqueous peroxytitanic acid solution used in the present invention is preferably aged at 50 to 90 ° C. after dissolution. When this aging is carried out, it is substantially amorphous but exhibits an anatase-like X-ray diffraction pattern, and particles having an average particle diameter in the range of 10 to 50 nm are generated, and have the pore volume and the average pore diameter. A titanium oxide thin film can be obtained with good reproducibility.
熟成時間は熟成温度によっても異なるが、通常１〜２５時間である。
また、本発明に用いるペルオキシチタン酸水溶液は増粘剤を含んでいてもよく、増粘剤としてはエチレングリコール、ポリエチレングリコール、ポリビニルピロリドン、ヒドロキシプロピルセルロース、ポリアクリル酸、エチルセルロース、ポリビニルアルコール、メタノール、エタノール、イソプロピルアルコール、ノルマルブタノール、ターシャリーブタノール等が含まれていてもよい。このような増粘剤がペルオキシチタン酸水溶液中に含まれていると、塗布液の粘度が高くなり、これにより均一に塗布することができ、クラックのない均一な膜厚の酸化チタン薄膜が得られ、下層の電極層、上層の多孔質金属酸化物半導体膜との密着性の高い酸化チタン薄膜を得ることができる。
The aging time varies depending on the aging temperature, but is usually 1 to 25 hours.
Moreover, the peroxytitanic acid aqueous solution used in the present invention may contain a thickener, and as the thickener, ethylene glycol, polyethylene glycol, polyvinyl pyrrolidone, hydroxypropyl cellulose, polyacrylic acid, ethyl cellulose, polyvinyl alcohol, methanol, Ethanol, isopropyl alcohol, normal butanol, tertiary butanol and the like may be contained. When such a thickener is contained in the peroxytitanic acid aqueous solution, the viscosity of the coating solution increases, and this enables uniform coating, resulting in a titanium oxide thin film having a uniform thickness without cracks. Thus, a titanium oxide thin film having high adhesion to the lower electrode layer and the upper porous metal oxide semiconductor film can be obtained.
ペルオキシチタン酸水溶液中の増粘剤の濃度は増粘剤の種類によっても異なるが１．０〜６０．０重量％、さらには３．０〜３５．０重量％の範囲にあることが好ましい。増粘剤の濃度が低すぎると、前記増粘剤を用いた効果が不充分であり、高すぎても塗布性が低下し、膜厚が厚くなりすぎたり、クラックが生じることがあり、前記酸化チタン薄膜を設ける効果が得られないことがある。 The concentration of the thickener in the peroxytitanic acid aqueous solution varies depending on the type of the thickener, but is preferably in the range of 1.0 to 60.0% by weight, more preferably 3.0 to 35.0% by weight. If the concentration of the thickener is too low, the effect using the thickener is insufficient, and if it is too high, the applicability is lowered, the film thickness becomes too thick, or cracks may occur, The effect of providing a titanium oxide thin film may not be obtained.
ペルオキシチタン酸水溶液の塗布方法が(A)スピンコート法、(B)ディップコート法、(C)フレキソ印刷法、(D)ロールコーター法(E)電気泳動法のいずれかであれば、電極層との
密着性に優れ、膜厚が均一で、クラックがなく、かつ強度に優れた酸化チタン薄膜(1)を
形成することができ、特に工業的にはフレキソ印刷法が好適に採用することができる。
If the coating method of the peroxytitanic acid aqueous solution is any one of (A) spin coating method, (B) dip coating method, (C) flexographic printing method, (D) roll coater method (E) electrophoresis method, electrode layer It is possible to form a titanium oxide thin film (1) that has excellent adhesion with the film, has a uniform film thickness, is free of cracks, and is excellent in strength, and is particularly suitable for industrial use in flexographic printing. it can.
乾燥は分散媒である水を除去できる温度であればよく、従来公知の方法を採用することができ、風乾することも可能であるが、通常５０〜１５０℃で０．２〜５時間程度乾燥する。本発明では、乾燥後、後述する多孔質金属酸化物半導体膜を形成することができるが、乾燥後硬化した後多孔質金属酸化物半導体膜を形成してもよい。 The drying may be performed at any temperature that can remove water as a dispersion medium, and a conventionally known method can be adopted and air drying is also possible, but drying is usually performed at 50 to 150 ° C. for about 0.2 to 5 hours. To do. In the present invention, a porous metal oxide semiconductor film to be described later can be formed after drying, but the porous metal oxide semiconductor film may be formed after curing after drying.
乾燥処理のみでも硬化するが、さらに必要に応じて紫外線を照射し、ついで加熱処理によってアニーリングする。
紫外線の照射はペルオキソチタン酸が分解して硬化するに必要な量照射すればよい。
加熱処理は、通常、１００〜５００℃、さらには３００〜４５０℃で概ね１〜４８時間処理する。
Although it hardens | cures only by a drying process, it irradiates with an ultraviolet-ray as needed and then anneals by heat processing.
Irradiation with ultraviolet rays may be performed in an amount necessary to decompose and cure peroxotitanic acid.
The heat treatment is usually performed at 100 to 500 ° C., further at 300 to 450 ° C. for about 1 to 48 hours.
なお、基板が樹脂フィルムである場合の酸化チタン薄膜(1)の形成方法は、１００〜２
００℃、さらには１５０〜１９５℃で概ね１〜７２時間加熱処理すればよい。
多孔質金属酸化物半導体膜
前記電極層(1)上（酸化チタン薄膜(1)が設けられている場合、該薄膜上）に、前記塗料を用いて多孔質金属酸化物半導体膜(1)が形成されている。
In addition, when a board | substrate is a resin film, the formation method of a titanium oxide thin film (1) is 100-2.
What is necessary is just to heat-process at 1 to 72 hours at 00 degreeC and also 150-195 degreeC.
Porous metal oxide semiconductor film A porous metal oxide semiconductor film (1) is formed on the electrode layer (1) (when the titanium oxide thin film (1) is provided, on the thin film) using the paint. Is formed.
この多孔質金属酸化物半導体膜の膜厚は、０．５〜５０μｍの範囲にあることが好ましい。
前記塗料を用いると細孔容積が０．３０〜０．６０ｍｌ／ｇの範囲にある多孔質金属酸化物半導体膜(1)が得られる。
The thickness of the porous metal oxide semiconductor film is preferably in the range of 0.5 to 50 μm.
When the paint is used, a porous metal oxide semiconductor film (1) having a pore volume in the range of 0.30 to 0.60 ml / g can be obtained.
なお、多孔質金属酸化物半導体膜(1)の細孔容積が低いと、電解質の拡散性が低下して
バックカレントを引き起こすことがあり、変換効率が不充分となることがあり、細孔容積が高すぎると多孔質金属酸化物半導体膜の強度が不充分となることがあるが、本発明の塗料を用いると、前記範囲の細孔容積が得られる。
In addition, if the pore volume of the porous metal oxide semiconductor film (1) is low, the diffusibility of the electrolyte may be reduced, causing back current, and conversion efficiency may be insufficient. Is too high, the strength of the porous metal oxide semiconductor film may be insufficient. However, when the coating material of the present invention is used, a pore volume in the above range can be obtained.
細孔容積は、金属酸化物粒子のW/O型なら水分量、O/W型なら有機溶媒の量によって調製可能となる。
前記塗料を用いると、平均細孔径が１０〜５０ｎｍの範囲の範囲にある多孔質金属酸化物半導体膜が得られる。
The pore volume can be adjusted by the amount of water if the W / O type of metal oxide particles is used, and by the amount of organic solvent if it is the O / W type.
When the paint is used, a porous metal oxide semiconductor film having an average pore diameter in the range of 10 to 50 nm can be obtained.
多孔質金属酸化物半導体膜の平均細孔径が小さすぎると、色素の吸着に時間を要したり、色素吸着量が不十分となる場合があり、さらに、電解質の浸透・拡散が不十分となったり、電荷の拡散が阻害されることがあったりする。また、平均細孔径が大きすぎると、膜強度が低下したり、クラックが発生したりする場合がある。本発明の塗料を用いると、前記範囲の細孔径のものが得られる。細孔径は、エマルジョンや金属酸化物粒子の大きさ、膜形成時の加熱温度などによって調製可能となる。 If the average pore size of the porous metal oxide semiconductor film is too small, it may take time to adsorb the dye, the dye adsorption amount may be insufficient, and the electrolyte penetration and diffusion will be insufficient. Or the diffusion of charge may be hindered. On the other hand, if the average pore diameter is too large, the film strength may decrease or cracks may occur. When the paint of the present invention is used, one having a pore diameter in the above range is obtained. The pore diameter can be adjusted depending on the size of the emulsion and metal oxide particles, the heating temperature during film formation, and the like.
このような、多孔質金属酸化物半導体膜形成用塗料を電極層上または必要に応じて設ける酸化チタン薄膜上に塗布し、必要に応じて乾燥し、ついで、１５０〜６００℃、好ましくは３５０〜５００℃で概ね１〜４８時間加熱処理する。形成される多孔質金属酸化物半導体膜の膜厚は、特に制限されないが、効果が顕現できる点で、０．５〜５０μｍの範囲にあることが好ましい。 Such a coating material for forming a porous metal oxide semiconductor film is applied on the electrode layer or a titanium oxide thin film provided as necessary, and dried as necessary, and then 150 to 600 ° C., preferably 350 to Heat treatment is generally performed at 500 ° C. for 1 to 48 hours. The thickness of the formed porous metal oxide semiconductor film is not particularly limited, but is preferably in the range of 0.5 to 50 μm from the viewpoint that the effect can be manifested.
塗布方法はディップ法、スピナー法、ロールコーター法、フレキソ印刷、スクリーンプリント法等が好適である。
乾燥は分散媒を除去できる温度であればよく、従来公知の方法を採用することができ、通常５０〜１５０℃で０．２〜５時間程度乾燥する。
As a coating method, a dip method, a spinner method, a roll coater method, flexographic printing, a screen printing method, and the like are suitable.
The drying may be performed at a temperature at which the dispersion medium can be removed, and a conventionally known method can be adopted.
加熱処理温度が低いと、多孔質金属酸化物半導体膜の硬化が不充分となったり、基材との密着性が不十分となり、剥離を引き起こしたり、光電変換効率が不充分となる場合がある。加熱処理温度が高すぎても、多孔質金属酸化物半導体膜の強度はさらに向上するものの焼結により十分な細孔容積を得ることが困難であったり、基材に使用する導電性材料の導電性が低下したりすることにより、光電変換効率が低下する場合がある。 If the heat treatment temperature is low, curing of the porous metal oxide semiconductor film may be insufficient, adhesion to the substrate may be insufficient, peeling may occur, and photoelectric conversion efficiency may be insufficient. . Even if the heat treatment temperature is too high, although the strength of the porous metal oxide semiconductor film is further improved, it is difficult to obtain a sufficient pore volume by sintering, or the conductivity of the conductive material used for the base material. In some cases, the photoelectric conversion efficiency may decrease due to a decrease in the property.
なお、基材に軟化温度の低い樹脂フィルムを用いた場合、加熱処理温度は２００℃以下（下限は150℃）である。
多孔質金属酸化物半導体膜を電極層上または必要に応じて設ける酸化チタン薄膜上に形成した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を担持した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セルを作成することができる。
光増感材
本発明に係る光電気セルでは、多孔質金属酸化物半導体膜(1)が光増感材を吸着してい
る。光増感材としては、可視光領域、紫外光領域、赤外光領域の光を吸収して励起するものであれば特に制限はなく、たとえば有機色素、金属錯体などを用いることができる。
In addition, when the resin film with a low softening temperature is used for the base material, the heat treatment temperature is 200 ° C. or lower (the lower limit is 150 ° C.).
An electrode formed on the electrode layer or on the titanium oxide thin film provided on the electrode layer as necessary is formed as one electrode, and fluorine doped tin oxide is formed as the other electrode as an electrode, and platinum is formed thereon. The transparent glass substrate carrying the electrode is placed facing each other, the side surfaces are sealed with resin, the electrolyte solution is sealed between the electrodes, and the electrodes are connected with lead wires to create a photoelectric cell. it can.
Photosensitizer In the photoelectric cell according to the present invention, the porous metal oxide semiconductor film (1) adsorbs the photosensitizer. The photosensitizer is not particularly limited as long as it absorbs and excites light in the visible light region, the ultraviolet light region, and the infrared light region, and for example, an organic dye or a metal complex can be used.
有機色素としては、分子中にカルボキシル基、ヒドロキシアルキル基、ヒドロキシル基、スルホン基、カルボキシアルキル基等の官能基を有する従来公知の有機色素が使用できる。 具体的には、メタルフリーフタロシアニン、シアニン系色素、メタロシアニン系色素、トリフェニルメタン系色素およびウラニン、エオシン、ローズベンガル、ローダミンＢ、ジブロムフルオレセイン等のキサンテン系色素等が挙げられる。これらの有機色素は金属酸化物半導体膜への吸着速度が早いという特性を有している。 As the organic dye, a conventionally known organic dye having a functional group such as a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfone group, or a carboxyalkyl group in the molecule can be used. Specific examples include metal-free phthalocyanine, cyanine dyes, methocyanine dyes, triphenylmethane dyes, and xanthene dyes such as uranin, eosin, rose bengal, rhodamine B, and dibromofluorescein. These organic dyes have a characteristic that the adsorption rate to the metal oxide semiconductor film is fast.
また、金属錯体としては、特開平1-220380号公報、特表平5-504023号公報などに記載された銅フタロシアニン、チタニルフタロシアニンなどの金属フタロシアニン、クロロフィル、ヘミン、ルテニウム-トリス(2,2'-ビスピリジル-4,4'-ジカルボキシラート)、シス-(ＳＣＮ-)-ビス(2,2'-ビピリジル-4,4'-ジカルボキシレート)ルテニウム、ルテニウム-シ
ス-ジアクア-ビス(2,2'-ビピリジル-4,4'-ジカルボキシラート)などのルテニウム-シス-
ジアクア-ビピリジル錯体、亜鉛-テトラ(4-カルボキシフェニル)ポルフィンなどのポルフィリン、鉄-ヘキサシアニド錯体等のルテニウム、オスミウム、鉄、亜鉛などの錯体を挙
げることができる。これらの金属錯体は分光増感の効果や耐久性に優れている。
Examples of the metal complex include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine described in JP-A-1-220380 and JP-A-5-504023, chlorophyll, hemin, ruthenium-tris (2,2 ′ -Bispyridyl-4,4′-dicarboxylate), cis- (SCN − ) -bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium, ruthenium-cis-diaqua-bis (2, Ruthenium-cis-, such as 2'-bipyridyl-4,4'-dicarboxylate)
Examples include complexes of ruthenium, osmium, iron, zinc and the like, such as diaqua-bipyridyl complexes, porphyrins such as zinc-tetra (4-carboxyphenyl) porphine, and iron-hexocyanide complexes. These metal complexes are excellent in the effect of spectral sensitization and durability.
上記の光増感材としての有機色素または金属錯体は単独で用いてもよく、有機色素または金属錯体の２種以上を混合して用いてもよく、さらに有機色素と金属錯体とを併用してもよい。 The organic dye or metal complex as the above-mentioned photosensitizer may be used alone, or may be used by mixing two or more kinds of organic dyes or metal complexes. Further, the organic dye and the metal complex are used in combination. Also good.
多孔質金属酸化物半導体膜の光増感材の吸着量は多孔質金属酸化物半導体膜の比表面積１cm2あたり１００μg以上、さらには１５０μg以上であることが好ましい。
多孔質金属酸化物半導体膜の光増感材の吸着量が１００μｇ未満の場合は光電変換効率が不充分となる。
The adsorption amount of the photosensitizer on the porous metal oxide semiconductor film is preferably 100 μg or more, more preferably 150 μg or more per 1 cm 2 of the specific surface area of the porous metal oxide semiconductor film.
When the adsorption amount of the photosensitizer on the porous metal oxide semiconductor film is less than 100 μg, the photoelectric conversion efficiency is insufficient.
このような光増感材の吸着方法は、特に制限はなく、光増感材を溶媒に溶解した溶液を、ディッピング法、スピナー法、スプレー法等の方法により多孔質金属酸化物半導体膜に吸収させ、次いで乾燥する等の一般的な方法が採用できる。さらに必要に応じて前記吸収工程を繰り返してもよい。また、光増感材溶液を加熱環流しながら前記基板と接触させて光増感材を多孔質金属酸化物半導体膜に吸着させることもできる
光増感材を溶解させる溶媒としては、光増感材を溶解するものであればよく、具体的には、水、アルコール類、トルエン、ジメチルホルムアミド、クロロホルム、エチルセルソルブ、Nーメチルピロリドン、テトラヒドロフラン等を用いることができる。
The adsorption method of such a photosensitizer is not particularly limited, and a solution obtained by dissolving the photosensitizer in a solvent is absorbed into the porous metal oxide semiconductor film by a method such as a dipping method, a spinner method, or a spray method. General methods such as drying and then drying can be employed. Furthermore, you may repeat the said absorption process as needed. In addition, the photosensitizer can be adsorbed to the porous metal oxide semiconductor film by bringing the photosensitizer solution into contact with the substrate while heating and refluxing. Any material that dissolves the material may be used. Specifically, water, alcohols, toluene, dimethylformamide, chloroform, ethyl cellosolve, N-methylpyrrolidone, tetrahydrofuran and the like can be used.
光増感材溶液の光増感材の濃度は多孔質金属酸化物半導体膜の比表面積１ｃｍ2あたり
１００μｇ以上、さらには２００μｇ以上となる濃度が好ましい。
本発明では、前記した表面に電極層(1)を有し、該電極層(1)上に必用に応じて酸化チタン薄膜(1)を有し、かつ電極層(1)上または酸化チタン薄膜(1)上に光増感材を吸着した多
孔質金属酸化物半導体膜を有する基板(1)と、表面に電極層(2)を有する基板(2)とを、電
極層(1)および電極層(2)が対向するように配置し、側面を樹脂にてシールし、多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質を封入し、さらに電極間をリード線で接続することによって光電気セルを製造することができる。
The concentration of the photosensitizer in the photosensitizer solution is preferably 100 μg or more, more preferably 200 μg or more per 1 cm 2 of the specific surface area of the porous metal oxide semiconductor film.
In the present invention, the electrode layer (1) is provided on the surface described above, the titanium oxide thin film (1) is optionally provided on the electrode layer (1), and the electrode layer (1) or the titanium oxide thin film is provided. (1) A substrate (1) having a porous metal oxide semiconductor film on which a photosensitizer is adsorbed and a substrate (2) having an electrode layer (2) on the surface, the electrode layer (1) and the electrode Arrange the layers (2) so that they face each other, seal the sides with resin, enclose the electrolyte between the porous metal oxide semiconductor film (1) and the electrode layer (2), and lead between the electrodes Photoelectric cells can be manufactured by connecting with wires.
電解質層
電解質としては、電気化学的に活性な塩とともに酸化還元系を形成する少なくとも１種の化合物との混合物が使用される。
The electrolyte layer electrolyte, a mixture of at least one compound forming a redox system is used in conjunction with electrochemically active salt.
電気化学的に活性な塩としては、テトラプロピルアンモニウムアイオダイドなどの４級アンモニウム塩が挙げられる。酸化還元系を形成する化合物としては、キノン、ヒドロキノン、沃素（Ｉ-／Ｉ- 3）、沃化カリウム、臭素（Ｂr-／Ｂr- 3）、臭化カリウム等が挙げられる。場合によってはこれらを混合して使用することもできる。 Examples of the electrochemically active salt include quaternary ammonium salts such as tetrapropylammonium iodide. Examples of the compound forming the redox system, quinone, hydroquinone, iodine (I - / I - 3) , potassium iodide, bromine (Br - / Br - 3) , potassium bromide, and the like. In some cases, these may be used in combination.
このような電解質の使用量は、電解質の種類、後述する溶媒の種類によっても異なるが、概ね０.１〜５モル／リットルの範囲にあることが好ましい。
電解質層には、従来公知の溶媒を用いることができる。具体的には水、アルコール類、オリゴエーテル類、プロピオンカーボネート等のカーボネート類、燐酸エステル類、ジメチルホルムアミド、ジメチルスルホキシド、N-メチルピロリドン、N-ビニルピロリドン、スルホラン６６の硫黄化合物、炭酸エチレン、アセトニトリル、γ−ブチロラクトン等が挙げられる。
The amount of the electrolyte used is preferably approximately in the range of 0.1 to 5 mol / liter, although it varies depending on the type of electrolyte and the type of solvent described later.
A conventionally well-known solvent can be used for an electrolyte layer. Specifically, water, alcohols, oligoethers, carbonates such as propionate carbonate, phosphate esters, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, sulfolane 66 sulfur compound, ethylene carbonate, acetonitrile , Γ-butyrolactone and the like.
多孔質金属酸化物半導体膜を電極層上または必要に応じて設ける酸化チタン薄膜上に形成した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を担持した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セルを作成することができる。 An electrode formed on a titanium oxide thin film provided with a porous metal oxide semiconductor film on an electrode layer or as necessary is formed as one electrode, and fluorine doped tin oxide is formed as an electrode as the other electrode, and platinum is formed thereon. The transparent glass substrate carrying the electrode is placed facing each other, the side surfaces are sealed with resin, the electrolyte solution is sealed between the electrodes, and the electrodes are connected with lead wires to create a photoelectric cell. it can.
［実施例］
以下、本発明を実施例により説明するが、本発明はこれらに実施例により限定されるものではない。
［実施例１］
多孔質金属酸化物半導体膜形成用塗料(1)の調製
有機溶媒としてテルピネオールを５０ｇに界面活性剤（シグマ-アルドリッチ製：Ｔｏ
ｒｉｔｏｎ−Ｘ １００）２５ｇを溶解し、この混合溶液に水２５ｇを混合し、エマルジョン溶液(1)を得た。この時のエマルジョンの大きさを表に示す。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to an Example by these.
[Example 1]
Preparation of Porous Metal Oxide Semiconductor Film Forming Paint (1) 50 g of terpineol as an organic solvent, surfactant (manufactured by Sigma-Aldrich: To
25 g of Riton-X 100) was dissolved, and 25 g of water was mixed with this mixed solution to obtain an emulsion solution (1). The size of the emulsion at this time is shown in the table.
酸化チタンゾル（日揮触媒化成（株）製：ＨＰＷ−１８ＮＲ、平均粒子径２０ｎｍ、ＴiＯ2濃度２０重量％、分散媒：水）１００ｇに、エタノール２００ｍｌ加えてよく攪拌した後、エチルセルロース８ｇを１０重量％濃度となるようにエタノールで溶解した溶液を加えよく混合し、ついで、スクリーン印刷用の溶媒としてテルピネオールを７２ｇ加えてよく混合し後、５０℃に加温しながらロータリーエバポレータにて水およびアルコールを除去しながらＴiＯ2濃度２０重量％となるように濃縮した。その後、エマルジョン溶液(1)を１５ｇ加え、ロールミルで３０ｍｉｎ混合を行い、多孔質金属酸化物半導体膜形成用
塗料(1)を得た。
200 g of ethanol was added to 100 g of titanium oxide sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-18NR, average particle size 20 nm, TiO 2 concentration 20 wt%, dispersion medium: water) and stirred well, and then 8 g of ethyl cellulose 10 wt% Add a solution dissolved in ethanol to a concentration, mix well, then add 72 g of terpineol as a solvent for screen printing, mix well, then remove water and alcohol with a rotary evaporator while heating to 50 ° C. While concentrating, the TiO 2 concentration was 20% by weight. Thereafter, 15 g of the emulsion solution (1) was added and mixed for 30 minutes by a roll mill to obtain a coating material (1) for forming a porous metal oxide semiconductor film.
ペルオキシチタン酸コーティング液の調製
１８．３ｇの４塩化チタンを純水で希釈してＴｉＯ2として１．０重量％含有する水溶
液を得た。これを撹拌しながら、濃度１５重量％のアンモニア水を添加し、ｐＨ９．５の白色スラリーを得た。このスラリーを濾過洗浄し、ＴｉＯ2として濃度１０．２重量％の
水和酸化チタンゲルのケーキを得た。このケーキと濃度５％過酸化水素液４００ｇを混合し、ついで８０℃で２時間加熱して溶解し、ＴｉＯ2として濃度１．０重量％のペルオキ
ソチタン酸水溶液(1)を得た。さらに、ＴｉＯ2濃度０．５％、エチレングリコール濃度２０％となるように水およびペルオキソチタン酸水溶液にエチレングリコールを加えペルオキソチタン酸コーティング液を得た。
Preparation of Peroxytitanic Acid Coating Solution 18.3 g of titanium tetrachloride was diluted with pure water to obtain an aqueous solution containing 1.0% by weight as TiO 2 . While stirring this, ammonia water having a concentration of 15% by weight was added to obtain a white slurry having a pH of 9.5. This slurry was washed by filtration to obtain a hydrated titanium oxide gel cake having a concentration of 10.2% by weight as TiO 2 . This cake was mixed with 400 g of a 5% hydrogen peroxide solution and dissolved by heating at 80 ° C. for 2 hours to obtain a 1.0 wt% aqueous peroxotitanic acid solution (1) as TiO 2 . Further, ethylene glycol was added to water and a peroxotitanic acid aqueous solution so that the TiO 2 concentration was 0.5% and the ethylene glycol concentration was 20% to obtain a peroxotitanic acid coating solution.
酸化チタン薄膜(1)の形成
ペルオキソチタン酸コーティング溶液(1)をフッ素ドープした酸化スズを電極として形
成した透明ガラス基板にフレキソ印刷法で塗布し、自然乾燥し、引き続き低圧水銀ランプを用いて６０００ｍＪ／ｃｍ2の紫外線を照射してペルオキソ酸を分解させ、膜を硬化さ
せた。さらに、４５０℃で３０分間加熱して硬化およびアニーリングを行って酸化チタン薄膜(1)を形成した。
Formation of Titanium Oxide Thin Film (1) A peroxotitanic acid coating solution (1) was coated on a transparent glass substrate formed with fluorine-doped tin oxide as an electrode by flexographic printing, dried naturally, and then 6000 mJ using a low-pressure mercury lamp. The film was cured by irradiating UV light of / cm 2 to decompose the peroxoacid. Furthermore, the titanium oxide thin film (1) was formed by heating and curing at 450 ° C. for 30 minutes for curing and annealing.
得られた酸化チタン薄膜(1)の膜厚は４０ｎｍ、窒素吸着法によって求めた細孔容積は
０．１２ｍｌ／ｇ、平均細孔径は２ｎｍであった。
多孔質金属酸化物半導体膜(1)の形成
酸化チタン薄膜(1)を形成した透明ガラス基板上に多孔質金属酸化物半導体膜形成用塗
料(1)をスクリーン印刷および乾燥を膜厚が１５μｍになるまで繰り返し形成し、その後
４５０℃での焼成アニーリングを行って多孔質金属酸化物半導体膜(1)を形成した。
The obtained titanium oxide thin film (1) had a thickness of 40 nm, a pore volume determined by a nitrogen adsorption method of 0.12 ml / g, and an average pore diameter of 2 nm.
Formation of porous metal oxide semiconductor film (1) On the transparent glass substrate on which the titanium oxide thin film (1) is formed, the porous metal oxide semiconductor film forming paint (1) is screen-printed and dried to a film thickness of 15 μm. Then, the porous metal oxide semiconductor film (1) was formed by repeatedly forming the film and then performing baking annealing at 450 ° C.
得られた多孔質金属酸化物半導体膜(1)の膜厚および窒素吸着法によって求めた細孔容
積と平均細孔径を表に示した。また、多孔質金属酸化物半導体膜(1)の密着性を評価し、
結果を表１に示した。
The film thickness of the obtained porous metal oxide semiconductor film (1) and the pore volume and average pore diameter determined by the nitrogen adsorption method are shown in the table. Also, evaluate the adhesion of the porous metal oxide semiconductor film (1),
The results are shown in Table 1.
密着性
多孔質金属酸化物半導体膜(1)の表面にナイフで縦横１ｍｍの間隔で１１本の平行な傷
を付け１００個の升目を作り、これにセロハンテ−プを接着し、ついで、セロハンテ−プを剥離したときに被膜が剥離せず残存している升目の数を、以下の４段階に分類することにより密着性を評価した。結果を表に示す。
The surface of the adhesive porous metal oxide semiconductor film (1) is made with 11 parallel scratches with a knife at intervals of 1 mm in length and width to make 100 squares, and a cellophane tape is bonded to this, and then the cellophane tape is attached. Adhesiveness was evaluated by classifying the number of squares remaining without peeling of the film when the film was peeled into the following four stages. The results are shown in the table.
残存升目の数１００個 ：◎
残存升目の数９０〜９９個 ：○
残存升目の数８５〜８９個 ：△
残存升目の数８４個以下 ：×
光増感材の吸着
光増感材としてＤＹＥＳＯＬ社製Ｂ２色素を濃度０．１％となるようにエタノール溶液を調製した。この溶液に多孔質金属酸化物半導体膜(1)を形成したガラスを５時間漬込み
、取り出した後エタノール水溶液で洗浄し、色素を吸着させた。光増感材の吸着量を表に示した。
Number of remaining squares: ◎
Number of remaining squares 90-99: ○
Number of remaining squares: 85 to 89: Δ
Number of remaining squares: 84 or less: ×
As an adsorption photosensitizer for the photosensitizer, an ethanol solution was prepared so that the concentration of B2 dye manufactured by DYESOL was 0.1%. The glass on which the porous metal oxide semiconductor film (1) was formed was immersed in this solution for 5 hours, taken out, washed with an aqueous ethanol solution, and the dye was adsorbed. The adsorption amount of the photosensitizer is shown in the table.
光電気セル(1)の作成
先ず、溶媒としてアセトニトリルと炭酸エチレンの体積比が１：４の比で混合した溶媒にテトラプロピルアンモニウムアイオダイドとヨウ素とを、それぞれの濃度が０.４６モ
ル／Ｌ、０.０６モル／Ｌとなるように溶解して電解質溶液を調製した。
Preparation of Photoelectric Cell (1) First, tetrapropylammonium iodide and iodine are mixed in a solvent in which acetonitrile and ethylene carbonate are mixed at a volume ratio of 1: 4, and each concentration is 0.46 mol / L. An electrolyte solution was prepared by dissolving to 0.06 mol / L.
前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を担持した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(1)を作成した。 The electrode prepared above is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode. The transparent glass substrate carrying platinum is placed on the opposite side, and the sides are sealed with resin. Then, the above-described electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (1).
光電気セル(1)は、ソーラーシュミレーターで１００Ｗ／ｍ2の強度の光を入射角９０°（セル面と９０°）で照射して、Ｖｏｃ（開回路状態の電圧）、Ｊｏｃ（回路を短絡したときに流れる電流の密度）、ＦＦ（曲線因子）およびη（変換効率）を測定し結果を表１に示した。
［実施例２］
多孔質金属酸化物半導体膜形成用塗料(2)の調製
有機溶媒としてテルピネオールを５０ｇに界面活性剤（シグマ-アルドリッチ製：Ｔｏ
ｒｉｔｏｎ−Ｘ １００）３５ｇを溶解し、この混合溶液に水１５ｇを混合し、エマルジ
ョン溶液(２)を得た。この時のエマルジョンの大きさを表に示す。
Photoelectric cell (1) is a solar simulator that irradiates light with an intensity of 100 W / m 2 at an incident angle of 90 ° (90 ° with the cell surface), Voc (voltage in open circuit state), Joc (short circuit) Table 1 shows the results of measurement of the density of the current that flows when the test was performed, FF (fill factor) and η (conversion efficiency).
[Example 2]
Preparation of paint for forming porous metal oxide semiconductor film (2) Terpineol as an organic solvent was added to 50 g of a surfactant (manufactured by Sigma-Aldrich: To
(riton-X 100) (35 g) was dissolved, and 15 g of water was mixed with this mixed solution to obtain an emulsion solution (2). The size of the emulsion at this time is shown in the table.
酸化チタンゾル（日揮触媒化成（株）製：ＨＰＷ−１８ＮＲ、平均粒子径２０ｎｍ、ＴiＯ2濃度２０重量％、分散媒：水）１００ｇに、エタノール２００ｍｌ加えてよく攪拌した後、エチルセルロース８ｇを１０重量％濃度となるようにエタノールで溶解した溶液を加えよく混合し、ついで、スクリーン印刷用の溶媒としてテルピネオールを７６ｇ加えてよく混合し後、５０℃に加温しながらロータリーエバポレータにて水およびアルコールを除去しながらＴiＯ2濃度２０重量％となるように濃縮した。その後、エマルジョン溶液(2)を１０ｇ加え、ロールミルで３０ｍｉｎ混合を行い、多孔質金属酸化物半導体膜形成用
塗料(2)を得た。
200 g of ethanol was added to 100 g of titanium oxide sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-18NR, average particle size 20 nm, TiO 2 concentration 20 wt%, dispersion medium: water) and stirred well, and then 8 g of ethyl cellulose 10 wt% Add a solution dissolved in ethanol to a concentration, mix well, then add 76 g of terpineol as a solvent for screen printing, mix well, and then remove water and alcohol with a rotary evaporator while heating to 50 ° C. While concentrating, the TiO 2 concentration was 20% by weight. Thereafter, 10 g of the emulsion solution (2) was added and mixed for 30 minutes with a roll mill to obtain a coating material (2) for forming a porous metal oxide semiconductor film.
多孔質金属酸化物半導体膜(2)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(2)を用いた以外は同様にし
て多孔質金属酸化物半導体膜(2)を形成した。
Formation of porous metal oxide semiconductor film (2) In Example 1, the porous metal oxide semiconductor film (2) was formed in the same manner except that the paint (2) for forming a porous metal oxide semiconductor film was used. did.
得られた多孔質金属酸化物半導体膜(2)の膜厚、細孔容積、平均細孔径および密着性を
評価し、結果を表１に示した。
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(２)を形成した透明ガラス基板を用いた以外は同様にして色素を吸着させた。
The film thickness, pore volume, average pore diameter and adhesion of the obtained porous metal oxide semiconductor film (2) were evaluated, and the results are shown in Table 1.
Adsorption of photosensitizer The dye was adsorbed in the same manner as in Example 1 except that the transparent glass substrate on which the porous metal oxide semiconductor film (2) was formed was used.
光電気セル(2)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(2)を用いた以外は同
様にして光電気セル(2)を作成した。
Production of Photoelectric Cell (2) A photoelectric cell (2) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (2) adsorbed with the dye was used.
光電気セル(2)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した
。
［実施例３］
多孔質金属酸化物半導体膜形成用塗料(3)の調製
酸化チタンゾル（日揮触媒化成（株）製：ＨＰＷ−１８ＮＲ、平均粒子径２０ｎｍ、ＴiＯ2濃度２０重量％、分散媒：水）１００ｇに、エタノール２００ｍｌ加えてよく攪拌した後、エチルセルロース８ｇを１０重量％濃度となるようにエタノールで溶解した溶液を加えよく混合し、ついで、スクリーン印刷用の溶媒としてテルピネオールを６７ｇ加えてよく混合し後、５０℃に加温しながらロータリーエバポレータにて水およびアルコールを除去しながらＴiＯ2濃度２０重量％となるように濃縮した。その後、実施例１で調製したエマルジョン溶液(1)を２０ｇ加え、ロールミルで３０ｍｉｎ混合を行い、多孔質金属酸
化物半導体膜形成用塗料(3)を得た。
With respect to the photoelectric cell (2), Voc, Joc, FF and η were measured, and the results are shown in Table 1.
[Example 3]
Preparation of paint for forming porous metal oxide semiconductor film (3 ) To 100 g of titanium oxide sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-18NR, average particle diameter 20 nm, TiO 2 concentration 20 wt%, dispersion medium: water) After adding 200 ml of ethanol and stirring well, a solution prepared by dissolving 8 g of ethylcellulose in ethanol to a concentration of 10% by weight was added and mixed well. Then, 67 g of terpineol was added as a solvent for screen printing and mixed well. The mixture was concentrated to a TiO 2 concentration of 20% by weight while removing water and alcohol with a rotary evaporator while heating at 0 ° C. Thereafter, 20 g of the emulsion solution (1) prepared in Example 1 was added and mixed for 30 minutes with a roll mill to obtain a porous metal oxide semiconductor film-forming coating material (3).
多孔質金属酸化物半導体膜(3)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(3)を用いた以外は同様にし
て多孔質金属酸化物半導体膜(3)を形成した。得られた多孔質金属酸化物半導体膜(3)の膜厚、細孔容積、平均細孔径および密着性を評価し、結果を表１に示した。
Formation of porous metal oxide semiconductor film (3) In Example 1, the porous metal oxide semiconductor film (3) was formed in the same manner except that the paint (3) for forming a porous metal oxide semiconductor film was used. did. The film thickness, pore volume, average pore diameter and adhesion of the obtained porous metal oxide semiconductor film (3) were evaluated, and the results are shown in Table 1.
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(3)を形成した透明ガラス基板を用いた
以外は同様にして色素を吸着させた。
Adsorption of photosensitizer The dye was adsorbed in the same manner as in Example 1 except that the transparent glass substrate on which the porous metal oxide semiconductor film (3) was formed was used.
光電気セル(3)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(3)を用いた以外は同
様にして光電気セル(3)を作成した。
Production of Photoelectric Cell (3) A photoelectric cell (3) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (3) adsorbed with the dye was used.
光電気セル(3)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した
。
［実施例４］
多孔質金属酸化物半導体膜形成用塗料(4)の調製
水５０ｇに界面活性剤（シグマ-アルドリッチ製：Ｔｏｒｉｔｏｎ−Ｘ １００）２５
ｇを溶解し、この混合溶液に、有機溶剤としてｎ-ブタノールを２５ｇ加え攪拌しエマル
ジョン溶液(4)を得た。
With respect to the photoelectric cell (3), Voc, Joc, FF and η were measured, and the results are shown in Table 1.
[Example 4]
Preparation of Porous Metal Oxide Semiconductor Film Forming Coating Material (4) 50 g of water and a surfactant (Sigma-Aldrich: Toriton-X 100) 25
Then, 25 g of n-butanol as an organic solvent was added to this mixed solution and stirred to obtain an emulsion solution (4).
酸化チタンゾル（日揮触媒化成（株）製：ＨＰＷ−１８ＮＲ、平均粒子径２０ｎｍ、ＴiＯ2濃度２０重量％、分散媒：水）１００ｇに、１０％濃度のポリエチレングリコール水溶液８ｇを加えよく混合した後、エマルジョン溶液(4)を２０ｇ加え、自公転式ミキサー
で１５ｍｉｎ混合を行い、多孔質金属酸化物半導体膜形成用塗料(4)を得た。
To 100 g of titanium oxide sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-18NR, average particle size 20 nm, TiO 2 concentration 20% by weight, dispersion medium: water) was added 8 g of 10% aqueous polyethylene glycol solution and mixed well. 20 g of the emulsion solution (4) was added and mixed for 15 minutes with a self-revolving mixer to obtain a porous metal oxide semiconductor film-forming coating material (4).
多孔質金属酸化物半導体膜(4)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(4)を用いた以外は同様にし
て多孔質金属酸化物半導体膜(4)を形成した。得られた多孔質金属酸化物半導体膜(4)の膜厚、細孔容積、平均細孔径および密着性を評価し、結果を表１に示した。
Formation of porous metal oxide semiconductor film (4) The porous metal oxide semiconductor film (4) was formed in the same manner as in Example 1 except that the paint (4) for forming a porous metal oxide semiconductor film was used. did. The film thickness, pore volume, average pore diameter and adhesion of the obtained porous metal oxide semiconductor film (4) were evaluated, and the results are shown in Table 1.
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(4)を形成した透明ガラス基板を用いた
以外は同様にして色素を吸着させた。
Adsorption of photosensitizer The dye was adsorbed in the same manner as in Example 1 except that the transparent glass substrate on which the porous metal oxide semiconductor film (4) was formed was used.
光電気セル(4)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(4)を用いた以外は同
様にして光電気セル(4)を作成した。
Production of Photoelectric Cell (4) A photoelectric cell (4) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (4) adsorbed with the dye was used.
光電気セル(4)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した
。
［実施例５］
多孔質金属酸化物半導体膜形成用塗料(5)の調製
水５０ｇに界面活性剤（シグマ-アルドリッチ製：Ｔｏｒｉｔｏｎ−Ｘ １００）３５
ｇを溶解し、この混合溶液に、有機溶剤としてｎ-ブタノールを２５ｇ加え攪拌しエマル
ジョン溶液(5)を得た。
With respect to the photoelectric cell (4), Voc, Joc, FF and η were measured and the results are shown in Table 1.
[Example 5]
Preparation of Porous Metal Oxide Semiconductor Film Forming Paint (5) Surfactant (Sigma-Aldrich: Toriton-X 100) 35 in 50 g of water
Then, 25 g of n-butanol as an organic solvent was added to the mixed solution and stirred to obtain an emulsion solution (5).
酸化チタンゾル（日揮触媒化成（株）製：ＨＰＷ−１８ＮＲ、平均粒子径２０ｎｍ、ＴiＯ2濃度２０重量％、分散媒：水）１００ｇに、１０％濃度のポリエチレングリコール水溶液８ｇを加えよく混合した後、エマルジョン溶液(5)を３０ｇ加え、自公転式ミキサー
で１５ｍｉｎ混合を行い、多孔質金属酸化物半導体膜形成用塗料(5)を得た。
To 100 g of titanium oxide sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-18NR, average particle size 20 nm, TiO 2 concentration 20% by weight, dispersion medium: water) was added 8 g of 10% aqueous polyethylene glycol solution and mixed well. 30 g of the emulsion solution (5) was added, and the mixture was mixed for 15 min with a self-revolving mixer to obtain a coating material (5) for forming a porous metal oxide semiconductor film.
多孔質金属酸化物半導体膜(5)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(5)を用いた以外は同様にし
て多孔質金属酸化物半導体膜(5)を形成した。
Formation of porous metal oxide semiconductor film (5) In Example 1, the porous metal oxide semiconductor film (5) was formed in the same manner except that the paint (5) for forming a porous metal oxide semiconductor film was used. did.
得られた多孔質金属酸化物半導体膜(5)の膜厚、細孔容積、平均細孔径および密着性を
評価し、結果を表１に示した。
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(5)を形成した透明ガラス基板を用いた
以外は同様にして色素を吸着させた。
The film thickness, pore volume, average pore diameter and adhesion of the obtained porous metal oxide semiconductor film (5) were evaluated, and the results are shown in Table 1.
Adsorption of photosensitizer In Example 1, a dye was adsorbed in the same manner except that a transparent glass substrate on which a porous metal oxide semiconductor film (5) was formed was used.
光電気セル(5)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(5)を用いた以外は同
様にして光電気セル(5)を作成した。
Production of Photoelectric Cell (5) A photoelectric cell (5) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (5) adsorbed with the dye was used.
光電気セル(5)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した
。
［実施例６］
多孔質金属酸化物半導体膜形成用塗料(6)の調製
水５０ｇに界面活性剤（シグマ-アルドリッチ製：Ｔｏｒｉｔｏｎ−Ｘ １００）２５
ｇを溶解し、この混合溶液に、有機溶剤としてｎ-ブタノールを２５ｇ加え攪拌しエマル
ジョン溶液(6)を得た。
With respect to the photoelectric cell (5), Voc, Joc, FF and η were measured, and the results are shown in Table 1.
[Example 6]
Preparation of Porous Metal Oxide Semiconductor Film Forming Paint (6) 50 g of water and surfactant (Sigma-Aldrich: Toriton-X 100) 25
Then, 25 g of n-butanol as an organic solvent was added to the mixed solution and stirred to obtain an emulsion solution (6).
酸化チタンゾル（日揮触媒化成（株）製：ＨＰＷ−１８ＮＲ、平均粒子径２０ｎｍ、ＴiＯ2濃度２０重量％、分散媒：水）１００ｇに、１０％濃度のポリエチレングリコール水溶液８ｇを加えよく混合した後、エマルジョン溶液(6)を３０ｇ加え、自公転式ミキサー
で１５ｍｉｎ混合を行い、多孔質金属酸化物半導体膜形成用塗料(6)を得た。
To 100 g of titanium oxide sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-18NR, average particle size 20 nm, TiO 2 concentration 20% by weight, dispersion medium: water) was added 8 g of 10% aqueous polyethylene glycol solution and mixed well. 30 g of the emulsion solution (6) was added and mixed for 15 minutes with a self-revolving mixer to obtain a porous metal oxide semiconductor film-forming coating material (6).
多孔質金属酸化物半導体膜(6)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(6)を用いた以外は同様にし
て多孔質金属酸化物半導体膜(6)を形成した。
Formation of porous metal oxide semiconductor film (6) In Example 1, the porous metal oxide semiconductor film (6) was formed in the same manner except that the paint (6) for forming a porous metal oxide semiconductor film was used. did.
得られた多孔質金属酸化物半導体膜(6)の膜厚、細孔容積、平均細孔径および密着性を
評価し、結果を表１に示した。
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(6)を形成した透明ガラス基板を用いた
以外は同様にして色素を吸着させた。
The film thickness, pore volume, average pore diameter and adhesion of the obtained porous metal oxide semiconductor film (6) were evaluated, and the results are shown in Table 1.
Adsorption of photosensitizer In Example 1, a dye was adsorbed in the same manner except that a transparent glass substrate on which a porous metal oxide semiconductor film (6) was formed was used.
光電気セル(6)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(6)を用いた以外は同
様にして光電気セル(6)を作成した。
Production of Photoelectric Cell (6) A photoelectric cell (6) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (6) adsorbed with the dye was used.
光電気セル(6)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した
。
［実施例７］
多孔質金属酸化物半導体膜形成用塗料(7)の調製
実施例１において、酸化チタンゾルを日揮触媒化成（株）製：ＨＰＷ−３０ＮＲＤ（平均粒子径３０ｎｍ、ＴiＯ2濃度２０重量％、分散媒：水）を用いた以外は同様にして調製した。
With respect to the photoelectric cell (6), Voc, Joc, FF and η were measured and the results are shown in Table 1.
[Example 7]
Preparation of Porous Metal Oxide Semiconductor Film Forming Paint (7) In Example 1, titanium oxide sol was manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-30NRD (average particle size 30 nm, TiO 2 concentration 20% by weight, dispersion medium: It was prepared in the same manner except that (water) was used.
多孔質金属酸化物半導体膜(7)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(7)を用いた以外は同様にし
て多孔質金属酸化物半導体膜(7)を形成した。
Formation of porous metal oxide semiconductor film (7) In Example 1, the porous metal oxide semiconductor film (7) was formed in the same manner except that the paint (7) for forming a porous metal oxide semiconductor film was used. did.
得られた多孔質金属酸化物半導体膜(7)の膜厚、細孔容積、平均細孔径および密着性を
評価し、結果を表１に示した。
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(7)を形成した透明ガラス基板を用いた
以外は同様にして色素を吸着させた。
The film thickness, pore volume, average pore diameter and adhesion of the obtained porous metal oxide semiconductor film (7) were evaluated, and the results are shown in Table 1.
Adsorption of photosensitizer In Example 1, a dye was adsorbed in the same manner except that a transparent glass substrate on which a porous metal oxide semiconductor film (7) was formed was used.
光電気セル(7)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(7)を用いた以外は同
様にして光電気セル(7)を作成した。
Production of Photoelectric Cell (7) A photoelectric cell (7) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (7) adsorbed with the dye was used.
光電気セル(7)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した
。
［比較例１］
多孔質金属酸化物半導体膜形成用塗料(R1)の調製
実施例1において、エマルジョン溶液(1)を添加せずに、テルピネオールを用いてＴｉＯ2濃度１７．４％となるように調整し、多孔質金属酸化物半導体膜形成用塗料(R1)を調製
した。
With respect to the photoelectric cell (7), Voc, Joc, FF and η were measured and the results are shown in Table 1.
[Comparative Example 1]
Preparation of Porous Metal Oxide Semiconductor Film Forming Paint (R1) In Example 1, the TiO 2 concentration was adjusted to 17.4% using terpineol without adding the emulsion solution (1), A paint (R1) for forming a porous metal oxide semiconductor film was prepared.
多孔質金属酸化物半導体膜(R1)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(R1)を用いた以外は同様にして多孔質金属酸化物半導体膜(R1)を形成した。
Formation of porous metal oxide semiconductor film (R1) In Example 1, the porous metal oxide semiconductor film (R1) was formed in the same manner except that the coating material (R1) for forming the porous metal oxide semiconductor film was used. did.
得られた多孔質金属酸化物半導体膜(R1)の膜厚、細孔容積、平均細孔径および密着性を評価し、結果を表１に示した。
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(R1)を形成した透明ガラス基板を用いた以外は同様にして色素を吸着させた。
The film thickness, pore volume, average pore diameter and adhesion of the obtained porous metal oxide semiconductor film (R1) were evaluated, and the results are shown in Table 1.
Adsorption of photosensitizer In Example 1, a dye was adsorbed in the same manner except that a transparent glass substrate on which a porous metal oxide semiconductor film (R1) was formed was used.
光電気セル(R1)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(R1)を用いた以外は同様にして光電気セル(R1)を作成した。
Production of Photoelectric Cell (R1) A photoelectric cell (R1) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (R1) adsorbed with the dye was used.
光電気セル(R1)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した。
［比較例２］
多孔質金属酸化物半導体膜形成用塗料(R2)の調製
実施例７において、エマルジョン溶液(1)を添加せずに、テルピネオールを用いてＴｉ
Ｏ2濃度１７．４％となるように調整し、多孔質金属酸化物半導体膜形成用塗料(R2)を調
製した。
With respect to the photoelectric cell (R1), Voc, Joc, FF and η were measured and the results are shown in Table 1.
[Comparative Example 2]
Preparation of Porous Metal Oxide Semiconductor Film Coating Material (R2) In Example 7, using terpineol without adding the emulsion solution (1), Ti
The O 2 concentration was adjusted to 17.4% to prepare a porous metal oxide semiconductor film-forming coating material (R2).
多孔質金属酸化物半導体膜(R2)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(R2)を用いた以外は同様にして多孔質金属酸化物半導体膜(R2)を形成した。
Formation of porous metal oxide semiconductor film (R2) In Example 1, the porous metal oxide semiconductor film (R2) was formed in the same manner except that the coating material (R2) for forming the porous metal oxide semiconductor film was used. did.
得られた多孔質金属酸化物半導体膜(R2)の膜厚、細孔容積、平均細孔径および密着性を評価し、結果を表１に示した。
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(R2)を形成した透明ガラス基板を用いた以外は同様にして色素を吸着させた。
The film thickness, pore volume, average pore diameter, and adhesion of the obtained porous metal oxide semiconductor film (R2) were evaluated, and the results are shown in Table 1.
Adsorption of photosensitizer The dye was adsorbed in the same manner as in Example 1 except that a transparent glass substrate on which a porous metal oxide semiconductor film (R2) was formed was used.
光電気セル(R2)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(R2)を用いた以外は同様にして光電気セル(R2)を作成した。
Production of Photoelectric Cell (R2) A photoelectric cell (R2) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (R2) adsorbed with the dye was used.
光電気セル(R2)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した。
［比較例３］
多孔質金属酸化物半導体膜形成用塗料(R3)の調製
実施例１において、金属酸化物微粒子として酸化チタンゾル（日揮触媒化成（株）製：ＨＰＷ―４００Ｃ、平均粒子径４００ｎｍ、ＴiＯ2濃度２０重量％、分散媒：水）を用いた以外は同様にして多孔質金属酸化物半導体膜形成用塗料(R3)を調製した。
With respect to the photoelectric cell (R2), Voc, Joc, FF and η were measured and the results are shown in Table 1.
[Comparative Example 3]
Preparation of paint for forming porous metal oxide semiconductor film (R3) In Example 1, titanium oxide sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-400C, average particle diameter of 400 nm, TiO 2 concentration of 20 wt. %, Dispersion medium: water) was used in the same manner to prepare a porous metal oxide semiconductor film-forming coating material (R3).
多孔質金属酸化物半導体膜(R3)の形成
実施例１において、多孔質金属酸化物半導体膜形成用塗料(R3)を用いた以外は同様にして多孔質金属酸化物半導体膜(R3)を形成した。
Formation of porous metal oxide semiconductor film (R3) In Example 1, the porous metal oxide semiconductor film (R3) was formed in the same manner except that the coating material (R3) for forming the porous metal oxide semiconductor film was used. did.
得られた多孔質金属酸化物半導体膜(R3)の膜厚、細孔容積、平均細孔径および密着性を評価し、結果を表１に示した。
光増感材の吸着
実施例１において、多孔質金属酸化物半導体膜(R3)を形成した透明ガラス基板を用いた以外は同様にして色素を吸着させた。
The film thickness, pore volume, average pore diameter and adhesion of the obtained porous metal oxide semiconductor film (R3) were evaluated, and the results are shown in Table 1.
Adsorption of photosensitizer The dye was adsorbed in the same manner as in Example 1 except that a transparent glass substrate on which a porous metal oxide semiconductor film (R3) was formed was used.
光電気セル(R3)の作成
実施例１において、色素を吸着させた多孔質金属酸化物半導体膜(R3)を用いた以外は同様にして光電気セル(R3)を作成した。
Production of Photoelectric Cell (R3) A photoelectric cell (R3) was produced in the same manner as in Example 1 except that the porous metal oxide semiconductor film (R3) adsorbed with the dye was used.
光電気セル(R3)について、Ｖｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示した。 With respect to the photoelectric cell (R3), Voc, Joc, FF and η were measured and the results are shown in Table 1.
１・・・・・電極層(1)
２・・・・・半導体膜(1)
３・・・・・電極層(2)
４・・・・・電解質層(2)
５・・・・・基板(1)
６・・・・・基板(2)
７・・・・・酸化チタン薄膜
1. Electrode layer (1)
2 ... Semiconductor film (1)
3. Electrode layer (2)
4 ... Electrolyte layer (2)
5 ... Board (1)
6 ... Board (2)
7. Titanium oxide thin film
Claims (11)
該混合溶媒がエマルジョンを形成していることを特徴とする多孔質金属酸化物半導体膜形成用塗料。 Consisting of metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm, and a mixed solvent of water and an organic solvent,
A paint for forming a porous metal oxide semiconductor film, wherein the mixed solvent forms an emulsion.
表面に電極層(2)を有する基板(2)とが、
前記電極層(1)および電極層(2)が対向するように配置してなり、
多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質層を設けてなる光電気セルにおいて、
多孔質金属酸化物半導体膜(1)が、請求項１〜７のいずれかに記載の多孔質金属酸化物
半導体膜形成用塗料を用いて形成されてなることを特徴とする光電気セル。 A substrate (1) having a porous metal oxide semiconductor film (1) having an electrode layer (1) on the surface and adsorbing a photosensitizer on the surface of the electrode layer (1);
A substrate (2) having an electrode layer (2) on the surface,
The electrode layer (1) and the electrode layer (2) are arranged so as to face each other,
In the photoelectric cell in which an electrolyte layer is provided between the porous metal oxide semiconductor film (1) and the electrode layer (2),
A photoelectric cell, wherein the porous metal oxide semiconductor film (1) is formed using the porous metal oxide semiconductor film-forming paint according to any one of claims 1 to 7.
、平均細孔径が１０〜５０ｎｍの範囲にあることを特徴とする請求項８に記載の光電気セルの製造方法。 The pore volume of the porous metal oxide semiconductor film (1) is in the range of 0.30 to 0.60 ml / g, and the average pore diameter is in the range of 10 to 50 nm. Manufacturing method for photovoltaic cells.
。 10. The titanium oxide thin film (1) derived from peroxotitanic acid is provided between the electrode layer (1) and the porous metal oxide semiconductor film (1). Photoelectric cell.
０．２０ｍｌ／ｇの範囲にあり、平均細孔径が０．５〜５．０ｎｍの範囲にあることを特徴とする請求項８〜１０のいずれかに記載の光電気セル。 The thickness of the titanium oxide thin film (1) is in the range of 10 to 70 nm, and the pore volume is 0.01 to
The photoelectric cell according to any one of claims 8 to 10, wherein the photoelectric cell is in a range of 0.20 ml / g and an average pore diameter is in a range of 0.5 to 5.0 nm.
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