JP2012048835A - Dye-sensitized solar cell and method of manufacturing the same - Google Patents

Dye-sensitized solar cell and method of manufacturing the same Download PDF

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JP2012048835A
JP2012048835A JP2010187045A JP2010187045A JP2012048835A JP 2012048835 A JP2012048835 A JP 2012048835A JP 2010187045 A JP2010187045 A JP 2010187045A JP 2010187045 A JP2010187045 A JP 2010187045A JP 2012048835 A JP2012048835 A JP 2012048835A
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dye
solar cell
sensitized solar
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JP5537336B2 (en
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Takashi Okubo
貴志 大久保
Kyung-Ho Kim
敬鎬 金
Naoya Tanaka
直也 田中
Masahiko Maekawa
雅彦 前川
Takayoshi Kuroda
孝義 黒田
Naoto Mimura
尚登 三村
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Kinki University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell that achieves adsorption to a titanium oxide surface without having a reactive group in a dye molecule although using an inexpensive material, and a method of manufacturing the dye-sensitized solar cell.SOLUTION: The dye-sensitized solar cell is characterized in using a coordination polymer containing a ligand consisting of one kind or two or more kinds of metal ion selected from transition metal elements and one kind or two or more kinds of nitrogen-containing compound or oxygen-containing compound which can be coordinated with the metal ions.

Description

本発明は、色素増感太陽電池に係り、さらに詳しくは配位高分子を用いた色素増感太陽電池およびその色素増感太陽電池の製造方法に関するものである。   The present invention relates to a dye-sensitized solar cell, and more particularly to a dye-sensitized solar cell using a coordination polymer and a method for producing the dye-sensitized solar cell.

近年、グリーンエネルギーとして太陽光が注目されるようになっており、太陽光を使用する太陽電池の開発が盛んになっている。太陽電池には、シリコン太陽電池、無機化合物を用いた太陽電池、有機化合物を用いた色素増感太陽電池などがある。   In recent years, sunlight has attracted attention as green energy, and the development of solar cells using sunlight has become active. Solar cells include silicon solar cells, solar cells using inorganic compounds, and dye-sensitized solar cells using organic compounds.

そしてその中でも色素増感太陽電池は、多孔性酸化チタンと太陽光を吸収するための色素を用いた太陽電池であり、シリコン太陽電池に比べて製造コストが低いことから、新しいタイプの太陽電池として実用化への期待が近年急速に高くなっている。   Among them, the dye-sensitized solar cell is a solar cell using porous titanium oxide and a dye for absorbing sunlight, and has a lower production cost than a silicon solar cell. Expectation for practical use has been rapidly increasing in recent years.

ここで、従来の色素増感太陽電池は、ガラスなどの基板上に酸化チタンを焼結して被膜を形成した後、太陽光が酸化チタンに照射された際に励起される電荷を電解液などに伝達するための色素を酸化チタン表面に吸着することによって陽極を形成する。   Here, in the conventional dye-sensitized solar cell, after a titanium oxide is sintered on a substrate such as glass to form a film, the electric charge excited when the titanium oxide is irradiated to the titanium oxide is used as an electrolyte solution or the like. The anode is formed by adsorbing the dye for transmitting to the titanium oxide surface.

従前においては、これらに使用される色素には非特許文献１または非特許文献２に示すようにグレッツェルによって発明されたルテニウム錯体が広く用いられている。また、このルテニウム錯体については光電変換効率が高いという点から、例えば特許文献１または特許文献２に示すような各種の技術開発が行われている。   Conventionally, ruthenium complexes invented by Gretzel as shown in Non-Patent Document 1 or Non-Patent Document 2 are widely used as the dyes used in these. In addition, for this ruthenium complex, various technical developments such as those shown in Patent Document 1 or Patent Document 2 have been performed from the viewpoint of high photoelectric conversion efficiency.

また、ルテニウム錯体以外の化合物を色素に用いた色素増感太陽電池も開発されており、例えば特許文献３に示すようなベンゾインドール系染料を用いた色素増感太陽電池が開示されている。   In addition, a dye-sensitized solar cell using a compound other than a ruthenium complex as a dye has been developed. For example, a dye-sensitized solar cell using a benzoindole-based dye as disclosed in Patent Document 3 is disclosed.

特開２００５−１２００４２号公報JP 2005-120042 A 特開２００６−２９８８８２号公報JP 2006-298882 A 特開２００９−１７３９２８号公報JP 2009-173928 A

Ｂ．Ｏ‘Ｒｅｇａｎ，Ｍ．Ｇｒａｔｚｅｌ，Ｎａｔｕｒｅ １９９１，３５３，７３７B. O'Regan, M.M. Gratzel, Nature 1991, 353, 737 Ｍ．Ｇｒａｔｚｅｌ，Ｎａｔｕｒｅ ２００１，４１４，３３８M.M. Gratzel, Nature 2001, 414, 338

しかしながら、特許文献１や特許文献２に代表される、色素にルテニウム錯体を用いる色素増感太陽電池は、酸化チタンに吸着させるために色素分子内にカルボキシル基などの反応基を有している必要があり、色素として使用できる分子に制限があるという課題がある。また、希少金属であるルテニウムを使用することから、製造コストが高くなるという課題もある。   However, dye-sensitized solar cells represented by Patent Document 1 and Patent Document 2 that use a ruthenium complex as a dye need to have a reactive group such as a carboxyl group in the dye molecule in order to adsorb to titanium oxide. There is a problem that there is a limit to the molecules that can be used as the dye. In addition, since ruthenium, which is a rare metal, is used, there is a problem that the manufacturing cost increases.

一方、特許文献３に記載のベンゾインドール系染料を用いた色素増感太陽電池は、ルテニウムを用いるよりは安価に製造できるものの、ルテニウム錯体と同様に色素分子内には酸化チタンに吸着させるためのカルボキシル基などの反応基が必要であることから、色素として使用できる分子に制限があるという課題は依然として存在する。   On the other hand, the dye-sensitized solar cell using the benzoindole-based dye described in Patent Document 3 can be manufactured at a lower cost than using ruthenium. However, like the ruthenium complex, the dye-sensitized solar cell is adsorbed to titanium oxide in the dye molecule. Since a reactive group such as a carboxyl group is necessary, there is still a problem that there are limitations on the molecules that can be used as the dye.

本発明は、上記した従来の問題点に鑑みてなされたものであって、安価な原料を使用しながら、色素分子内に反応基を有することなく酸化チタン表面に吸着することができる色素増感太陽電池およびその色素増感太陽電池の製造方法の提供を目的とする。   The present invention has been made in view of the above-described conventional problems, and is capable of adsorbing to the surface of titanium oxide without using a reactive group in the dye molecule while using an inexpensive raw material. It aims at providing the manufacturing method of a solar cell and its dye-sensitized solar cell.

また、太陽光が色素に照射された際に励起される電荷を効率よく酸化チタンなどに伝達することができる色素増感太陽電池およびその色素増感太陽電池の製造方法の提供を目的とする。   It is another object of the present invention to provide a dye-sensitized solar cell that can efficiently transfer charges excited when sunlight is irradiated to the dye to titanium oxide and the like, and a method for manufacturing the dye-sensitized solar cell.

さらに、可視光領域においても高い吸収を示し、照射された太陽光をより効率よく電気に変換することができる色素増感太陽電池およびその色素増感太陽電池の製造方法の提供を目的とする。   Furthermore, it aims at provision of the manufacturing method of the dye-sensitized solar cell which shows high absorption also in visible region, and can convert the irradiated sunlight into electricity more efficiently.

上記目的を達成するために、本発明の請求項１に係る色素増感太陽電池は、遷移金属元素の中から選ばれる１種または２種以上の金属イオンと、金属イオンに配位可能な１種または２種以上の含硫黄化合物または含窒素化合物からなる配位子を含有する配位高分子を用いることを特徴とする。   In order to achieve the above object, a dye-sensitized solar cell according to claim 1 of the present invention is one or two or more metal ions selected from transition metal elements, and 1 capable of coordinating to metal ions. A coordination polymer containing a ligand composed of a seed or two or more sulfur-containing compounds or nitrogen-containing compounds is used.

本発明の請求項２に係る色素増感太陽電池は、遷移金属元素が、Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, Auの中から選ばれる１種または２種以上の金属元素であることを特徴とする。   In the dye-sensitized solar cell according to claim 2 of the present invention, the transition metal element is one selected from Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au. Or it is 2 or more types of metal elements, It is characterized by the above-mentioned.

本発明の請求項３に係る色素増感太陽電池は、配位子が、下記の化１または化２で表わされるジチオカルバミン酸イオンの誘導体の中から選ばれる１種または２種以上の誘導体であることを特徴とする。
（Ｒ1およびＲ2は、同一または異なる脂肪族炭化水素基、置換脂肪族炭化水素基、芳香族炭化水素基、置換芳香族炭化水素基、複素環基および置換複素環基を示す。）
（Ｒ3は、少なくとも１つの窒素原子を含む複素環基または置換複素環基を示す。） In the dye-sensitized solar cell according to claim 3 of the present invention, the ligand is one or two or more derivatives selected from dithiocarbamate ion derivatives represented by the following chemical formula 1 or chemical formula 2. It is characterized by that.
(R 1 and R 2 represent the same or different aliphatic hydrocarbon group, substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, substituted aromatic hydrocarbon group, heterocyclic group and substituted heterocyclic group.)
(R 3 represents a heterocyclic group or a substituted heterocyclic group containing at least one nitrogen atom.)

本発明の請求項４に係る色素増感太陽電池は、配位高分子が、さらに臭素イオンまたはヨウ素イオンを含むことによって構成されたものであることを特徴とする。   The dye-sensitized solar cell according to claim 4 of the present invention is characterized in that the coordination polymer further comprises bromine ions or iodine ions.

本発明の請求項５に係る色素増感太陽電池は、配位高分子が、遷移金属元素に銅を用い、配位子にヘキサメチレンジチオカルバミン酸を用い、かつ臭素イオンまたはヨウ素イオンを用いて構成されたものであることを特徴とする。   In the dye-sensitized solar cell according to claim 5 of the present invention, the coordination polymer is composed of copper as a transition metal element, hexamethylenedithiocarbamic acid as a ligand, and bromine ion or iodine ion. It is characterized by being made.

本発明の請求項６に係る色素増感太陽電池の製造方法は、酸化チタンのペーストと配位高分子とを混合する工程を備えることを特徴とする。   The method for producing a dye-sensitized solar cell according to claim 6 of the present invention includes a step of mixing a titanium oxide paste and a coordination polymer.

まず、本発明の色素増感太陽電池について以下に説明する。   First, the dye-sensitized solar cell of the present invention will be described below.

本発明に係る色素増感太陽電池は、酸化チタンの表面に吸着する色素に配位高分子を用いることを特徴とし、さらに配位高分子として遷移金属元素の中から選ばれる１種または２種以上の金属イオンと、金属イオンに配位可能な１種または２種以上の含硫黄化合物または含窒素化合物からなる配位子を必須成分として用いることを特徴とする。   The dye-sensitized solar cell according to the present invention is characterized by using a coordination polymer as a dye adsorbed on the surface of titanium oxide, and further, one or two kinds selected from transition metal elements as the coordination polymer. A ligand comprising the above metal ions and one or more sulfur-containing compounds or nitrogen-containing compounds capable of coordinating to the metal ions is used as an essential component.

ここで、本発明における「配位高分子」とは、金属イオンを中心にその周囲に有機化合物の配位子が結合している金属錯体が繋がっている構造を取っているものをいう。具体的には、図８に示す一次元構造を取るものや、図９に示す二次元構造を取るものや、図１０に示す三次元構造を取るものなどがあげられる。
なお、かかる配位高分子は、各金属錯体の中心に位置する金属イオン同士が配位子によって架橋された繰り返し構造を取っているものだけでなく、必要に応じて金属錯体の各ユニットを架橋するために、後記するような臭素イオンやヨウ素イオンなど、配位子とは別の架橋剤成分を含有し、当該架橋剤成分によっても架橋された繰り返し構造を取っているものも含まれる。
また、配位高分子骨格が正電荷もしくは負電荷を帯びている場合は、その電荷を打ち消すためにフェロセニウムイオンやアンモニウムイオンなどのカチオンやアニオンが図８、図９、図１０に代表される配位高分子骨格の間に入り込む場合があり、その様な化合物も配位高分子に含まれる。 Here, the “coordinating polymer” in the present invention refers to one having a structure in which a metal complex in which a ligand of an organic compound is bound around a metal ion is connected. Specifically, the one having the one-dimensional structure shown in FIG. 8, the one having the two-dimensional structure shown in FIG. 9, the one having the three-dimensional structure shown in FIG.
Such coordination polymers are not only those having a repeating structure in which metal ions located at the center of each metal complex are cross-linked by a ligand, but also each unit of the metal complex is cross-linked as necessary. In order to do so, the following include a crosslinking agent component other than the ligand, such as bromine ion and iodine ion, which will be described later, and a repeating structure crosslinked by the crosslinking agent component.
When the coordination polymer skeleton has a positive charge or a negative charge, cations and anions such as ferrocenium ion and ammonium ion are represented in FIG. 8, FIG. 9, and FIG. 10 in order to cancel the charge. Such a compound is also included in the coordination polymer.

次に、配位高分子を構成する各成分について説明する。   Next, each component constituting the coordination polymer will be described.

本発明に用いられる金属イオンは、遷移金属元素の中から選ばれる１種または２種以上の元素の金属イオンが用いられる。そして、遷移金属元素の中でもFe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, Auという、いわゆる８族および１Ｂ族の元素の金属イオンを用いることが好ましく、さらに、その中でも下記する配位子を配位することによって配位高分子全体に電子を非局在化させることができ、安価であるという点から銅イオンを用いることが好ましい。
なお、これらの金属イオンについては、１種だけではなく異なる金属イオンを併用することによって、それぞれの金属イオンが有する特性を発現させることができる。例えば、銅イオンとともにプラチナイオンやイリジウムイオンなどの重原子効果を有する金属イオンを用いることによって、銅イオンが有する電子の非局在化効果だけでなく、プラチナイオンやイリジウムイオンなどが有する励起寿命延長効果を発現させることができる。 As the metal ions used in the present invention, metal ions of one or more elements selected from transition metal elements are used. Among the transition metal elements, it is preferable to use metal ions of so-called group 8 and group 1B elements such as Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au. Of these, by coordinating the ligands described below, it is possible to delocalize electrons throughout the coordination polymer, and it is preferable to use copper ions from the viewpoint of being inexpensive.
In addition, about these metal ions, the characteristic which each metal ion has can be expressed by using not only 1 type but different metal ions together. For example, by using metal ions having heavy atom effects such as platinum ions and iridium ions together with copper ions, not only the electron delocalization effect of copper ions but also the excitation lifetime extension of platinum ions and iridium ions, etc. An effect can be expressed.

本発明に用いられる配位子は、上記した金属イオンに配位可能な１種または２種以上の含硫黄化合物または含窒素化合物が用いられる。含硫黄化合物の例としては、ジチオオキサレート、テトラチオオキサレート、ジチオカルボン酸置換基を有する配位子などがあげられ、含窒素化合物の例としては、ピラジン、ビピリジン、イミダゾール骨格を有する配位子などがあげられる。
そして、含硫黄化合物または含窒素化合物の中でも、下記の化１または化２で表わされるジチオカルバミン酸イオンの誘導体を用いることが好ましく、さらに、上記した金属イオンと電子を非局在化させることができるという点から、ヘキサメチレンジチオカルバミン酸を用いることが好ましい。 As the ligand used in the present invention, one or two or more sulfur-containing compounds or nitrogen-containing compounds capable of coordinating with the above metal ions are used. Examples of sulfur-containing compounds include dithiooxalate, tetrathiooxalate, and ligands having a dithiocarboxylic acid substituent. Examples of nitrogen-containing compounds include coordination with pyrazine, bipyridine, and imidazole skeletons. Child etc. are given.
Among the sulfur-containing compounds or nitrogen-containing compounds, it is preferable to use a dithiocarbamate ion derivative represented by the following chemical formula 1 or chemical formula 2, and further, the above metal ions and electrons can be delocalized. Therefore, it is preferable to use hexamethylene dithiocarbamic acid.

（Ｒ1およびＲ2は、同一または異なる脂肪族炭化水素基、置換脂肪族炭化水素基、芳香族炭化水素基、置換芳香族炭化水素基、複素環基および置換複素環基を示す。） (R 1 and R 2 represent the same or different aliphatic hydrocarbon group, substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, substituted aromatic hydrocarbon group, heterocyclic group and substituted heterocyclic group.)

（Ｒ3は、少なくとも１つの窒素原子を含む複素環基または置換複素環基を示す。） (R 3 represents a heterocyclic group or a substituted heterocyclic group containing at least one nitrogen atom.)

なお、Ｒ3の具体例としては、以下の化３で表わされる複素環基または置換複素環基があげられる。またＲ3には、化３で表わされる複素環基または置換複素環基に、さらに同一または異なる脂肪族炭化水素基、置換脂肪族炭化水素基、芳香族炭化水素基、置換芳香族炭化水素基、複素環基および置換複素環基が結合しているものを用いることもできる。 Specific examples of R 3 include heterocyclic groups and substituted heterocyclic groups represented by the following chemical formula 3. R 3 represents a heterocyclic group or a substituted heterocyclic group represented by Chemical Formula 3, and the same or different aliphatic hydrocarbon group, substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, substituted aromatic hydrocarbon group. In addition, those in which a heterocyclic group and a substituted heterocyclic group are bonded can also be used.

本発明の配位高分子には、金属イオンと配位子以外に、金属イオン同士を架橋するための架橋剤成分としてハロゲン元素を用いることができる。なお、その中でも電子の非局在化効果を向上させるという点から、臭素イオンまたはヨウ素イオンを用いることが好ましい。
かかる架橋剤成分を用いることによって、さらに配位高分子全体への電子の非局在化効果を向上させることができる。
例えば、化４に示すように、金属イオンに銅イオンを用い、配位子にヘキサメチレンジチオカルバミン酸を用いて配位した単核錯体同士を、臭素イオンまたはヨウ素イオンを用いて架橋することで銅イオンの禁制遷移状態を破ることができ、よって配位高分子全体への電子の非局在化効果をさらに向上させることができる。 In the coordination polymer of the present invention, in addition to the metal ion and the ligand, a halogen element can be used as a cross-linking agent component for cross-linking metal ions. Of these, bromine ions or iodine ions are preferably used from the viewpoint of improving the delocalization effect of electrons.
By using such a crosslinking agent component, it is possible to further improve the delocalization effect of electrons on the entire coordination polymer.
For example, as shown in Chemical Formula 4, copper ions are cross-linked using bromide ions or iodine ions by cross-linking mononuclear complexes coordinated using copper ions as metal ions and hexamethylenedithiocarbamic acid as ligands. The forbidden transition state of ions can be broken, and thus the delocalization effect of electrons on the entire coordination polymer can be further improved.

（ＸはＢｒまたはＩ） (X is Br or I)

なお、本発明の配位高分子の製造方法としては、原料となる化合物を有機溶媒中で混合するなど、公知の方法で製造することができる。また、架橋剤成分として臭素イオンまたはヨウ素イオンを用いる場合には、まず、単核錯体を作製した後、当該単核錯体と臭素イオン化合物またはヨウ素イオン化合物とを混合することによって製造することができる。具体的には、例えば、銅イオンとヘキサメチレンジチオカルバミン酸を用いて配位した単核錯体を作製しておき、その後作製した単核錯体と臭化銅を有機溶媒中で混合することなどによって製造する。   In addition, as a manufacturing method of the coordination polymer of this invention, it can manufacture by a well-known method, such as mixing the compound used as a raw material in an organic solvent. When bromine ions or iodine ions are used as the cross-linking agent component, the mononuclear complex can be prepared first and then mixed with the mononuclear complex and the bromine ion compound or iodine ion compound. . Specifically, for example, a mononuclear complex coordinated using copper ions and hexamethylenedithiocarbamic acid is prepared, and then the produced mononuclear complex and copper bromide are mixed in an organic solvent. To do.

本発明の配位高分子の分子量や繰り返し単位（ｎ）数としては、特に限定されるものではないが、分子量としては１０００以上であることが好ましく、繰り返し単位数としては１００以上であることが好ましい。なお、分子量と繰り返し単位（ｎ）数の上限については、使用に支障がない範囲において適宜設定することができる。   The molecular weight and the number of repeating units (n) of the coordination polymer of the present invention are not particularly limited, but the molecular weight is preferably 1000 or more, and the number of repeating units is 100 or more. preferable. In addition, about the upper limit of molecular weight and the number of repeating units (n), it can set suitably in the range which does not have trouble in use.

次に、本発明の色素増感太陽電池の製造方法について説明する。   Next, the manufacturing method of the dye-sensitized solar cell of this invention is demonstrated.

本発明に係る色素増感太陽電池の製造方法は、酸化チタンのペーストと配位高分子とを混合する工程を備えることを特徴とするものである。
すなわち、酸化チタンのペーストと上記した配位高分子とを混合することによって、色素としての配位高分子を酸化チタン表面に吸着させ、その後色素が吸着した酸化チタンをガラスなどの基板上に塗布し焼結して陽極を形成するのである。
かかる方法によって、従来のような色素分子内にカルボキシル基などの反応基を有していなくても、色素を酸化チタン表面に吸着させることができ、色素として使用できる分子の選択肢を拡げることができる。
なお、混合の方法としては、必要に応じた配合量の酸化チタンのペーストと配位高分子とを乳鉢などで直接混ぜ合わせる方法などがあげられる。また、酸化チタンのペーストとしてはペクセル・テクノロジー社製のものなど市販のものを用いることができる。 The method for producing a dye-sensitized solar cell according to the present invention includes a step of mixing a titanium oxide paste and a coordination polymer.
That is, by mixing the titanium oxide paste and the coordination polymer described above, the coordination polymer as a dye is adsorbed on the titanium oxide surface, and then the titanium oxide on which the dye is adsorbed is applied onto a substrate such as glass. It is then sintered to form the anode.
By this method, the dye can be adsorbed on the surface of titanium oxide even if the dye molecule does not have a reactive group such as a carboxyl group as in the past, and the choice of molecules that can be used as the dye can be expanded. .
Examples of the mixing method include a method in which a titanium oxide paste having a blending amount as required is directly mixed with a coordination polymer in a mortar or the like. As the titanium oxide paste, commercially available products such as those manufactured by Pexel Technology, Inc. can be used.

本発明の請求項１に係る色素増感太陽電池によれば、単核錯体として用いた場合よりも変換効率の高い色素増感太陽電池を得ることができる。また、安価に色素増感太陽電池を作製することができる。   According to the dye-sensitized solar cell according to claim 1 of the present invention, a dye-sensitized solar cell having higher conversion efficiency than that when used as a mononuclear complex can be obtained. Moreover, a dye-sensitized solar cell can be produced at low cost.

本発明の請求項２に係る色素増感太陽電池によれば、遷移元素の中でも特定の元素を用いることによって、配位高分子における可視領域の吸収の増加、電気伝導性の増大、もしくは励起寿命の増大による高い変換効率の色素増感太陽電池を得ることができる。   According to the dye-sensitized solar cell according to claim 2 of the present invention, by using a specific element among the transition elements, the absorption in the visible region in the coordination polymer is increased, the electrical conductivity is increased, or the excitation lifetime is increased. Thus, a dye-sensitized solar cell with high conversion efficiency can be obtained.

本発明の請求項３に係る色素増感太陽電池によれば、配位子の中でもジチオカルバミン酸イオンの誘導体を用いることによって、効率よく可視光を吸収する配位高分子を得ることができる。
これは遷移元素のイオン化エネルギーとジチオカルバミン酸イオンの誘導体のイオン化エネルギーが近接しているために、本来は禁制遷移である遷移元素の光励起が金属イオンと配位子の軌道の混成によって許容になるためである。また同時に軌道の混成によって、光励起によって生じた電子が配位高分子全体に非局在化するために電気伝導性が増大する。
以上の理由により、ジチオカルバミン酸イオンの誘導体を含む配位高分子全体として光を吸収することができ、可視光域の波長でも高い吸収を有する色素増感太陽電池を得ることができる。 According to the dye-sensitized solar cell of claim 3 of the present invention, a coordination polymer that efficiently absorbs visible light can be obtained by using a derivative of dithiocarbamate ion among the ligands.
This is because the ionization energy of the transition element and the ionization energy of the derivative of the dithiocarbamate ion are close to each other. It is. At the same time, due to the orbital hybridization, the electrons generated by photoexcitation are delocalized throughout the coordination polymer, increasing the electrical conductivity.
For the above reasons, it is possible to obtain a dye-sensitized solar cell that can absorb light as a whole coordination polymer including a derivative of dithiocarbamate ion and has high absorption even at a wavelength in the visible light region.

本発明の請求項４に係る色素増感太陽電池によれば、 遷移元素と、含硫黄化合物からなる配位子に加えて、さらに臭素イオンまたはヨウ素イオンによって構成された配位高分子を用いることによって、より電気伝導性が高く、変換効率の高い色素増感太陽電池を得ることができる。   According to the dye-sensitized solar cell of claim 4 of the present invention, in addition to the transition element and the ligand composed of the sulfur-containing compound, the coordination polymer further composed of bromine ion or iodine ion is used. Thus, a dye-sensitized solar cell with higher electrical conductivity and higher conversion efficiency can be obtained.

本発明の請求項５に係る色素増感太陽電池によれば、遷移元素に銅を、配位子にヘキサメチレンジチオカルバミン酸イオンの誘導体を、さらに臭素イオンまたはヨウ素イオンを用いて配位高分子を構成することによって、上記した全ての効果を発現する色素増感太陽電池を得ることができる。   According to the dye-sensitized solar cell of claim 5 of the present invention, the coordination polymer is formed using copper as a transition element, a derivative of hexamethylenedithiocarbamate ion as a ligand, and bromine ion or iodine ion. By comprising, the dye-sensitized solar cell which expresses all the above-mentioned effects can be obtained.

本発明の請求項６に係る色素増感太陽電池の製造方法によれば、陽極に使用する酸化チタンをペースト状にして配位高分子と混合することによって、配位高分子の末端にカルボキシル基などの反応基を導入することなく、どのような配位高分子でも酸化チタンの表面に吸着させることができる。   According to the method for producing a dye-sensitized solar cell according to claim 6 of the present invention, a carboxyl group is formed at the end of the coordination polymer by mixing titanium oxide used for the anode in a paste form with the coordination polymer. Any coordination polymer can be adsorbed on the surface of titanium oxide without introducing reactive groups such as.

実施例１、実施例２、比較例の電流密度ー電圧特性を示すグラフである。It is a graph which shows the current density-voltage characteristic of Example 1, Example 2, and a comparative example. 実施例１〜４の電流密度ー電圧特性を示すグラフである。It is a graph which shows the current density-voltage characteristic of Examples 1-4. 実施例５、実施例６の電流密度ー電圧特性を示すグラフである。It is a graph which shows the current density-voltage characteristic of Example 5 and Example 6. FIG. 実施例７の電流密度ー電圧特性を示すグラフである。10 is a graph showing current density-voltage characteristics of Example 7. 実施例１、実施例２、比較例の拡散反射スペクトルを示すグラフである。It is a graph which shows the diffuse reflection spectrum of Example 1, Example 2, and a comparative example. 実施例１、実施例２、比較例の光電子分光測定の結果を示すグラフである。It is a graph which shows the result of the photoelectron spectroscopy measurement of Example 1, Example 2, and a comparative example. 実施例１、実施例２、比較例のコールコールプロットを示すグラフである。It is a graph which shows the Cole-Cole plot of Example 1, Example 2, and a comparative example. 一次元構造を取る配位高分子を示す模式図である。It is a schematic diagram which shows the coordination polymer which takes a one-dimensional structure. 二次元構造を取る配位高分子を示す模式図である。It is a schematic diagram which shows the coordination polymer which takes a two-dimensional structure. 三次元構造を取る配位高分子を示す模式図である。It is a schematic diagram which shows the coordination polymer which takes a three-dimensional structure.

次に、実施例および比較例ならびに図面に基づいて、本発明の色素増感太陽電池およびその製造方法を詳細に説明する。なお、以下に述べる実施例は本発明を具体化した一例に過ぎず、本発明の技術的範囲を限定するものでない。   Next, based on an Example and a comparative example, and drawing, the dye-sensitized solar cell of this invention and its manufacturing method are demonstrated in detail. In addition, the Example described below is only an example which actualized this invention, and does not limit the technical scope of this invention.

（単核錯体の作製）
まず、１０ｍｍｏｌの水酸化ナトリウムを溶かしたメタノール溶液１００ｍｌに１０ｍｍｏｌのヘキサメチレンイミンを加え、更に１０ｍｍｏｌの二硫化炭素を反応させた。
次に、この溶液に５ｍｍｏｌの塩化銅二水和物を１００ｍｌのメタノールに溶かした溶液を加え、５分間撹拌し反応させた。
得られた沈殿物をろ過して集めた後、クロロホルム２００ｍｌに溶かし、その溶解液に２００ｍｌのメタノールを加え、約１００ｍｌに減圧濃縮した。更にメタノール２００ｍｌを加え、約５０ｍｌに減圧濃縮した後、得られた微結晶を吸引ろ過によって集め、少量のエーテルで洗浄し乾燥することで化５に示す、単核錯体Ｃｕ（Ｈｍ−ｄｔｃ）2を得た。
(Preparation of mononuclear complex)
First, 10 mmol of hexamethyleneimine was added to 100 ml of a methanol solution in which 10 mmol of sodium hydroxide was dissolved, and 10 mmol of carbon disulfide was further reacted.
Next, a solution obtained by dissolving 5 mmol of copper chloride dihydrate in 100 ml of methanol was added to this solution, and the mixture was stirred and reacted for 5 minutes.
The resulting precipitate was collected by filtration, dissolved in 200 ml of chloroform, 200 ml of methanol was added to the solution, and the mixture was concentrated under reduced pressure to about 100 ml. After adding 200 ml of methanol and concentrating under reduced pressure to about 50 ml, the resulting microcrystals were collected by suction filtration, washed with a small amount of ether and dried to show the mononuclear complex Cu (Hm-dtc) 2 shown in Chemical Formula 5. Got.

（配位高分子の作製）
化５に示す単核錯体０．１ｍｏｌをクロロホルム２０ｍｌに溶解し、臭化銅を０．２ｍｏｌをアセトニトリル３ｍｌとアセトン１７ｍｌの混合溶媒に溶解した後、それぞれの溶解液を混合し、１日室温で放置することによって、化６に示す実施例１に使用する配位高分子（［ＣｕI 2ＣｕIIＢｒ2（Ｈｍ−ｄｔｃ）2（ＣＨ3ＣＮ）2］n (ＣｕＢｒＨｍ１Ｄ)の黒色単結晶）を作製した。
（ＸはＢｒ） (Production of coordination polymer)
After dissolving 0.1 mol of the mononuclear complex shown in Chemical formula 5 in 20 ml of chloroform and 0.2 mol of copper bromide in a mixed solvent of 3 ml of acetonitrile and 17 ml of acetone, the respective solutions are mixed and mixed at room temperature for 1 day. By allowing to stand, the coordination polymer used in Example 1 shown in Chemical formula 6 ([Cu I 2 Cu II Br 2 (Hm-dtc) 2 (CH 3 CN) 2 ] n (CuBrHm1D) black single crystal) Was made.
(X is Br)

（色素増感太陽電池の作製）
低温焼結用酸化チタンペースト（品番：ＰＥＣＣ−ｋ０１、ペクセル・テクノロジー社製）０．１ｍｏｌと、上記で作製した配位高分子０．３ｍｏｌを乳鉢の中で混合し、ガラス基板上に形成した透明電極（ＩＴＯ）に５０μｍの厚さで塗布した。そして、この電極を５０℃で３０分乾燥させることによって陽極を作製した。
次に、ガラス基板上に形成した透明電極（ＩＴＯ）にＰＥＤＯＴ−ＴＭＡ（ポリ（３，４−エチレンジオキシチオフェン）テトラメタクリレート）を同重量のメタノールで溶解したものをスピンコートを行うことによって０．５ｍｇ塗布し、５０℃で３０分乾燥させることによって陰極を作製した。
次に、ポリエチレングリコール２００に、ヨウ化リチウムを０．５ｍｏｌ／Ｌの濃度で、さらにヨウ素を０．００５ｍｏｌ／Ｌの濃度で溶解することによって電解液を作製した。
最後に、ポリイミドフィルムをスペーサに用いて、作製した陽極と陰極を５０μｍのすき間を介在させるようにして貼り合わせ、電極の間に電解液を注入することで実施例１の色素増感太陽電池を得た。 (Preparation of dye-sensitized solar cell)
A titanium oxide paste for low-temperature sintering (product number: PECC-k01, manufactured by Pexel Technology) 0.1 mol and the coordination polymer 0.3 mol prepared above were mixed in a mortar and formed on a glass substrate. It apply | coated to the transparent electrode (ITO) with the thickness of 50 micrometers. Then, this electrode was dried at 50 ° C. for 30 minutes to produce an anode.
Next, spin coating is applied to a transparent electrode (ITO) formed on a glass substrate by dissolving PEDOT-TMA (poly (3,4-ethylenedioxythiophene) tetramethacrylate) with methanol of the same weight. A negative electrode was prepared by applying 0.5 mg and drying at 50 ° C. for 30 minutes.
Next, an electrolytic solution was prepared by dissolving lithium iodide in polyethylene glycol 200 at a concentration of 0.5 mol / L and further iodine at a concentration of 0.005 mol / L.
Finally, using the polyimide film as a spacer, the produced anode and cathode were bonded together with a 50 μm gap interposed therebetween, and the electrolyte solution was injected between the electrodes to thereby obtain the dye-sensitized solar cell of Example 1. Obtained.

実施例１に使用した臭化銅の代わりにヨウ化銅を用いた以外は実施例１と同様にして実施例２の色素増感太陽電池を得た。   A dye-sensitized solar cell of Example 2 was obtained in the same manner as in Example 1 except that copper iodide was used instead of the copper bromide used in Example 1.

（単核錯体の作製）
まず、１０ｍｍｏｌの水酸化ナトリウムを溶かしたメタノール溶液１００ｍｌに１０ｍｍｏｌのピぺリジンを加え、更に１０ｍｍｏｌの二硫化炭素を反応させた。
次に、この溶液に５ｍｍｏｌの塩化銅二水和物を１００ｍｌのメタノールに溶かした溶液を加え、５分間撹拌し反応させた。
得られた沈殿物をろ過して集めた後、クロロホルム２００ｍｌに溶かし、その溶解液に２００ｍｌのメタノールを加え、約１００ｍｌに減圧濃縮した。更にメタノール２００ｍｌを加え、約５０ｍｌに減圧濃縮した後、得られた微結晶を吸引ろ過によって集め、少量のエーテルで洗浄し乾燥することで化７に示す、単核錯体Ｃｕ（Ｐｉｐ−ｄｔｃ）2を得た。
(Preparation of mononuclear complex)
First, 10 mmol of piperidine was added to 100 ml of a methanol solution in which 10 mmol of sodium hydroxide was dissolved, and 10 mmol of carbon disulfide was further reacted.
Next, a solution obtained by dissolving 5 mmol of copper chloride dihydrate in 100 ml of methanol was added to this solution, and the mixture was stirred and reacted for 5 minutes.
The resulting precipitate was collected by filtration, dissolved in 200 ml of chloroform, 200 ml of methanol was added to the solution, and the mixture was concentrated under reduced pressure to about 100 ml. After adding 200 ml of methanol and concentrating under reduced pressure to about 50 ml, the resulting microcrystals were collected by suction filtration, washed with a small amount of ether and dried to show the mononuclear complex Cu (Pip-dtc) 2 shown in Chemical formula 7. Got.

（配位高分子の作製）
化７に示す単核錯体０．１ｍｏｌをクロロホルム２０ｍｌに溶解し、臭化銅を０．２ｍｏｌをアセトニトリル３ｍｌとアセトン１７ｍｌの混合溶媒に溶解した後、それぞれの溶解液を混合し、１日室温で放置することによって、実施例３に使用する配位高分子（［ＣｕI 2ＣｕIIＢｒ2（Ｐｉｐ−ｄｔｃ）2（ＣＨ3ＣＮ）2］n (ＣｕＢｒＰｉｐ１Ｄ)の黒色単結晶）を作製した。 (Production of coordination polymer)
After dissolving 0.1 mol of the mononuclear complex shown in Chemical Formula 7 in 20 ml of chloroform and 0.2 mol of copper bromide in a mixed solvent of 3 ml of acetonitrile and 17 ml of acetone, the respective solutions are mixed and mixed at room temperature for 1 day. By allowing to stand, the coordination polymer ([Cu I 2 Cu II Br 2 (Pip-dtc) 2 (CH 3 CN) 2 ] n (CuBrPip1D) black single crystal) used in Example 3 was produced.

（色素増感太陽電池の作製）
実施例１と同様の手法にて実施例３の色素増感太陽電池を得た。 (Preparation of dye-sensitized solar cell)
A dye-sensitized solar cell of Example 3 was obtained in the same manner as in Example 1.

実施例３に使用した臭化銅の代わりにヨウ化銅を用いた以外は実施例３と同様にして実施例４の色素増感太陽電池を得た。   A dye-sensitized solar cell of Example 4 was obtained in the same manner as Example 3 except that copper iodide was used instead of copper bromide used in Example 3.

（単核錯体の作製）
まず、１０ｍｍｏｌの水酸化ナトリウムを溶かしたメタノール溶液１００ｍｌに１０ｍｍｏｌのジプロピルアミンを加え、更に１０ｍｍｏｌの二硫化炭素を反応させた。
次に、この溶液に５ｍｍｏｌの塩化銅二水和物を１００ｍｌのメタノールに溶かした溶液を加え、５分間撹拌し反応させた。
得られた沈殿物をろ過して集めた後、クロロホルム２００ｍｌに溶かし、その溶解液に２００ｍｌのメタノールを加え、約１００ｍｌに減圧濃縮した。更にメタノール２００ｍｌを加え、約５０ｍｌに減圧濃縮した後、得られた微結晶を吸引ろ過によって集め、少量のエーテルで洗浄し乾燥することで化８に示す、単核錯体Ｃｕ（ｎＰｒ2−ｄｔｃ）2を得た。
(Preparation of mononuclear complex)
First, 10 mmol of dipropylamine was added to 100 ml of a methanol solution in which 10 mmol of sodium hydroxide had been dissolved, and 10 mmol of carbon disulfide was further reacted.
Next, a solution obtained by dissolving 5 mmol of copper chloride dihydrate in 100 ml of methanol was added to this solution, and the mixture was stirred and reacted for 5 minutes.
The resulting precipitate was collected by filtration, dissolved in 200 ml of chloroform, 200 ml of methanol was added to the solution, and the mixture was concentrated under reduced pressure to about 100 ml. After adding 200 ml of methanol and concentrating under reduced pressure to about 50 ml, the resulting microcrystals were collected by suction filtration, washed with a small amount of ether and dried to show the mononuclear complex Cu (nPr 2 -dtc) 2 got.

（配位高分子の作製）
化８に示す単核錯体０．１ｍｏｌをクロロホルム２０ｍｌに溶解し、塩化銅二水和物０．４ｍｏｌをアセトン２０ｍｌに溶解した後、それぞれの溶解液を混合し、１日室温で放置することによって、実施例５に使用する配位高分子（［ＣｕI 6ＣｕIIIＣｌ7 (ｎＰｒ2−ｄｔｃ)2］n (ＣｕＣｌｎＰｒ２Ｄ)の黒色単結晶）を作製した。 (Production of coordination polymer)
By dissolving 0.1 mol of the mononuclear complex shown in Chemical Formula 8 in 20 ml of chloroform and 0.4 mol of copper chloride dihydrate in 20 ml of acetone, the respective solutions are mixed and left at room temperature for 1 day. Then, a coordination polymer ([Cu I 6 Cu III Cl 7 (nPr 2 -dtc) 2 ] n (CuClnPr2D) black single crystal) used in Example 5 was produced.

（色素増感太陽電池の作製）
実施例１と同様の手法にて実施例５の色素増感太陽電池を得た。 (Preparation of dye-sensitized solar cell)
A dye-sensitized solar cell of Example 5 was obtained in the same manner as in Example 1.

まず、１０ｍｍｏｌの水酸化ナトリウムを溶かしたメタノール溶液１００ｍｌに１０ｍｍｏｌのジブチルアミンを加え、更に１０ｍｍｏｌの二硫化炭素を反応させた。
次に、この溶液に５ｍｍｏｌの塩化銅二水和物を１００ｍｌのメタノールに溶かした溶液を加え、５分間撹拌し反応させた。
得られた沈殿物をろ過して集めた後、クロロホルム２００ｍｌに溶かし、その溶解液に２００ｍｌのメタノールを加え、約１００ｍｌに減圧濃縮した。更にメタノール２００ｍｌを加え、約５０ｍｌに減圧濃縮した後、得られた微結晶を吸引ろ過によって集め、少量のエーテルで洗浄し乾燥することで化９に示す、単核錯体Ｃｕ（ｎＢｕ2−ｄｔｃ）2を得た。
First, 10 mmol of dibutylamine was added to 100 ml of methanol solution in which 10 mmol of sodium hydroxide was dissolved, and 10 mmol of carbon disulfide was further reacted.
Next, a solution obtained by dissolving 5 mmol of copper chloride dihydrate in 100 ml of methanol was added to this solution, and the mixture was stirred and reacted for 5 minutes.
The resulting precipitate was collected by filtration, dissolved in 200 ml of chloroform, 200 ml of methanol was added to the solution, and the mixture was concentrated under reduced pressure to about 100 ml. After adding 200 ml of methanol and concentrating under reduced pressure to about 50 ml, the resulting microcrystals were collected by suction filtration, washed with a small amount of ether and dried to give a mononuclear complex Cu (nBu 2 -dtc) 2 got.

（配位高分子の作製）
化９に示す単核錯体０．１ｍｏｌをクロロホルム２０ｍｌに溶解し、臭化銅０．２ｍｏｌを数滴の水になじませてからアセトン２０ｍｌに溶解した後、それぞれの溶解液を混合し、１日室温で放置することによって、実施例６に使用する配位高分子（［ＣｕI 7ＣｕIIＢｒ7（ｎＢｕ2−ｄｔｃ）2］n (ＣｕＢｒｎＢｕ２Ｄ)の黒色単結晶）を作製した。 (Production of coordination polymer)
After dissolving 0.1 mol of the mononuclear complex shown in Chemical Formula 9 in 20 ml of chloroform, dissolving 0.2 mol of copper bromide in several drops of water and then dissolving in 20 ml of acetone, the respective solutions are mixed and mixed for 1 day. by leaving at room temperature to prepare a coordination polymer used in example 6 ([Cu I 7 Cu II Br 7 (nBu 2 -dtc) 2] black single crystal n (CuBrnBu2D)).

（色素増感太陽電池の作製）
実施例１と同様の手法にて実施例６の色素増感太陽電池を得た。 (Preparation of dye-sensitized solar cell)
A dye-sensitized solar cell of Example 6 was obtained in the same manner as in Example 1.

（単核錯体の作製）
まず、１０ｍｍｏｌの水酸化ナトリウムを溶かしたメタノール溶液１００ｍｌに１０ｍｍｏｌのピロリジンを加え、更に１０ｍｍｏｌの二硫化炭素を反応させた。
次に、この溶液に５ｍｍｏｌの塩化銅二水和物を１００ｍｌのメタノールに溶かした溶液を加え、５分間撹拌し反応させた。
得られた沈殿物をろ過して集めた後、クロロホルム２００ｍｌに溶かし、その溶解液に２００ｍｌのメタノールを加え、約１００ｍｌに減圧濃縮した。更にメタノール２００ｍｌを加え、約５０ｍｌに減圧濃縮した後、得られた微結晶を吸引ろ過によって集め、少量のエーテルで洗浄し乾燥することで化１０に示す、単核錯体Ｃｕ（Ｐｙｒ−ｄｔｃ）2を得た。
(Preparation of mononuclear complex)
First, 10 mmol of pyrrolidine was added to 100 ml of a methanol solution in which 10 mmol of sodium hydroxide was dissolved, and 10 mmol of carbon disulfide was further reacted.
Next, a solution obtained by dissolving 5 mmol of copper chloride dihydrate in 100 ml of methanol was added to this solution, and the mixture was stirred and reacted for 5 minutes.
The resulting precipitate was collected by filtration, dissolved in 200 ml of chloroform, 200 ml of methanol was added to the solution, and the mixture was concentrated under reduced pressure to about 100 ml. After adding 200 ml of methanol and concentrating under reduced pressure to about 50 ml, the resulting microcrystals were collected by suction filtration, washed with a small amount of ether and dried to show the mononuclear complex Cu (Pyr-dtc) 2 shown in Chemical formula 10. Got.

（配位高分子の作製）
化１０に示す単核錯体０．１ｍｏｌをクロロホルム２０ｍｌに溶解し、ＣｕＢｒＳ（ＣＨ3）2０．４ｍｏｌをアセトニトリル１０ｍｌに溶解してから１０ｍｌのアセトンで希釈した後、それぞれの溶解液を混合し、１日室温で放置することによって、実施例７に使用する配位高分子（｛［ＣｕI 4ＣｕII 2Ｂｒ4（Ｐｙｒ−ｄｔｃ）4］ＣＨＣｌ3｝n（ＣｕＢｒＰｙｒ３Ｄ）の黒色単結晶）を作製した。 (Production of coordination polymer)
After dissolving 0.1 mol of the mononuclear complex shown in Chemical Formula 10 in 20 ml of chloroform, dissolving 0.4 mol of CuBrS (CH 3 ) 2 in 10 ml of acetonitrile and then diluting with 10 ml of acetone, the respective solutions are mixed, The coordination polymer ({[Cu I 4 Cu II 2 Br 4 (Pyr-dtc) 4 ] CHCl 3 } n (CuBrPyr3D) black single crystal) used in Example 7 was allowed to stand at room temperature for 1 day. Produced.

（色素増感太陽電池の作製）
実施例１と同様の手法にて実施例７の色素増感太陽電池を得た。 (Preparation of dye-sensitized solar cell)
A dye-sensitized solar cell of Example 7 was obtained in the same manner as in Example 1.

比較例Comparative example

実施例１に使用した配位高分子の代わりに、化５に示す単核錯体を用いた以外は実施例１と同様にして比較例の色素増感太陽電池を得た。   A dye-sensitized solar cell of Comparative Example was obtained in the same manner as in Example 1 except that the mononuclear complex shown in Chemical Formula 5 was used instead of the coordination polymer used in Example 1.

次に、上記によって得た実施例１〜７および比較例の色素増感太陽電池について、各特性の測定を行った。   Next, each characteristic was measured about the dye-sensitized solar cell of Examples 1-7 obtained by the above, and a comparative example.

（電流密度ー電圧特性の測定）
電流密度ー電圧特性はソーラーシミュレータ（ＡＭ１．５、１００ｍＷ／ｃｍ2）を用いて測定した。測定結果を図１〜４に示す。
そして、図１から得られる、電圧がゼロの時の電流密度を短絡電流密度（Ｊｓｃ）、負荷電圧をかけて電流密度がゼロになった時の電圧を開放電圧（Ｖｏｃ）、電流密度―電圧曲線から得られる最大出力を短絡電流密度と開放電圧の積で除したものをフィルファクタ（ＦＦ）、最大出力を入射光強度で除したものを変換効率ηとした。
その結果、実施例１の色素増感太陽電池は、Ｊｓｃ＝０．４１ｍＡ／ｃｍ2、Ｖｏｃ＝０．５０Ｖ、ＦＦ＝０．５３、η＝０．１１％であった。実施例２の色素増感太陽電池は、Ｊｓｃ＝０．３９ｍＡ／ｃｍ2、Ｖｏｃ＝０．５６Ｖ、ＦＦ＝０．５３、η＝０．１１％であった。一方、比較例の色素増感太陽電池は、Ｊｓｃ＝０．２０ｍＡ／ｃｍ2、Ｖｏｃ＝０．５５Ｖ、ＦＦ＝０．５８、η＝０．０６％であった。
以上のことから、色素に配位高分子を用いることによって、単核錯体を色素に用いた場合よりも短絡電流密度（Ｊｓｃ）が増大し、その結果変換効率ηも約２倍になることがわかる。
また、図２〜４は実施例１〜７の色素増感太陽電池における、電流密度ー電圧特性の測定結果である。 (Measurement of current density vs. voltage characteristics)
The current density-voltage characteristics were measured using a solar simulator (AM1.5, 100 mW / cm 2 ). The measurement results are shown in FIGS.
1, the current density when the voltage is zero is the short-circuit current density (Jsc), the voltage when the load voltage is applied and the current density is zero is the open circuit voltage (Voc), and the current density-voltage The value obtained by dividing the maximum output obtained from the curve by the product of the short-circuit current density and the open-circuit voltage was defined as the fill factor (FF), and the value obtained by dividing the maximum output by the incident light intensity was defined as the conversion efficiency η.
As a result, the dye-sensitized solar cell of Example 1 was Jsc = 0.41 mA / cm 2 , Voc = 0.50 V, FF = 0.53, and η = 0.11%. The dye-sensitized solar cell of Example 2 had Jsc = 0.39 mA / cm 2 , Voc = 0.56V, FF = 0.53, and η = 0.11%. On the other hand, the dye-sensitized solar cell of the comparative example had Jsc = 0.20 mA / cm 2 , Voc = 0.55V, FF = 0.58, and η = 0.06%.
From the above, by using a coordination polymer for the dye, the short-circuit current density (Jsc) increases as compared with the case where the mononuclear complex is used for the dye, and as a result, the conversion efficiency η is also approximately doubled. Recognize.
2 to 4 show measurement results of current density-voltage characteristics in the dye-sensitized solar cells of Examples 1 to 7.

（拡散反射スペクトルの測定）
拡散反射スペクトルは、実施例１、実施例２、比較例の色素増感太陽電池０．０１ｍｏｌを８０ｍｇの酸化マグネシウム（ＭｇＯ）に混合したものについて測定を行った。測定結果を図５に示す。
その結果、配位高分子を色素に用いた実施例１と実施例２の色素増感太陽電池は、単核錯体を色素に用いた比較例の色素増感太陽電池に比べ、６００〜８００ｎｍのいわゆる可視光域において高い吸収を示すことがわかる。なおこのことは、本発明の色素増感太陽電池の変換効率ηが高い理由の１つであると考えられる。 (Measurement of diffuse reflection spectrum)
The diffuse reflection spectrum was measured for a mixture of 0.01 mol of the dye-sensitized solar cell of Example 1, Example 2, and Comparative Example in 80 mg of magnesium oxide (MgO). The measurement results are shown in FIG.
As a result, the dye-sensitized solar cells of Example 1 and Example 2 using the coordination polymer as the dye are 600 to 800 nm in comparison with the dye-sensitized solar cell of the comparative example using the mononuclear complex as the dye. It can be seen that high absorption is shown in the so-called visible light region. This is considered to be one of the reasons why the conversion efficiency η of the dye-sensitized solar cell of the present invention is high.

（最高被占軌道：ＨＯＭＯと最低空軌道：ＬＵＭＯの測定）
図５に示す拡散反射スペクトルの結果から最低空軌道（ＬＵＭＯ）を、図６に示す光電子分光測定の結果から最高被占軌道（ＨＯＭＯ）を算出した。
その結果、実施例１の色素増感太陽電池はＨＯＭＯが−５．２０ｅＶ、ＬＵＭＯが−３．７２ｅＶであり、実施例２の色素増感太陽電池はＨＯＭＯが−５．１０ｅＶ、ＬＵＭＯが−３．６２ｅＶであり、比較例の色素増感太陽電池はＨＯＭＯが−４．９５ｅＶ、ＬＵＭＯが−３．５０ｅＶであった。
ここで、酸化チタンの伝導帯は−３．８０ｅＶであることから、実施例１、実施例２の色素増感太陽電池のＬＵＭＯレベルよりも低いエネルギー準位にあることがわかる。従って、実施例１、実施例２の色素増感太陽電池に太陽光が照射されて励起した電子はスムースに酸化チタンへと送られることがわかる。
また、実施例１、実施例２に使用した電解液（ヨウ化リチウム／ヨウ素溶液）の酸化還元電位は−４．８０ｅＶであることから、実施例１、実施例２の色素増感太陽電池のＨＯＭＯレベルよりも高いエネルギー準位にあることがわかる。従って、太陽光が照射されて励起した電子が酸化チタンに送られることによって欠損した配位高分子の空軌道に、電解液から電子がスムースに送られることがわかる。 (Measurement of highest occupied orbit: HOMO and lowest empty orbit: LUMO)
The lowest unoccupied orbit (LUMO) was calculated from the diffuse reflection spectrum result shown in FIG. 5, and the highest occupied orbit (HOMO) was calculated from the result of photoelectron spectroscopy measurement shown in FIG.
As a result, the dye-sensitized solar cell of Example 1 has a HOMO of −5.20 eV and a LUMO of −3.72 eV, and the dye-sensitized solar cell of Example 2 has a HOMO of −5.10 eV and a LUMO of −3. The dye-sensitized solar cell of the comparative example had a HOMO of −4.95 eV and a LUMO of −3.50 eV.
Here, since the conduction band of titanium oxide is −3.80 eV, it can be seen that the energy level is lower than the LUMO level of the dye-sensitized solar cells of Examples 1 and 2. Therefore, it can be seen that the electrons excited when the dye-sensitized solar cells of Example 1 and Example 2 are irradiated with sunlight are smoothly sent to titanium oxide.
Moreover, since the oxidation-reduction potential of the electrolyte solution (lithium iodide / iodine solution) used in Example 1 and Example 2 is −4.80 eV, the dye-sensitized solar cells of Examples 1 and 2 are used. It can be seen that the energy level is higher than the HOMO level. Therefore, it can be seen that electrons are smoothly sent from the electrolyte solution to the vacant orbits of the coordination polymer that is lost when the electrons excited by irradiation of sunlight are sent to titanium oxide.

（インピーダンス特性の測定：Ｃｏｌｅ−Ｃｏｌｅ Ｐｌｏｔ）
６４４０Ｂ Ｓｅｒｉｅｓ Ｐｒｅｃｉｓｉｏｎ Ｃｏｍｐｏｎｅｎｔ Ａｎａｌｙｚｅｒ（Ｗａｙｎｅ Ｋｅｒｒ Ｅｌｅｃｔｒｏｎｉｃｓ社製）によって実施例１、実施例２、比較例のインピーダンス特性を測定し、図７に示すようにインピーダンスの実部及び虚部の測定値について、コールコールプロットを行った。ここで、コールコールプロットにおいては、グラフ内においてプロットされた半円の直径が色素−酸化チタン界面での抵抗に相当する。
従って、図７に示す通り、実施例１、実施例２の色素増感太陽電池は、比較例の色素増感太陽電池に比べて半円の半径が小さいことから、色素−酸化チタン界面における抵抗を減少させることができ、スムースな電子移動を行うことができることがわかる。 (Measurement of impedance characteristics: Cole-Cole Plot)
The impedance characteristics of Example 1, Example 2, and Comparative Example were measured by 6440B Series Precision Component Analyzer (manufactured by Wayne Kerr Electronics), and the measured values of the real part and the imaginary part of the impedance as shown in FIG. A plot was made. Here, in the Cole-Cole plot, the diameter of the semicircle plotted in the graph corresponds to the resistance at the dye-titanium oxide interface.
Therefore, as shown in FIG. 7, the dye-sensitized solar cells of Example 1 and Example 2 have a semicircular radius smaller than that of the dye-sensitized solar cell of the comparative example. It can be seen that the electron can be reduced and smooth electron movement can be performed.

本発明は色素増感太陽電池に用いることができる。   The present invention can be used for a dye-sensitized solar cell.

１ 金属イオン
２ 配位子 1 Metal ion 2 Ligand

Claims (6)

遷移金属元素の中から選ばれる１種または２種以上の金属イオンと、
前記金属イオンに配位可能な１種または２種以上の含硫黄化合物または含窒素化合物からなる配位子を含有する配位高分子を用いることを特徴とする色素増感太陽電池。 One or more metal ions selected from transition metal elements;
A dye-sensitized solar cell comprising a coordination polymer containing a ligand composed of one or more sulfur-containing compounds or nitrogen-containing compounds capable of coordinating with the metal ions. 前記遷移金属元素が、
Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, Auの中から選ばれる１種または２種以上の金属元素であることを特徴とする請求項１に記載の色素増感太陽電池。 The transition metal element is
2. The metal element according to claim 1, which is one or more metal elements selected from Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au. Dye-sensitized solar cell. 前記配位子が、
下記の化１または化２で表わされるジチオカルバミン酸イオンの誘導体の中から選ばれる１種または２種以上の誘導体であることを特徴とする請求項１または請求項２に記載の色素増感太陽電池。
（Ｒ1およびＲ2は、同一または異なる脂肪族炭化水素基、置換脂肪族炭化水素基、芳香族炭化水素基、置換芳香族炭化水素基、複素環基および置換複素環基を示す。）
（Ｒ3は、少なくとも１つの窒素原子を含む複素環基または置換複素環基を示す。） The ligand is
3. The dye-sensitized solar cell according to claim 1, wherein the dye-sensitized solar cell is one or more derivatives selected from derivatives of dithiocarbamate ions represented by the following chemical formula 1 or chemical formula 2: .
(R 1 and R 2 represent the same or different aliphatic hydrocarbon group, substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, substituted aromatic hydrocarbon group, heterocyclic group and substituted heterocyclic group.)
(R 3 represents a heterocyclic group or a substituted heterocyclic group containing at least one nitrogen atom.) 前記配位高分子が、
さらに臭素イオンまたはヨウ素イオンを含むことによって構成されたものであることを特徴とする請求項１から請求項３のいずれか一項に記載の色素増感太陽電池。 The coordination polymer is
The dye-sensitized solar cell according to any one of claims 1 to 3, further comprising bromine ions or iodine ions. 前記配位高分子が、
遷移金属元素に銅を用い、
前記配位子にヘキサメチレンジチオカルバミン酸を用い、
かつ臭素イオンまたはヨウ素イオンを用いて構成されたものであることを特徴とする請求項４に記載の色素増感太陽電池。 The coordination polymer is
Using copper as the transition metal element,
Hexamethylenedithiocarbamic acid is used as the ligand,
The dye-sensitized solar cell according to claim 4, wherein the dye-sensitized solar cell is configured using bromine ions or iodine ions. 酸化チタンのペーストと前記配位高分子とを混合する工程を備えることを特徴とした請求項１から請求項５のいずれか一項に記載の色素増感太陽電池の製造方法。 The method for producing a dye-sensitized solar cell according to any one of claims 1 to 5, further comprising a step of mixing a titanium oxide paste and the coordination polymer.
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