JP2008016405A6 - Dye-sensitized solar cell and method for producing the same - Google Patents
Dye-sensitized solar cell and method for producing the same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000004065 semiconductor Substances 0.000 claims abstract description 115
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 21
- 239000010419 fine particle Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 196
- 239000010408 film Substances 0.000 description 64
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 16
- 229910001929 titanium oxide Inorganic materials 0.000 description 16
- 239000011521 glass Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005118 spray pyrolysis Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N Ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K Butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 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
- RKCAIXNGYQCCAL-UHFFFAOYSA-N Porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 239000005092 Ruthenium Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000001747 exhibiting Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- -1 iodide ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating Effects 0.000 description 1
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
【課題】多孔質半導体層の厚みを厚くする等した場合においても高い変換効率を得ることができる色素増感太陽電池およびその製造方法を提供する。
【解決手段】色素増感太陽電池１０は、透明基板１２と、透明導電膜１４と、導電膜１６および基板１８で構成される導電性基板を備え、透明導電膜１４と導電性基板の間に色素を吸着した多孔質半導体層２０と電解質２２を有する。多孔質半導体層２０は、酸化スズを主成分とする導電層部２０ａと、導電層部２０ａの透明基板１４に対向する側の表面に設けられる第１の多孔質半導体層部２０ｂおよび導電層部２０ａの他方の表面に設けられる第２の多孔質半導体層部２０ｃで構成される。導電層部２０ａは、貫通孔２１を有し、透明導電膜１４に電気的に接続される。
【選択図】図１Disclosed is a dye-sensitized solar cell capable of obtaining high conversion efficiency even when the thickness of a porous semiconductor layer is increased.
A dye-sensitized solar cell includes a conductive substrate including a transparent substrate, a transparent conductive film, a conductive film, and a substrate, and the transparent conductive film is interposed between the transparent conductive film and the conductive substrate. It has the porous semiconductor layer 20 and the electrolyte 22 which adsorb | sucked the pigment | dye. The porous semiconductor layer 20 includes a conductive layer portion 20a mainly composed of tin oxide, and a first porous semiconductor layer portion 20b and a conductive layer portion provided on the surface of the conductive layer portion 20a on the side facing the transparent substrate 14. It is comprised by the 2nd porous semiconductor layer part 20c provided in the other surface of 20a. The conductive layer portion 20 a has a through hole 21 and is electrically connected to the transparent conductive film 14.
[Selection] Figure 1
Description
本発明は、色素増感太陽電池およびその製造方法に関する。 The present invention relates to a dye-sensitized solar cell and a method for producing the same.
色素増感太陽電池は、湿式太陽電池あるいはグレッツェル電池等と呼ばれ、シリコン半導体を用いることなくヨウ素溶液に代表される電気化学的なセル構造を持つ点に特徴がある。具体的には、透明な導電性ガラス板（透明導電膜を積層した透明基板）に二酸化チタン粉末等を焼付け、これに色素を吸着させて形成したチタニア層等の多孔質半導体層と導電性ガラス板（導電性基板）からなる対極の間に電解液としてヨウ素溶液等を配置した、簡易な構造を有する。
色素増感太陽電池は、材料が安価であり、作製に大掛かりな設備を必要としないことから、低コストの太陽電池として注目されている。
The dye-sensitized solar cell is called a wet solar cell or a Gretzel battery, and is characterized in that it has an electrochemical cell structure typified by an iodine solution without using a silicon semiconductor. Specifically, a porous semiconductor layer such as a titania layer formed by baking a titanium dioxide powder or the like on a transparent conductive glass plate (transparent substrate on which a transparent conductive film is laminated) and adsorbing a pigment thereto, and conductive glass It has a simple structure in which an iodine solution or the like is disposed as an electrolytic solution between counter electrodes made of a plate (conductive substrate).
Dye-sensitized solar cells are attracting attention as low-cost solar cells because they are inexpensive and do not require large-scale equipment for production.
色素増感太陽電池は、太陽光の変換効率が現状で１１％程度であり、さらなる効率の向上が求められている。 The dye-sensitized solar cell currently has a conversion efficiency of sunlight of about 11%, and further improvement in efficiency is required.
太陽光の変換効率を向上させために種々の観点から検討がなされているが、そのうちのひとつとして、多孔質半導体層の厚みを厚くして太陽光の吸収効率を上げる方法が考えられる。 In order to improve the conversion efficiency of sunlight, studies have been made from various viewpoints. One of them is a method of increasing the absorption efficiency of sunlight by increasing the thickness of the porous semiconductor layer.
また、通常の厚みの金属酸化物半導体層を有する色素増感太陽電池についてのものではあるが、電子を効率的に透明導電膜に移動させて変換効率を上げることを目的として、厚みが１０〜１３μｍ程度の金属酸化物半導体層（多孔質半導体層）中に櫛型等の形状に形成された導電層が形成され、導電層と基板上の透明導電層が短絡された色素増感太陽電池が提案されている。導電層は、例えば８μｍ程度の厚みに形成された金属酸化物半導体層の端部を透明導電層の表面が出るまでレーザスクライビングによって削った後、櫛型等の形状のマスクを固定することにより、真空蒸着法等で形成される（特許文献１参照）。
しかしながら、多孔質半導体層の厚みを厚くする場合、多孔質半導体層内での電子の拡散距離が長くなることによって直列抵抗が大きくなり、その結果フィルファクター（ＦＦ）の値が低くなることで、かえって変換効率が低下する問題がある。
また、金属酸化物半導体層中に真空蒸着法等によって櫛型等の形状を有する導電層を形成する方法は、変換効率向上効果はあるものの、製造方法として煩雑でかつコストもかかるものと考えられる。また、この方法を多孔質半導体層の厚みが１３μｍを超えるように厚くした場合においても好適に適用できるものかどうかは定かではない。
However, when the thickness of the porous semiconductor layer is increased, the series resistance is increased by increasing the electron diffusion distance in the porous semiconductor layer, and as a result, the value of the fill factor (FF) is decreased. On the contrary, there is a problem that the conversion efficiency is lowered.
In addition, a method of forming a conductive layer having a comb shape or the like in a metal oxide semiconductor layer by vacuum deposition or the like is thought to be complicated and costly as a manufacturing method, although it has an effect of improving conversion efficiency. . Moreover, it is not certain whether this method can be suitably applied even when the thickness of the porous semiconductor layer is increased to exceed 13 μm.
本発明は、上記の課題に鑑みてなされたものであり、多孔質半導体層の厚みを厚くする等した場合においても高い変換効率を得ることができる色素増感太陽電池およびその製造方法を提供することを目的とする。 The present invention has been made in view of the above problems, and provides a dye-sensitized solar cell capable of obtaining high conversion efficiency even when the thickness of a porous semiconductor layer is increased, and a method for manufacturing the same. For the purpose.
本発明に係る色素増感太陽電池は、透明基板と、該透明基板の表面に形成される透明導電膜と、該透明導電膜と対向して設けられる導電性基板を備え、該透明導電膜と該導電性基板の間に色素を吸着した多孔質半導体層と電解質を有する色素増感太陽電池において、
該多孔質半導体層が、酸化スズを主成分とし、貫通孔を有するとともに該透明導電膜に電気的に接続された導電層部（１）と、該導電層部の該透明基板側の表面に設けられる第１の多孔質半導体層部（２）および該導電層部の他方の表面に設けられる第２の多孔質半導体層部（３）で構成されてなることを特徴とする。
The dye-sensitized solar cell according to the present invention includes a transparent substrate, a transparent conductive film formed on the surface of the transparent substrate, and a conductive substrate provided to face the transparent conductive film, In a dye-sensitized solar cell having a porous semiconductor layer and an electrolyte in which a dye is adsorbed between the conductive substrates,
The porous semiconductor layer is mainly composed of tin oxide, has a through-hole, and is electrically connected to the transparent conductive film, and on the surface of the conductive layer on the transparent substrate side. It comprises a first porous semiconductor layer portion (2) provided and a second porous semiconductor layer portion (3) provided on the other surface of the conductive layer portion.
また、本発明に係る色素増感太陽電池は、前記第１の多孔質半導体層部および前記第２の多孔質半導体層部の合計厚みが１４〜３１μｍであることを特徴とする。 The dye-sensitized solar cell according to the present invention is characterized in that a total thickness of the first porous semiconductor layer portion and the second porous semiconductor layer portion is 14 to 31 μm.
また、本発明に係る色素増感太陽電池は、前記第１の多孔質半導体層部が複数層で構成され、該複数層のうちの前記導電層部に接する側の層が、該導電層部に接する側の層に隣り合う層よりも微細な半導体材料で形成されてなることを特徴とする。 Further, in the dye-sensitized solar cell according to the present invention, the first porous semiconductor layer portion is composed of a plurality of layers, and the layer in contact with the conductive layer portion of the plurality of layers is the conductive layer portion. It is characterized by being formed of a finer semiconductor material than the layer adjacent to the layer on the side in contact with.
また、本発明に係る色素増感太陽電池は、前記第１の多孔質半導体層部の厚みが１０〜２０μｍであることを特徴とする。 In the dye-sensitized solar cell according to the present invention, the thickness of the first porous semiconductor layer portion is 10 to 20 μm.
また、本発明に係る色素増感太陽電池は、前記導電層部の厚みが１２０ｎｍ以下であることを特徴とする。 In the dye-sensitized solar cell according to the present invention, the conductive layer portion has a thickness of 120 nm or less.
また、本発明に係る色素増感太陽電池は、前記導電層部の厚みが７５ｎｍ以上であることを特徴とする。 In the dye-sensitized solar cell according to the present invention, the conductive layer portion has a thickness of 75 nm or more.
また、本発明に係る色素増感太陽電池は、前記導電層部が、フッ素を０．２質量％以下および塩素を０．４質量％以下含有することを特徴とする。 The dye-sensitized solar cell according to the present invention is characterized in that the conductive layer portion contains 0.2% by mass or less of fluorine and 0.4% by mass or less of chlorine.
また、本発明に係る色素増感太陽電池は、前記導電層部が、熱分解反応によって形成されてなることを特徴とする。 The dye-sensitized solar cell according to the present invention is characterized in that the conductive layer portion is formed by a thermal decomposition reaction.
また、本発明に係る色素増感太陽電池は、前記第２の多孔質半導体層部が複数層で構成され、該複数層のうちの前記導電層部に接する側の層が、他の層よりも微細な半導体材料で形成されてなることを特徴とする。 In the dye-sensitized solar cell according to the present invention, the second porous semiconductor layer portion is composed of a plurality of layers, and the layer on the side in contact with the conductive layer portion of the plurality of layers is more than the other layers. Is formed of a fine semiconductor material.
また、本発明に係る色素増感太陽電池は、前記微細な半導体材料で形成される層の該半導体材料が、平均粒径１０ｎｍ以下のチタニア微粒子であることを特徴とする。 The dye-sensitized solar cell according to the present invention is characterized in that the semiconductor material of the layer formed of the fine semiconductor material is titania fine particles having an average particle diameter of 10 nm or less.
また、本発明に係る色素増感太陽電池の製造方法は、透明基板と、該透明基板の表面に形成される透明導電膜と、該透明導電膜と対向して設けられる導電性基板を備え、該透明導電膜と該導電性基板の間に色素を吸着した多孔質半導体層と電解質を有する色素増感太陽電池の製造方法において、
該透明導電膜の表面に、他の層よりも微細な半導体材料で形成される層を少なくとも最表層に含むように２以上の層からなる多孔質半導体層部を形成する工程と、
該多孔質半導体層部の表面に導電層を形成する工程と、
を有することを特徴とする。
Moreover, the method for producing a dye-sensitized solar cell according to the present invention includes a transparent substrate, a transparent conductive film formed on the surface of the transparent substrate, and a conductive substrate provided to face the transparent conductive film, In the method for producing a dye-sensitized solar cell having a porous semiconductor layer and an electrolyte in which a dye is adsorbed between the transparent conductive film and the conductive substrate,
Forming a porous semiconductor layer composed of two or more layers on the surface of the transparent conductive film so that at least the outermost layer includes a layer formed of a semiconductor material finer than other layers;
Forming a conductive layer on the surface of the porous semiconductor layer portion;
It is characterized by having.
本発明に係る色素増感太陽電池は、多孔質半導体層が、酸化スズを主成分とし、貫通孔を有するとともに透明導電膜に電気的に接続された導電層部と、導電層部の透明基板に対向する側の表面に設けられる第１の多孔質半導体層部および導電層部の他方の表面に設けられる第２の多孔質半導体層部で構成されるので、多孔質半導体層の厚みを厚くする等した場合においても高い変換効率を得ることができる。
また、本発明に係る色素増感太陽電池の製造方法は、透明導電膜の表面に、他の層よりも微細な半導体材料で形成される層を少なくとも最表層に含むように２以上の層からなる多孔質半導体層部を形成する工程と、多孔質半導体層部の表面に導電層を形成する工程と、を有するので、透明導電膜の表面に導電層を容易に形成することができる。
The dye-sensitized solar cell according to the present invention includes a conductive layer portion in which a porous semiconductor layer is mainly composed of tin oxide, has a through-hole, and is electrically connected to a transparent conductive film, and a transparent substrate of the conductive layer portion Since the first porous semiconductor layer portion provided on the surface opposite to the first porous semiconductor layer portion and the second porous semiconductor layer portion provided on the other surface of the conductive layer portion are formed, the thickness of the porous semiconductor layer is increased. High conversion efficiency can be obtained even in the case of doing so.
Moreover, the manufacturing method of the dye-sensitized solar cell which concerns on this invention is the surface of a transparent conductive film from two or more layers so that the layer formed with a semiconductor material finer than another layer may be included in an outermost layer at least. Since it has the process of forming the porous semiconductor layer part which becomes, and the process of forming a conductive layer in the surface of a porous semiconductor layer part, a conductive layer can be easily formed in the surface of a transparent conductive film.
本発明に係る色素増感太陽電池およびその製造方法の好適な実施の形態について、図を参照して、以下に説明する。 Preferred embodiments of a dye-sensitized solar cell and a method for producing the same according to the present invention will be described below with reference to the drawings.
既に説明したように、色素増感太陽電池中の多孔質酸化チタン膜等の多孔質半導体層を厚膜にした場合やその面積を大きくした場合、光により生成された、拡散長が２０μｍ程度といわれている電子の拡散距離が長くなるために、直列抵抗が大きくなってしまう。そのため、電子は、酸化チタン多孔質膜を通って透明導電膜まで到達することが困難になる。その結果、形状因子であるフィルファクター(FF)の値が低くなり、光電変換効率の低下が起こることが問題となっていた。
この問題について、本発明者等が鋭意検討した結果、電子の拡散長と実験より得られた多孔質半導体層の膜厚と光電変換特性の結果を勘案すると、多孔質半導体層のなかに導電性の中間層を設けることで、光電変換効率の向上を図ることができることを見出し、本発明に想達した。
As already explained, when the porous semiconductor layer such as the porous titanium oxide film in the dye-sensitized solar cell is made thick or its area is increased, the diffusion length generated by light is about 20 μm. Since the so-called diffusion distance of electrons becomes long, the series resistance becomes large. Therefore, it becomes difficult for electrons to reach the transparent conductive film through the titanium oxide porous film. As a result, the value of the fill factor (FF), which is a form factor, is lowered, and the photoelectric conversion efficiency is lowered.
As a result of intensive studies by the present inventors on this problem, the results of the electron diffusion length, the thickness of the porous semiconductor layer obtained from the experiment, and the results of the photoelectric conversion characteristics are considered to be conductive in the porous semiconductor layer. It was found that the photoelectric conversion efficiency can be improved by providing the intermediate layer, and the present invention has been conceived.
例えば図１に模式的に示すように、本発明に係る色素増感太陽電池１０は、透明基板１２と、透明基板１２の表面に形成される透明導電膜１４と、透明導電膜１４と対向して設けられる導電性基板（図１では、導電膜１６および基板１８で構成される。）を備え、透明導電膜１４と導電性基板の間に色素（図１では表示していない。）を吸着した多孔質半導体層２０と電解質２２を有する。そして、多孔質半導体層２０は、酸化スズを主成分とする導電層部２０ａと、導電層部２０ａの透明基板１４に対向する側の表面に設けられる第１の多孔質半導体層部２０ｂおよび導電層部２０ａの他方の表面に設けられる第２の多孔質半導体層部２０ｃで構成される。導電層部２０ａは、貫通孔２１を有し、両端（二側）が透明導電膜１４に接続されている。なお、図１中、参照符号２４は電池内に電解質２２を密閉するために設けられるセパレータを示す。 For example, as schematically shown in FIG. 1, a dye-sensitized solar cell 10 according to the present invention faces a transparent substrate 12, a transparent conductive film 14 formed on the surface of the transparent substrate 12, and the transparent conductive film 14. The conductive substrate (constituted by the conductive film 16 and the substrate 18 in FIG. 1) is provided, and a dye (not shown in FIG. 1) is adsorbed between the transparent conductive film 14 and the conductive substrate. The porous semiconductor layer 20 and the electrolyte 22 are provided. The porous semiconductor layer 20 includes a conductive layer portion 20a mainly composed of tin oxide, a first porous semiconductor layer portion 20b provided on the surface of the conductive layer portion 20a facing the transparent substrate 14, and a conductive layer. It is comprised by the 2nd porous semiconductor layer part 20c provided in the other surface of the layer part 20a. The conductive layer portion 20 a has a through hole 21, and both ends (two sides) are connected to the transparent conductive film 14. In FIG. 1, reference numeral 24 denotes a separator provided for sealing the electrolyte 22 in the battery.
透明基板１２および基板１８は、例えば、ガラス板であってもよくあるいはプラスチック板であってもよい。
透明導電膜１４は、例えば、ＩＴＯ（スズをドープしたインジウム膜）であってもよく、またＦＴＯ（フッ素をドープした酸化スズ膜）であってもよく、あるいはまたアンチモンをドープしたＳｎＯ２(ATO)膜、またはアルミやインジュウムをドープした酸化亜鉛(ZnO)膜等であってもよい。このうち、比抵抗が３．５×１０−４（Ω・ｃｍ）と低く、また、その表面に多孔質半導体層２０を形成するときの熱安定性が高いＦＴＯがより好ましい。導電膜１６は、ITO、FTO、ATOやZnO等の膜の上にPt薄膜やカーボン皮膜を持つ導電体層である。
The transparent substrate 12 and the substrate 18 may be glass plates or plastic plates, for example.
The transparent conductive film 14 may be, for example, ITO (indium film doped with tin), FTO (tin oxide film doped with fluorine), or SnO 2 (ATO doped with antimony). ) Film or a zinc oxide (ZnO) film doped with aluminum or indium. Among these, FTO having a low specific resistance of 3.5 × 10 −4 (Ω · cm) and high thermal stability when the porous semiconductor layer 20 is formed on the surface thereof is more preferable. The conductive film 16 is a conductor layer having a Pt thin film or a carbon film on a film of ITO, FTO, ATO, ZnO or the like.
多孔質半導体層２０に吸着させる色素は、例えば、ルテニウム等の遷移金属錯体やフタロシアニン、ポルフィン等の金属あるいは非金属等を適宜用いることができる。 As the dye adsorbed on the porous semiconductor layer 20, for example, a transition metal complex such as ruthenium, a metal such as phthalocyanine or porphine, or a nonmetal can be used as appropriate.
電解質２２は、特に限定するものではなく、例えばヨウ化物イオンおよびヨウ素の組み合わせからなるもの等の適宜の酸化還元体を用いることができる。酸化還元体は、これを溶解可能な適宜の溶媒を含む。 The electrolyte 22 is not particularly limited, and an appropriate redox material such as a combination of iodide ions and iodine can be used. The redox form contains an appropriate solvent that can dissolve the redox form.
多孔質半導体層２０の第１の多孔質半導体層部２０ｂおよび第２の多孔質半導体層部２０ｃは、半導体材料として、例えば、チタン、スズ、ジルコニウム、亜鉛、インジウム、タングステン、鉄、ニッケルあるいは銀等の金属の酸化物を用いることができるが、このうち、チタン酸化物（チタニア）がより好ましい。 The first porous semiconductor layer portion 20b and the second porous semiconductor layer portion 20c of the porous semiconductor layer 20 are made of, for example, titanium, tin, zirconium, zinc, indium, tungsten, iron, nickel or silver as a semiconductor material. Among these, oxides of metals such as titanium oxide (titania) are more preferable.
第１の多孔質半導体層部２０ｂは、単層であってもよいが、例えば図１に示すように、より好ましくは、複数層で構成する。そして、複数層のうちの導電層部２０ａに接する側の層３０ａを導電層部２０ａに接する側の層３０ａに隣り合う層３０ｂよりも微細な半導体材料で形成する。例えば、層３０ａを平均粒径１０ｎｍ以下のチタニア微粒子で形成し、層３０ｂを、好ましくは、平均粒径１０ｎｍ以上の、例えば平均粒径１３〜３０ｎｍ程度のチタニア微粒子で多孔性を充分有するように形成する。なお、このとき、層３０ｂの外側（図１中、左側）にさらに層３０ａと同様の層３０ｃを設けてもよい。 Although the first porous semiconductor layer portion 20b may be a single layer, for example, as shown in FIG. 1, it is more preferably composed of a plurality of layers. Then, the layer 30a on the side in contact with the conductive layer portion 20a of the plurality of layers is formed with a finer semiconductor material than the layer 30b adjacent to the layer 30a on the side in contact with the conductive layer portion 20a. For example, the layer 30a is formed with titania fine particles having an average particle size of 10 nm or less, and the layer 30b is preferably sufficiently porous with titania fine particles having an average particle size of 10 nm or more, for example, an average particle size of about 13 to 30 nm. Form. At this time, a layer 30c similar to the layer 30a may be further provided outside the layer 30b (on the left side in FIG. 1).
また、このとき、第１の多孔質半導体層部の厚みは、１０〜２０μｍであることが好ましい。厚みが１０μｍを下回ると、本発明の効果が十二分に得られないおそれがあり、一方、厚みが２０μｍを超えると、多孔質半導体層２０の厚みが厚くなりすぎて、かえって本発明の効果を損なうおそれがある。 At this time, the thickness of the first porous semiconductor layer portion is preferably 10 to 20 μm. If the thickness is less than 10 μm, the effect of the present invention may not be sufficiently obtained. On the other hand, if the thickness exceeds 20 μm, the thickness of the porous semiconductor layer 20 becomes too thick, and the effect of the present invention is rather. May be damaged.
多孔質半導体層２０の第２の多孔質半導体層部２０ｃは、単層であってもよいが、より好ましくは、例えば図１に示すように、多孔質半導体層部２０ｂと同様に、複数層で構成し、複数層のうちの導電層部２０ａに接する側の層３２ａを他の層３２ｂよりも微細な半導体材料で形成する。これにより、電解質に溶出しやすく、あるいは第１の多孔質半導体層部２０ｂから剥離するおそれのある導電層部２０ａをより確実に保護することができ、あるいはまた、ダーク電流の生成によるＦ．Ｆの低下を防止することができる。なお、第２の多孔質半導体層部２０ｃについても、第１の多孔質半導体層部２０ｂと同様の、チタニア粒径の構成とすることができ、また、層３２ｂを複数層で構成してもよい。 The second porous semiconductor layer portion 20c of the porous semiconductor layer 20 may be a single layer, but more preferably, as shown in FIG. 1, for example, a plurality of layers as in the porous semiconductor layer portion 20b. The layer 32a on the side in contact with the conductive layer portion 20a of the plurality of layers is formed of a semiconductor material finer than the other layers 32b. As a result, the conductive layer portion 20a that is likely to be eluted into the electrolyte or may be peeled off from the first porous semiconductor layer portion 20b can be more reliably protected, or the F.D. A decrease in F can be prevented. The second porous semiconductor layer portion 20c can also have a titania particle size configuration similar to that of the first porous semiconductor layer portion 20b, and the layer 32b can be composed of a plurality of layers. Good.
導電層部２０ａは、透明導電膜１４に電気的に接続されるものである限り、図１の構成に変えて、透明導電膜１４の一端（一側）のみを透明導電膜１４に接続した構成としてもよく、あるいはまた、例えば、透明導電膜１４および導電層部２０ａの中央部等に掛け渡された垂直導電体柱で両者を接続した構成としてもよい。
導電層部２０ａの材料は、酸化スズを主成分とする、ＩＴＯ、ＦＴＯあるいはＺｎＯ等を用いることができ、このうち、ＩＴＯに比べて熱的な安定性が高いＦＴＯを用いることが、より好ましい。ＦＴＯを用いる場合、フッ素を０．２質量％以下および塩素を０．４質量％以下含有するものであると、透明導電層１４と同様に、多孔質半導体層２０への影響が少なく、抵抗値と透過率のバランスがとれるので、より好ましい。
導電層部２０ａは、本発明の効果を確実に奏する観点からは、厚みが１２０ｎｍ以下であることが好ましい。一方、本発明の効果を格段に発揮する観点からは、厚みが７５ｎｍ以上であることが好ましい。
導電層部２０ａは、熱分解反応によって形成されたものであることが好ましい。
また、導電層部２０ａは、多孔質半導体層を間に挟んで、すなわち、多孔質半導体層と交互に複数形成してもよい。
As long as the conductive layer portion 20a is electrically connected to the transparent conductive film 14, the configuration is such that only one end (one side) of the transparent conductive film 14 is connected to the transparent conductive film 14 instead of the configuration of FIG. Alternatively, for example, a configuration may be adopted in which both are connected by a vertical conductive pillar extending over the transparent conductive film 14 and the central portion of the conductive layer portion 20a.
As the material of the conductive layer portion 20a, ITO, FTO, ZnO or the like mainly composed of tin oxide can be used, and among these, it is more preferable to use FTO having higher thermal stability than ITO. . When FTO is used, if it contains 0.2% by mass or less of fluorine and 0.4% by mass or less of chlorine, as with the transparent conductive layer 14, there is little influence on the porous semiconductor layer 20, and the resistance value And the transmittance are more preferable.
The conductive layer portion 20a preferably has a thickness of 120 nm or less from the viewpoint of reliably achieving the effects of the present invention. On the other hand, the thickness is preferably 75 nm or more from the viewpoint of remarkably exhibiting the effects of the present invention.
The conductive layer portion 20a is preferably formed by a thermal decomposition reaction.
Further, the conductive layer portion 20a may be formed in plural with the porous semiconductor layer interposed therebetween, that is, alternately with the porous semiconductor layer.
ここで、本発明に係る色素増感太陽電池の製造方法について説明する。
本発明に係る色素増感太陽電池の製造方法は、透明導電膜の表面に、他の層よりも微細な半導体材料で形成される層を少なくとも最表層に含むように２以上の層からなる多孔質半導体層部を形成する工程と、多孔質半導体層部の表面に導電層を形成する工程と、を有するものである。これらの２つの工程以外については、一般的に用いられる適宜の方法を用いることができ、また、上記した本発明に係る色素増感太陽電池の場合は、さらに、導電層の表面に多孔質半導体層部を形成する工程を有するが、他の色素増感太陽電池の製造方法に本発明の製造方法を用いる場合は、この工程は必須ではない。
本発明に係る色素増感太陽電池において、上記のように、第１の多孔質半導体層部２０ｂは、層３０ａを導電層部２０ａに接する側の層３０ａに隣り合う層３０ｂよりも微細な半導体材料で形成する。ついで、微細な半導体材料で形成した層３０ａの表面に導電層部２０ａを形成する。
導電層部２０ａの形成方法は、スプレー法、ＣＶＤ法、スパッタリング法、ディップ法など種々の方法のなかから適宜選択することができるが、中でもスプレー法やＣＶＤ法が、得られる膜の特性の面からも優れており、また経済性の面でも優れる。これら方法において用いられる錫原料としては、ＳｎＣｌ４，（ＣｎＨ２ｎ＋１）４Ｓｎ（ｎ＝１〜４）、Ｃ４Ｈ９ＳｎＣｌ３、（ＣＨ３）２ＳｎＣｌ２等を使用することができる。また、フッ素をドーピングするための原料としては、スプレー法の場合、ＮＨ４Ｆ、ＣＶＤ法の場合、ＨＦ、ＣＣｌ２Ｆ２、ＣＨＣｌＦ２、ＣＨ３ＣＨＦ２、ＣＦ３Ｂｒ等を用いることができる。これらの原料を用いた酸化錫の製膜により、フッ素や塩素量を最適化した導電層部２０ａを形成することができる。
層３０ａを通常の、例えば１３μｍを超える粒径の半導体粒子で形成した場合、その表面の凹凸のために、層３０ａの表面に厚みの薄い導電層部２０ａを形成することは容易ではなく、膜の形状を保持すること自体がほとんど不可能であった。これに対して、本発明に係る色素増感太陽電池の製造方法によれば、微細な半導体材料は、層３０ｂや層３２ｂの多孔質半導体膜と同様に多孔性を持つが、その表面は比較的滑らかな状態を保ち、直径100nmから200ｎm程度の小さなくぼみが１μｍ２あたりにわずかに5個程度分布するにすぎない。この比較的平坦化された層３０ａの表面に対してスプレー熱分解法等の簡易な方法で導電層部２０ａを比較的容易に形成することができる。
そして、このとき、層３０ａの表面に厚みの薄い導電層部２０ａを形成することにより、導電層部２０ａには自然に貫通孔２１が形成される。貫通孔２１は製造条件によっては無数に形成されるが、電解質２２を適度に浸透、透過できるものである限り適当な数形成されれば十分である。ここでいう、適度に厚みの薄い導電層部２０ａの具体的な厚みは、多孔質半導体層部の条件等によって異なるが、例えば、５０〜１７０ｎｍ程度である。
また、上記本発明の製造方法に代えて、通常の、例えば１０ｎｍを超える粒径の半導体粒子で形成した多孔質半導体層部の表面に、上記に比べて厚みの厚い導電層部２０ａを形成してもよい。ただし、この場合、導電層部２０ａの厚みが厚すぎることおよび導電層部２０ａの被覆が十分でないことによる電解液との接触のための漏れ電流に起因して、電池の高い変換効率が得られなかったり、あるいはまた、貫通孔の形成が不十分になったりすることも考えられるので、上記本発明の製造方法のほうがより好ましい。
Here, the manufacturing method of the dye-sensitized solar cell concerning this invention is demonstrated.
In the method for producing a dye-sensitized solar cell according to the present invention, the surface of the transparent conductive film is a porous layer composed of two or more layers so that at least the outermost layer includes a layer formed of a semiconductor material finer than the other layers. A step of forming a porous semiconductor layer portion and a step of forming a conductive layer on the surface of the porous semiconductor layer portion. Except for these two steps, an appropriate method generally used can be used. In the case of the above-described dye-sensitized solar cell according to the present invention, a porous semiconductor is further formed on the surface of the conductive layer. Although it has the process of forming a layer part, when using the manufacturing method of this invention for the manufacturing method of another dye-sensitized solar cell, this process is not essential.
In the dye-sensitized solar cell according to the present invention, as described above, the first porous semiconductor layer portion 20b is a semiconductor finer than the layer 30b adjacent to the layer 30a on the side where the layer 30a is in contact with the conductive layer portion 20a. Form with material. Next, the conductive layer portion 20a is formed on the surface of the layer 30a formed of a fine semiconductor material.
The method for forming the conductive layer portion 20a can be appropriately selected from various methods such as a spray method, a CVD method, a sputtering method, and a dip method. Among these, the spray method and the CVD method are particularly advantageous in terms of the characteristics of the obtained film. It is also excellent in terms of economy. As a tin raw material used in these methods, SnCl 4 , (CnH 2n + 1 ) 4 Sn (n = 1 to 4), C 4 H 9 SnCl 3 , (CH 3 ) 2 SnCl 2 or the like can be used. As a raw material for doping fluorine, NH 4 F can be used in the spray method, HF, CCl 2 F 2 , CHClF 2 , CH 3 CHF 2 , CF 3 Br, or the like can be used in the CVD method. . By forming tin oxide using these raw materials, it is possible to form the conductive layer portion 20a with optimized amounts of fluorine and chlorine.
When the layer 30a is formed of normal semiconductor particles having a particle diameter exceeding, for example, 13 μm, it is not easy to form the thin conductive layer portion 20a on the surface of the layer 30a due to the unevenness of the surface. It was almost impossible to maintain the shape itself. On the other hand, according to the method for manufacturing a dye-sensitized solar cell according to the present invention, the fine semiconductor material has the same porosity as the porous semiconductor films of the layer 30b and the layer 32b, but the surface thereof is compared. The small indentation with a diameter of about 100 nm to 200 nm is distributed only about 5 per 1 μm 2 . The conductive layer portion 20a can be relatively easily formed on the surface of the relatively flattened layer 30a by a simple method such as spray pyrolysis.
At this time, by forming the thin conductive layer portion 20a on the surface of the layer 30a, the through hole 21 is naturally formed in the conductive layer portion 20a. An infinite number of through-holes 21 are formed depending on manufacturing conditions, but it is sufficient to form an appropriate number as long as the electrolyte 22 can permeate and permeate appropriately. Here, the specific thickness of the conductive layer portion 20a having an appropriately thin thickness varies depending on the conditions of the porous semiconductor layer portion, but is, for example, about 50 to 170 nm.
Further, instead of the manufacturing method of the present invention, a conductive layer portion 20a having a thickness larger than that of the above is formed on the surface of a normal porous semiconductor layer portion formed of semiconductor particles having a particle diameter exceeding 10 nm, for example. May be. However, in this case, high conversion efficiency of the battery can be obtained due to leakage current for contact with the electrolytic solution due to the thickness of the conductive layer portion 20a being too thick and the covering of the conductive layer portion 20a being insufficient. The production method of the present invention is more preferable because there may be no through hole formation or insufficient formation of the through hole.
以上説明した本発明に係る色素増感太陽電池は、集電体として機能する導電層部を多孔質半導体層の内部に設けたので、多孔質半導体層の厚みを例えば１４μｍ以上に厚くする等した場合においても高い変換効率を得ることができる。多孔質半導体層の厚みの上限は得られる変換効率の値等に応じて適宜設定されるが、例えば、３１μｍ程度である。なお、本発明を多孔質半導体層が通常の厚みを有する場合にも好適に適用できることは勿論である。
また、本発明の微細な半導体材料で形成した多孔質半導体層の最表層上に導電層部を形成する方法は、多孔質半導体層を構成要素とするものである限り、色素増感太陽電池以外の太陽電池にも適用することができる。
In the dye-sensitized solar cell according to the present invention described above, since the conductive layer portion functioning as a current collector is provided inside the porous semiconductor layer, the thickness of the porous semiconductor layer is increased to, for example, 14 μm or more. Even in the case, high conversion efficiency can be obtained. The upper limit of the thickness of the porous semiconductor layer is appropriately set according to the value of conversion efficiency obtained, and is, for example, about 31 μm. Needless to say, the present invention can also be suitably applied to the case where the porous semiconductor layer has a normal thickness.
In addition, the method of forming the conductive layer portion on the outermost layer of the porous semiconductor layer formed of the fine semiconductor material of the present invention is not a dye-sensitized solar cell as long as the porous semiconductor layer is a constituent element. This can also be applied to solar cells.
実施例および比較例を挙げて、本発明をさらに説明する。なお、本発明は、以下に説明する実施例に限定されるものではない。 The present invention will be further described with reference to examples and comparative examples. In addition, this invention is not limited to the Example demonstrated below.
（実施例１〜実施例５）
大きさが３０ｍｍ×３０ｍｍ、厚さ１ｍｍのホウケイ酸ガラスを十分洗浄乾燥し、ガラス基板とした。この基板上に以下のようにして透明導電膜を形成した。
ｎ−ブチル錫トリクロライド、水とエタノールの混合溶液に、フッ素ドープのためにフッ化アンモニュウムを加え、キャリアガスとしての窒素ガスに酸素ガスを混合してスプレーガンにて霧化したものを、380℃以上500℃以下に熱したガラス基板上に搬送し、スプレー熱分解によりＦＴＯを製膜した。このときのＦＴＯ膜中のフッ素含有量は、０．１３質量％であり、塩素含有量は０．１７質量％であった。
こうして得られたＦＴＯ膜付きガラス基板を十分に洗浄乾燥した後、酸化チタン微粒子ペーストを0.5ｃｍ×0.5ｃｍの面積にスキージ法により塗布した。具体的には、酸化チタン多孔質膜として、10nm以下の微粒子からなる緻密層を2μm程度、その上に10nm以上の微粒子からなる多孔質膜を6μm程度、その上に10nm以下の微粒子からなる緻密層を2μm程度順次製膜した。その後、500℃で１時間の間、電気炉で熱処理を行った。得られた酸化チタン多孔質膜（第１の多孔質半導体層部）の総膜厚は、ほぼ10μmであった。
さらに、ガラス基板上に形成したFTO膜と同様の条件で、スプレー熱分解法で、酸化チタン多孔質膜の上にFTOを製膜し、65nm〜150nmの範囲で厚みを変えた透明導電膜（導電層部）を形成した。
さらに、緻密酸化チタン層2μm程度と多孔質酸化チタン層3μm程度を順次製膜し、再度、500℃で１時間熱処理して酸化チタン多孔質膜（第２の多孔質半導体層部）を形成した。
これらの多孔質膜を形成したガラス基板をN３(RuL2(NCS)2, L: 4,4’-dicarboxy-2,2’-bipyridine)色素を含むエタノール溶液中に13時間程度浸して、酸化チタン厚膜に色素を吸着させた。さらに、スパッタ法により製膜した白金を持つＩＴＯまたはＦＴＯを対極として、２つの膜（極）を５０μｍのスペーサにより封止した。この封止した空間に、アセトニトリル中、I2 250 ml、t-BuPy 580 mMを調整した電解質を注入して、セル（電池セル）を作製し、評価した。
(Example 1 to Example 5)
A borosilicate glass having a size of 30 mm × 30 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a glass substrate. A transparent conductive film was formed on this substrate as follows.
A mixture of n-butyltin trichloride, water and ethanol, ammonium fluoride for fluorine doping, oxygen gas mixed with nitrogen gas as a carrier gas, and atomized with a spray gun, 380 It was transported onto a glass substrate heated to from ℃ to 500 ℃, and FTO was formed by spray pyrolysis. At this time, the fluorine content in the FTO film was 0.13% by mass, and the chlorine content was 0.17% by mass.
The glass substrate with the FTO film thus obtained was sufficiently washed and dried, and then the titanium oxide fine particle paste was applied to an area of 0.5 cm × 0.5 cm by a squeegee method. Specifically, as a porous titanium oxide film, a dense layer made of fine particles of 10 nm or less is about 2 μm, a porous film made of fine particles of 10 nm or more is further about 6 μm, and a dense layer made of fine particles of 10 nm or less is further formed thereon. The layers were sequentially formed to a thickness of about 2 μm. Thereafter, heat treatment was performed in an electric furnace at 500 ° C. for 1 hour. The total film thickness of the obtained titanium oxide porous film (first porous semiconductor layer portion) was approximately 10 μm.
Furthermore, under the same conditions as the FTO film formed on the glass substrate, the FTO film was formed on the titanium oxide porous film by spray pyrolysis, and the thickness was changed in the range of 65 nm to 150 nm. Conductive layer portion) was formed.
Further, a dense titanium oxide layer of about 2 μm and a porous titanium oxide layer of about 3 μm were sequentially formed, and again heat treated at 500 ° C. for 1 hour to form a titanium oxide porous film (second porous semiconductor layer part). .
The glass substrate on which these porous films are formed is immersed in an ethanol solution containing N3 (RuL 2 (NCS) 2 , L: 4,4'-dicarboxy-2,2'-bipyridine) dye for about 13 hours for oxidation. The dye was adsorbed on the titanium thick film. Furthermore, using ITO or FTO having platinum formed by sputtering as a counter electrode, the two films (electrodes) were sealed with a 50 μm spacer. Into this sealed space, an electrolyte prepared by adjusting I 2 250 ml and t-BuPy 580 mM in acetonitrile was injected to produce and evaluate a cell (battery cell).
（実施例６）
実施例１〜実施例５と同様に、第1の多孔質半導体層部は、１０ｎｍ以下の微粒子からなる緻密層を２μｍ程度、その上に１０ｎｍ以上の微粒子からなる多孔質膜を１２μｍ程度、その上に１０ｎｍ以下の微粒子からなる緻密層を２μｍ程度順次製膜した。その後、500℃で１時間の間、電気炉で熱処理を行った。得られた酸化チタン多孔質膜（第１の多孔質半導体層部）の総膜厚は、ほぼ１６μｍであった。さらに、ガラス基板上に形成したFTO膜と同様の条件で、スプレー熱分解法で、酸化チタン多孔質膜の上にFTOを製膜、85nm程度の透明導電膜（導電層部）を形成した。
さらに、緻密酸化チタン層を２μｍ程度と多孔質酸化チタン層を１２μｍ程度製膜、再度、500℃で１時間熱処理して酸化チタン多孔質膜（第２の多孔質半導体層部）を形成した。
(Example 6)
In the same manner as in Examples 1 to 5, the first porous semiconductor layer portion has a dense layer made of fine particles of 10 nm or less, about 2 μm, and a porous film made of fine particles of 10 nm or more on it, about 12 μm. A dense layer made of fine particles of 10 nm or less was successively formed on the top of the film to a thickness of about 2 μm. Thereafter, heat treatment was performed in an electric furnace at 500 ° C. for 1 hour. The total film thickness of the obtained titanium oxide porous film (first porous semiconductor layer portion) was approximately 16 μm. Furthermore, FTO was formed on the titanium oxide porous film by a spray pyrolysis method under the same conditions as the FTO film formed on the glass substrate, and a transparent conductive film (conductive layer part) of about 85 nm was formed.
Further, a dense titanium oxide layer was formed to a thickness of about 2 μm and a porous titanium oxide layer was formed to a thickness of about 12 μm, and heat treated again at 500 ° C. for 1 hour to form a titanium oxide porous film (second porous semiconductor layer portion).
（比較例１）
透明導電膜（導電層部）を省略した以外は実施例と同様の方法により、従来の構成のセル（電池セル）を作製し、実施例と同様に評価した。
(Comparative Example 1)
A cell (battery cell) having a conventional configuration was produced in the same manner as in the example except that the transparent conductive film (conductive layer part) was omitted, and evaluated in the same manner as in the example.
（比較例２〜比較例７）
酸化チタン多孔質膜として、１０ｎｍ以下の微粒子からなる緻密層を２μｍ程度、その上に１０ｎｍ以上の微粒子からなる多孔質膜を積層して、その合計厚みを８．１μｍ〜３０．３μｍの範囲で変えた以外は比較例１と同様の方法により、従来の構成のセル（電池セル）を作製し、実施例と同様に評価した。
(Comparative Example 2 to Comparative Example 7)
As a titanium oxide porous film, a dense layer composed of fine particles of 10 nm or less is laminated about 2 μm, and a porous film made of fine particles of 10 nm or more is laminated thereon, and the total thickness is in the range of 8.1 μm to 30.3 μm. A cell (battery cell) having a conventional configuration was produced in the same manner as in Comparative Example 1 except that the change was made, and evaluated in the same manner as in the example.
以上の結果をまとめて表１に示す。
表１中、太陽電池特性は、100mW/cm2、AM1.5の擬似太陽光を試料セルに照射し、ポテンショスタットと関数発生器を用い、電位掃引して得られた光電流電位曲線から、短絡電流、開放電圧、Ｆ．Ｆを求め、変換効率をそれらの値により求めた。
なお、実施例５の透明導電膜の厚みを１５０ｎｍとしたものは、比較例１よりも変換効率が低いが、多孔質半導体層部の厚み等の諸条件によっては透明導電膜の厚みを１５０ｎｍとすることに意義があることはいうまでもない。
The above results are summarized in Table 1.
In Table 1, the solar cell characteristics are short-circuited from the photocurrent potential curve obtained by irradiating the sample cell with 100mW / cm2, AM1.5 simulated sunlight, and using a potentiostat and a function generator to sweep the potential. Current, open voltage, F.V. F was determined and the conversion efficiency was determined from these values.
In addition, what converted the thickness of the transparent conductive film of Example 5 to 150 nm has lower conversion efficiency than Comparative Example 1, but depending on various conditions such as the thickness of the porous semiconductor layer portion, the thickness of the transparent conductive film is set to 150 nm. It goes without saying that there is significance in doing.
１０ 色素増感太陽電池
１２ 透明基板
１４ 透明導電膜
１６ 導電膜
１８ 基板
２０ 多孔質半導体層
２０ａ 導電層部
２０ｂ 第１の多孔質半導体層部
２０ｃ 第２の多孔質半導体層部
２２ 電解質
２４ セパレータ
３０ａ、３０ｂ、３０ｃ、３２ａ、３２ｂ 層
DESCRIPTION OF SYMBOLS 10 Dye sensitized solar cell 12 Transparent substrate 14 Transparent conductive film 16 Conductive film 18 Substrate 20 Porous semiconductor layer 20a Conductive layer part 20b First porous semiconductor layer part 20c Second porous semiconductor layer part 22 Electrolyte 24 Separator 30a 30b, 30c, 32a, 32b layers
Claims (11)
該多孔質半導体層が、酸化スズを主成分とし、貫通孔を有するとともに該透明導電膜に電気的に接続された導電層部と、該導電層部の該透明基板側の表面に設けられる第１の多孔質半導体層部および該導電層部の他方の表面に設けられる第２の多孔質半導体層部で構成されてなることを特徴とする色素増感太陽電池。 A transparent substrate, a transparent conductive film formed on the surface of the transparent substrate, and a conductive substrate provided opposite to the transparent conductive film are provided, and a dye is adsorbed between the transparent conductive film and the conductive substrate. In a dye-sensitized solar cell having a porous semiconductor layer and an electrolyte,
The porous semiconductor layer is mainly composed of tin oxide, has a through-hole and is electrically connected to the transparent conductive film, and a conductive layer portion provided on a surface of the conductive layer portion on the transparent substrate side. A dye-sensitized solar cell comprising: a porous semiconductor layer portion of 1 and a second porous semiconductor layer portion provided on the other surface of the conductive layer portion.
該透明導電膜の表面に、他の層よりも微細な半導体材料で形成される層を少なくとも最表層に含むように２以上の層からなる多孔質半導体層部を形成する工程と、
該多孔質半導体層部の表面に導電層を形成する工程と、
を有することを特徴とする色素増感太陽電池の製造方法。
A transparent substrate, a transparent conductive film formed on the surface of the transparent substrate, and a conductive substrate provided opposite to the transparent conductive film are provided, and a dye is adsorbed between the transparent conductive film and the conductive substrate. In a method for producing a dye-sensitized solar cell having a porous semiconductor layer and an electrolyte,
Forming a porous semiconductor layer composed of two or more layers on the surface of the transparent conductive film so that at least the outermost layer includes a layer formed of a semiconductor material finer than other layers;
Forming a conductive layer on the surface of the porous semiconductor layer portion;
The manufacturing method of the dye-sensitized solar cell characterized by having.
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