JP2005047857A - Ruthenium complex useful as sensitizer - Google Patents

Ruthenium complex useful as sensitizer Download PDF

Info

Publication number
JP2005047857A
JP2005047857A JP2003282160A JP2003282160A JP2005047857A JP 2005047857 A JP2005047857 A JP 2005047857A JP 2003282160 A JP2003282160 A JP 2003282160A JP 2003282160 A JP2003282160 A JP 2003282160A JP 2005047857 A JP2005047857 A JP 2005047857A
Authority
JP
Japan
Prior art keywords
group
ruthenium complex
formula
complex compound
compound represented
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2003282160A
Other languages
Japanese (ja)
Other versions
JP4292291B2 (en
Inventor
Takashi Yamaguchi
岳志 山口
Hideki Sugihara
秀樹 杉原
Shinri Yanagida
真利 柳田
Hironori Arakawa
裕則 荒川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
National Institute of Advanced Industrial Science and Technology AIST
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute of Advanced Industrial Science and Technology AIST filed Critical National Institute of Advanced Industrial Science and Technology AIST
Priority to JP2003282160A priority Critical patent/JP4292291B2/en
Publication of JP2005047857A publication Critical patent/JP2005047857A/en
Application granted granted Critical
Publication of JP4292291B2 publication Critical patent/JP4292291B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Landscapes

  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ruthenium complex useful as a sensitizer efficiently using light energy. <P>SOLUTION: The ruthenium complex compound is represented by formula(I): RuLL'X [ L is a 2,2'-6',2"-terpyridine derivative group containing either of at least one carboxy group, sulfo group or phosphate group as linkage group, wherein each of the linkage group(s) is one of alkali metal salt and ammonium salt of an acid; L' is an ethylenediamine derivative group of formula(a)( wherein, A, A', R, R', R" and R"' are each an alkyl, alkoxyalkyl, aminoalkyl, perfluoroalkyl, aryl or H; and X is a monodentate ligand selected from halide, cyano, isothiocyano and thiolato groups )]. This ruthenium complex compound is to be used as a sensitizer in transforming light energy to electric energy using a coloring matter-sensitive semiconductor. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、光エネルギーを効率よく利用する増感剤として有用なルテニウム錯体、このルテニウム錯体を用いた色素増感半導体電極及びこの電極を含む太陽電池に関するものである。   The present invention relates to a ruthenium complex useful as a sensitizer that efficiently utilizes light energy, a dye-sensitized semiconductor electrode using the ruthenium complex, and a solar cell including the electrode.

従来、酸化チタン等の酸化物半導体の表面に可視領域に吸収をもつルテニウム錯体等の化合物を吸着させてその増感作用を使って光エネルギーの利用効率を向上させることが知られていた。しかしながらこれまで増感剤として使用されている化合物は主にビピリジン誘導体を配位子としてもつルテニウム錯体であった。（非特許文献１及び特許文献１参照）
Md. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Mueller, P.Liska, N. Vlachopoulos, M. Graetzel, J. Am. Chem. Soc., 115 (1993) 6382 特開２００１−００６７６０号公報 Conventionally, it has been known that a compound such as a ruthenium complex having absorption in the visible region is adsorbed on the surface of an oxide semiconductor such as titanium oxide and the utilization efficiency of light energy is improved by using the sensitizing action. However, the compounds used so far as sensitizers are mainly ruthenium complexes having bipyridine derivatives as ligands. (See Non-Patent Document 1 and Patent Document 1)
Md. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Mueller, P. Liska, N. Vlachopoulos, M. Graetzel, J. Am. Chem. Soc., 115 (1993) 6382 JP 2001-006760 A

本発明は、従来のルテニウム錯体では、不十分であった長波長領域の光エネルギーの利用を、テルピリジン誘導体とエチレンジアミン誘導体を配位子とする新しいルテニウム錯体を用いて実現するものであり、より効率の高い光エネルギーの利用を可能とする増感剤材料を提供するものである。   The present invention realizes the utilization of light energy in the long wavelength region, which was insufficient with conventional ruthenium complexes, by using a new ruthenium complex having a terpyridine derivative and an ethylenediamine derivative as ligands, and is more efficient. It is an object of the present invention to provide a sensitizer material that enables the use of high light energy.

本発明者は、半導体を修飾する増感剤について鋭意研究を重ねた結果、ルテニウムを中心金属とし、カルボキシル基などの結合基をもつテルピリジン誘導体とエチレンジアミン誘導体を配位子としてもつ錯体が増感剤として有効であることを発見した。
公知のルテニウム錯体誘導体より吸収領域の広い本錯体が光電変換用色素として使用可能であることを見いだし、この知見に基づいて本発明をなすに至った。
即ち、本発明によれば、下記一般式（I)で表されるルテニウム錯体が提供される。

RuＬＬ’Ｘ （Ｉ）

（式中、Ｌは少なくとも１個の結合基であるカルボキシル基、スルホン酸基、リン酸基のうちのいずれかを含む、２，２’−６’、２’’−テルピリジン誘導体であり、それぞれの結合基は酸のアルカリ金属、アンモニウムから選ばれる１種であり、Ｌ’は式（ａ）で表されるエチレンジアミン誘導体であって、

Figure 2005047857
（ここでＡ、Ａ’、Ｒ、R’、R''及びＲ'''はそれぞれ独立にアルキル、アルコキシアルキル、アミノアルキル、パーフルオロアルキル、アリール又は水素原子であり、Ｘはハロゲン化物、シアノ基、イソチオシアノ基、チオシアノ基、チオラート、から選択される単座配位子である。））で表されるルテニウム錯体化合物を見出し、この化合物が光エネルギーを電気エネルギーに変換するに際し、増感剤として有用である事実を突き止めた。
さらに、本発明によれば、導電性表面に形成された酸化物半導体膜に前記ルテニウム錯体を吸着させてなる色素増感半導体電極が提供される。
さらにまた、本発明によれば、前記電極と、その対極と、それらの電極に接触するレドックス電解質とから構成されることを特徴とする太陽電池が提供される。 As a result of intensive research on a sensitizer for modifying a semiconductor, the present inventor has found that a complex having a ruthenium as a central metal and a terpyridine derivative having a bonding group such as a carboxyl group and an ethylenediamine derivative as a ligand is a sensitizer. As found to be effective.
It has been found that this complex having a wider absorption region than known ruthenium complex derivatives can be used as a dye for photoelectric conversion, and the present invention has been made based on this finding.
That is, according to the present invention, a ruthenium complex represented by the following general formula (I) is provided.

RuLL'X (I)

(In the formula, L is a 2,2′-6 ′, 2 ″ -terpyridine derivative containing any one of a carboxyl group, a sulfonic acid group, and a phosphoric acid group as at least one bonding group, Is a group selected from an alkali metal of acid and ammonium, and L ′ is an ethylenediamine derivative represented by the formula (a),
Figure 2005047857
 Wherein A, A ′, R, R ′, R ″ and R ′ ″ are each independently an alkyl, alkoxyalkyl, aminoalkyl, perfluoroalkyl, aryl or hydrogen atom, and X is a halide, cyano Is a monodentate ligand selected from a group, an isothiocyano group, a thiocyano group, and a thiolate.)) When a ruthenium complex compound represented by the following formula is found and this compound converts light energy into electric energy, I found out the fact that it was useful.
Furthermore, according to the present invention, there is provided a dye-sensitized semiconductor electrode obtained by adsorbing the ruthenium complex on an oxide semiconductor film formed on a conductive surface.
Furthermore, according to the present invention, there is provided a solar cell comprising the electrode, a counter electrode thereof, and a redox electrolyte in contact with the electrodes.

本発明により実現された金属錯体は、熱、光に対し安定であり、そのカルボキシル基等によって半導体表面に効果的に吸着することが出来、幅広い吸収領域と大きな吸光係数をもつことにより、高い光電変換効率を達成することが可能となった。   The metal complex realized by the present invention is stable against heat and light, can be effectively adsorbed on the semiconductor surface by its carboxyl group, etc., and has a wide absorption region and a large extinction coefficient. It became possible to achieve conversion efficiency.

前記一般式（I)におけるLは、少なくとも一つのアニオン基を含有する２，２’；２”，６’−テルピリジン系化合物からなる配位子を示す。
前記アニオン基には、従来公知の各種のもの、例えば、カルボキシル基、スルホン酸、リン酸基等が包含される。これらのアニオン基は、遊離酸基であることができる他、塩形成性陽イオン（Ｎａ、Ｋ等のアルカリ金属のイオン、アンモニウムイオン等）で中和された中和塩基であることができる。配位子Ｌに含まれるアニオン基の数は１つ以上、好ましくは２つ以上であり、その上限値は、通常、３つ程度である。
前記一般式（Ｉ）におけるＬ’は、一般式（ａ）で表されるエチレンジアミン誘導体である。

Figure 2005047857
前記式中、Ａ，Ａ’，Ｒ，Ｒ’，Ｒ”，Ｒ'''は、それぞれ独立にアルキル、アルコキシアルキル、アミノアルキル、パーフルオロアルキル、アリール又は水素原子である。前記アルキル基は、その炭素数は１〜２０であり、好ましくは１〜４である。
L in the general formula (I) represents a ligand composed of a 2,2 ′; 2 ″, 6′-terpyridine compound containing at least one anionic group.
Examples of the anionic group include conventionally known various groups such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. These anionic groups can be free acid groups, and can also be neutralized bases neutralized with salt-forming cations (alkali metal ions such as Na and K, ammonium ions, etc.). The number of anionic groups contained in the ligand L is 1 or more, preferably 2 or more, and the upper limit is usually about 3.
L ′ in the general formula (I) is an ethylenediamine derivative represented by the general formula (a).
Figure 2005047857
 In the above formula, A, A ′, R, R ′, R ″, and R ′ ″ each independently represent an alkyl, alkoxyalkyl, aminoalkyl, perfluoroalkyl, aryl, or hydrogen atom. The carbon number is 1-20, Preferably it is 1-4.

４，４’，４”−トリメトキシカルボニル−２，２’；２”，６’−テルピリジンとトリクロロルテニウムをアルゴン雰囲気下、エタノール中２時間加熱環流する。冷却後、得られたトリクロロ（４，４’，４”−トリメトキシカルボニル−２，２’；２”、６−テルピリジン）ルテニウム(II)のＮ，Ｎ−ジメチルホルムアミド溶液にエチレンジアミン１．５当量を加えさらに１０分間マイクロ波加熱装置を用いて加熱することによりクロロ（エチレンジアミン）（４，４’，４”−トリメトキシカルボニル−２，２’；２”、６−テルピリジン）ルテニウム(II)を得る。さらにＮ、Ｎ−ジメチルホルムアミド中、１．５当量のチオシアン化ナトリウムの水溶液を加え加熱する。得られたエチレンジアミン（チオシアナート−Ｎ）（４，４’，４”−トリメトキシカルボニル−２，２’；２”、６−テルピリジン）ルテニウム(II)を、トリエチルアミンを加え１２時間加熱環流する。反応混合物から溶媒をロータリーエバポレータで留去し、固形物を水にとかした後、塩酸酸性として生成する固体を濾別し乾燥することにより目的とする錯体、エチレンジアミン（チオシアナート−Ｎ）（４，４’，４”−トリカルボキシ−２，２’；２”、６−テルピリジン）ルテニウム(II)を得る。
この錯体は、暗緑色の固体でありレクトロスプレー質量分析装置による測定値として、Ｃ２１Ｈ１９Ｎ６Ｏ６ＲｕＳの分子量に相当する５８５（Ｍ＋）を示す。重水中の核磁気共鳴スペクトルとして、１Ｈ−ＮＭＲ（δ、４００ＭＨｚ）８．９５（ｄ，Ｊ＝６Ｈｚ，２Ｈ）、８．７７（ｓ，２Ｈ）、８．７５（ｓ，２Ｈ）、８．００（ｄｄ，Ｊ＝２Ｈｚ，Ｊ＝６Ｈｚ，２Ｈ）、５．７０（ｔ，２Ｈ）、４．７−４．９（溶媒ピークとの重なりのため確認困難）、３．２３（ｔ，２Ｈ）、２．４５（ｔ，２Ｈ）、可視吸収スペクトルとしてモル吸光係数５４００Ｍ−１ｃｍ−１の吸収極大を５６０ｎｍに示す。
このルテニウム錯体を導電性ガラス表面に作成した酸化チタン多孔質膜に吸着させることにより可視光応答性の電極を構成した。導電性ガラス表面に白金を蒸着した対電極との間に、0.1Mヨウ化リチウム、0.05Mヨウ素、0.6M1.2-ジメチル-3-プロピルイミダゾリウムヨージド、アセトニトリルから構成される電解質溶液をはさみ太陽電池を構成する。その結果AM1.5の擬似太陽光照射下において、短絡電流18.7ｍＡ／ｃｍ2、開放電圧0.57Ｖ、ＦＦ69%の光電流を取り出すことが出来た。
（従来例） 4,4 ′, 4 ″ -trimethoxycarbonyl-2,2 ′; 2 ″, 6′-terpyridine and trichlororuthenium are heated to reflux in ethanol for 2 hours under an argon atmosphere. After cooling, 1.5 eq. Of ethylenediamine was added to a solution of trichloro (4,4 ′, 4 ″ -trimethoxycarbonyl-2,2 ′; 2 ″, 6-terpyridine) ruthenium (II) in N, N-dimethylformamide. Chloro (ethylenediamine) (4,4 ′, 4 ″ -trimethoxycarbonyl-2,2 ′; 2 ″, 6-terpyridine) ruthenium (II) by heating for 10 minutes using a microwave heating apparatus. obtain. Further, 1.5 equivalent of an aqueous solution of sodium thiocyanide in N, N-dimethylformamide is added and heated. The obtained ethylenediamine (thiocyanate-N) (4,4 ′, 4 ″ -trimethoxycarbonyl-2,2 ′; 2 ″, 6-terpyridine) ruthenium (II) is added with triethylamine and heated to reflux for 12 hours. The solvent was distilled off from the reaction mixture with a rotary evaporator, the solid was dissolved in water, and then the solid produced as acidic with hydrochloric acid was filtered off and dried to obtain the target complex, ethylenediamine (thiocyanate-N) (4, 4 ', 4 ″ -tricarboxy-2,2 ′; 2 ″, 6-terpyridine) ruthenium (II).
This complex is a dark green solid, and shows 585 (M + ) corresponding to the molecular weight of C21H19N6O6RuS as a measurement value by a Letrotromass spectrometer. As nuclear magnetic resonance spectra in heavy water, 1 H-NMR (δ, 400 MHz) 8.95 (d, J = 6 Hz, 2H), 8.77 (s, 2H), 8.75 (s, 2H), 8 .00 (dd, J = 2 Hz, J = 6 Hz, 2H), 5.70 (t, 2H), 4.7-4.9 (difficult to confirm due to overlap with solvent peak), 3.23 (t, 2H), 2.45 (t, 2H), and an absorption maximum with a molar extinction coefficient of 5400 M −1 cm −1 as a visible absorption spectrum is shown at 560 nm.
Visible light-responsive electrodes were constructed by adsorbing this ruthenium complex on a titanium oxide porous film formed on the surface of conductive glass. An electrolyte solution composed of 0.1 M lithium iodide, 0.05 M iodine, 0.6 M 1.2-dimethyl-3-propylimidazolium iodide, and acetonitrile is sandwiched between the conductive glass surface and platinum counter electrode. Construct a solar cell. As a result, a photocurrent with a short-circuit current of 18.7 mA / cm 2 , an open-circuit voltage of 0.57 V, and an FF of 69% could be extracted under irradiation of AM1.5 simulated sunlight.
(Conventional example)

実施例１において、エチレンジアミン（チオシアナート−Ｎ）（４，４’，４”−トリカルボキシ−２，２’；２”、６−テルピリジン）ルテニウム(II)に代えて、トリチオシアナート−Ｎ（４，４’，４”−トリカルボキシ−２，２’；２”、６−テルピリジン）ルテニウム(II)を用いた電極を構成し、実施例１と同じく、導電性ガラス表面に白金を蒸着した対電極との間に、0.1Mヨウ化リチウム、0.05Mヨウ素、0.6M1.2-ジメチル-3-プロピルイミダゾリウムヨージド、アセトニトリルから構成される電解質溶液をはさみ太陽電池を構成する。その結果AM1.5の擬似太陽光照射下において、短絡電流１７．６／ｃｍ2、開放電圧０．５０Ｖ、ＦＦ６１%の光電流を取り出せた。 In Example 1, instead of ethylenediamine (thiocyanate-N) (4,4 ′, 4 ″ -tricarboxy-2,2 ′; 2 ″, 6-terpyridine) ruthenium (II), trithiocyanate-N (4 , 4 ′, 4 ″ -tricarboxy-2,2 ′; 2 ″, 6-terpyridine) ruthenium (II), and, as in Example 1, platinum was deposited on the conductive glass surface. A solar cell is formed by sandwiching an electrolyte solution composed of 0.1M lithium iodide, 0.05M iodine, 0.6M1.2-dimethyl-3-propylimidazolium iodide, and acetonitrile between the electrodes. As a result, a photocurrent having a short-circuit current of 17.6 / cm 2 , an open-circuit voltage of 0.50 V, and an FF of 61% was extracted under irradiation of pseudo sunlight of AM1.5.

この結果、本発明のルテニウム錯体が、増感剤として、優れた効果があることが確認された。
As a result, it was confirmed that the ruthenium complex of the present invention has an excellent effect as a sensitizer.

従来のルテニウム錯体では、不十分であった長波長領域の光エネルギーの利用を、テルピリジン誘導体とエチレンジアミン誘導体を配位子とする新しいルテニウム錯体を用いて実現するものであり、より効率の高い光エネルギーの利用を可能とする材料を提供するものであるから、効率の良い太陽電池を得ることができる。
The use of light energy in the long wavelength region, which was insufficient with conventional ruthenium complexes, is realized by using a new ruthenium complex with terpyridine derivatives and ethylenediamine derivatives as ligands. Therefore, an efficient solar cell can be obtained.

Claims (4)

式（Ｉ）で表されるルテニウム錯体化合物であって、
RuＬＬ’Ｘ （Ｉ）
（式中、Ｌは少なくとも１個の結合基であるカルボキシル基、スルホン酸基、リン酸基のうちのいずれかを含む、２，２’−６’、２’’−テルピリジン誘導体であり、それぞれの結合基は酸のアルカリ金属、アンモニウムから選ばれる１種であり、Ｌ’は次式（ａ）で表されるエチレンジアミン誘導体
Figure 2005047857
 （ここでＡ、Ａ’、Ｒ、R’、R''及びＲ'''はそれぞれ独立にアルキル、アルコキシアルキル、アミノアルキル、パーフルオロアルキル、アリール又は水素原子である。Ｘはハロゲン化物、シアノ基、イソチオシアノ基、チオシアノ基、チオラート、から選択される単座配位子。））で表されるルテニウム錯体化合物。 A ruthenium complex compound represented by the formula (I),
RuLL'X (I)
(In the formula, L is a 2,2′-6 ′, 2 ″ -terpyridine derivative containing any one of a carboxyl group, a sulfonic acid group, and a phosphoric acid group as at least one bonding group, Is a group selected from an alkali metal of acid and ammonium, and L ′ is an ethylenediamine derivative represented by the following formula (a)
Figure 2005047857
 Wherein A, A ′, R, R ′, R ″ and R ′ ″ are each independently an alkyl, alkoxyalkyl, aminoalkyl, perfluoroalkyl, aryl or hydrogen atom. X is a halide, cyano A ruthenium complex compound represented by a monodentate ligand selected from a group, an isothiocyano group, a thiocyano group, and a thiolate. 式（Ｉ）で表されるルテニウム錯体化合物であって、
RuＬＬ’Ｘ （Ｉ）
（式中、Ｌは少なくとも１個の結合基であるカルボキシル基、スルホン酸基、リン酸基のうちのいずれかを含む、２，２’−６’、２’’−テルピリジン誘導体であり、それぞれの結合基は酸のアルカリ金属、アンモニウムから選ばれる１種であり、Ｌ’は次式（ａ）で表されるエチレンジアミン誘導体
Figure 2005047857
 （ここでＡ、Ａ’、Ｒ、R’、R''及びＲ'''はそれぞれ独立にアルキル、アルコキシアルキル、アミノアルキル、パーフルオロアルキル、アリール又は水素原子である。Ｘはハロゲン化物、シアノ基、イソチオシアノ基、チオシアノ基、チオラート、から選択される単座配位子。））で表されるルテニウム錯体化合物を、色素増感半導体を用いて光エネルギーを電気エネルギーに変換するに際し、増感剤として用いること。
A ruthenium complex compound represented by the formula (I),
RuLL'X (I)
(In the formula, L is a 2,2′-6 ′, 2 ″ -terpyridine derivative containing any one of a carboxyl group, a sulfonic acid group, and a phosphoric acid group as at least one bonding group, Is a group selected from an alkali metal of acid and ammonium, and L ′ is an ethylenediamine derivative represented by the following formula (a)
Figure 2005047857
 Wherein A, A ′, R, R ′, R ″ and R ′ ″ are each independently an alkyl, alkoxyalkyl, aminoalkyl, perfluoroalkyl, aryl or hydrogen atom. X is a halide, cyano A monodentate ligand selected from a group, an isothiocyano group, a thiocyano group, and a thiolate.))) When a ruthenium complex compound represented by a dye-sensitized semiconductor is used to convert light energy into electrical energy, a sensitizer Use as.
導電性表面に形成された酸化物半導体膜に式(I)で表されるルテニウム錯体化合物が、吸着したものであることを特徴とする色素増感酸化物半導体電極。   A dye-sensitized oxide semiconductor electrode, wherein a ruthenium complex compound represented by the formula (I) is adsorbed on an oxide semiconductor film formed on a conductive surface. 請求項３の電極と、その対極と、それらの電極に接触するレドックス電解質とから構成されることを特徴とする太陽電池。

A solar cell comprising the electrode according to claim 3, a counter electrode thereof, and a redox electrolyte in contact with the electrode.

JP2003282160A 2003-07-29 2003-07-29 Ruthenium complexes useful as sensitizers Expired - Lifetime JP4292291B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003282160A JP4292291B2 (en) 2003-07-29 2003-07-29 Ruthenium complexes useful as sensitizers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2003282160A JP4292291B2 (en) 2003-07-29 2003-07-29 Ruthenium complexes useful as sensitizers

Publications (2)

Publication Number Publication Date
JP2005047857A true JP2005047857A (en) 2005-02-24
JP4292291B2 JP4292291B2 (en) 2009-07-08

Family

ID=34267452

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2003282160A Expired - Lifetime JP4292291B2 (en) 2003-07-29 2003-07-29 Ruthenium complexes useful as sensitizers

Country Status (1)

Country Link
JP (1) JP4292291B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006298882A (en) * 2005-04-25 2006-11-02 Sharp Corp Ruthenium complex, dye-sensitized oxide semiconductor electrode obtained using the same, and dye-sensitized solar cell
WO2007091525A1 (en) 2006-02-08 2007-08-16 Shimane Prefectural Government Photosensitizer dye

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000012882A (en) * 1998-06-25 2000-01-14 Fuji Photo Film Co Ltd Photosensor having contg. reactive aromatic amine in hole transport layer and manufacture thereof
JP2001203005A (en) * 2000-01-21 2001-07-27 Fuji Photo Film Co Ltd Photoelectric transducer element, photo cells and metal complex dyes
JP2001229983A (en) * 2000-02-15 2001-08-24 Fuji Photo Film Co Ltd Photoelectric conversion element and photoelectric cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000012882A (en) * 1998-06-25 2000-01-14 Fuji Photo Film Co Ltd Photosensor having contg. reactive aromatic amine in hole transport layer and manufacture thereof
JP2001203005A (en) * 2000-01-21 2001-07-27 Fuji Photo Film Co Ltd Photoelectric transducer element, photo cells and metal complex dyes
JP2001229983A (en) * 2000-02-15 2001-08-24 Fuji Photo Film Co Ltd Photoelectric conversion element and photoelectric cell

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006298882A (en) * 2005-04-25 2006-11-02 Sharp Corp Ruthenium complex, dye-sensitized oxide semiconductor electrode obtained using the same, and dye-sensitized solar cell
WO2007091525A1 (en) 2006-02-08 2007-08-16 Shimane Prefectural Government Photosensitizer dye
US8106198B2 (en) 2006-02-08 2012-01-31 Shimane Prefectural Government Photosensitizer dye

Also Published As

Publication number Publication date
JP4292291B2 (en) 2009-07-08

Similar Documents

Publication Publication Date Title
Hara et al. Dye-sensitized nanocrystalline TiO2 solar cells based on novel coumarin dyes
JP5003871B2 (en) Binuclear metal complex, metal complex dye, photoelectric conversion element, and photochemical battery
EP0983282B1 (en) Metal complex photosensitizer and photovoltaic cell
JP3985040B2 (en) Ruthenium complex useful as sensitizer, oxide semiconductor electrode, and solar cell using the same
Pandey et al. Alkyl and fluoro-alkyl substituted squaraine dyes: A prospective approach towards development of novel NIR sensitizers
Giribabu et al. A new familiy of heteroleptic ruthenium (ii) polypyridyl complexes for sensitization of nanocrystalline TiO 2 films
Pasunooti et al. Synthesis, characterization and application of trans-D–B–A-porphyrin based dyes in dye-sensitized solar cells
El-Shishtawy et al. Influence of redox electrolyte on the device performance of phenothiazine based dye sensitized solar cells
Abdellah et al. Structure-property relationship of novel monosubstituted Ru (II) complexes for high photocurrent and high efficiency DSSCs: Influence of donor versus acceptor ancillary ligand on DSSCs performance
Wang et al. Effects of the acceptors in triphenylamine-based D–A′–π–A dyes on photophysical, electrochemical, and photovoltaic properties
Heo et al. Synthesis and characterization of triphenylamine-based organic dyes for dye-sensitized solar cells
Abdellah et al. Influence of carbonyl group on photocurrent density of novel fluorene based D-π-A photosensitizers: Synthesis, photophysical and photovoltaic studies
Vougioukalakis et al. Novel Ru (II) sensitizers bearing an unsymmetrical pyridine-quinoline hybrid ligand with extended π-conjugation: synthesis and application in dye-sensitized solar cells
Cao et al. New D–π–A organic dyes containing a tert-butyl-capped indolo [3, 2, 1-jk] carbazole donor with bithiophene unit as π-linker for dye-sensitized solar cells
Degbia et al. Carbazole based hole transporting materials for solid state dye sensitizer solar cells: role of the methoxy groups
Bagheri et al. Pyridine derivatives; new efficient additives in bromide/tribromide electrolyte for dye sensitized solar cells
Kumar et al. Synthesis and characterization of simple cost-effective trans-A 2 BC porphyrins with various donor groups for dye-sensitized solar cells
Swetha et al. Panchromatic Ru (II) Dipyrrins as NCS free sensitizers showing highest efficiency for DSSCs
Chandrasekharam et al. Ruthenium (II)-bipyridyl with extended π-system: Improved thermo-stable sensitizer for efficient and long-term durable dye sensitized solar cells
JP2008222747A (en) Dye and dye-sensitized solar cell by using the same
Lee et al. Metal-free organic dyes with benzothiadiazole as an internal acceptor for dye-sensitized solar cells
JP5816111B2 (en) Metal complex dye composition, photoelectric conversion element and photoelectrochemical cell
Erten-Ela et al. Iridium dimer complex for dye sensitized solar cells using electrolyte combinations with different ionic liquids
Cisneros et al. Hydrophilic Ethylene‐Glycol‐Based Ruthenium Sensitizers for Aqueous Dye‐Sensitized Solar Cells
CN102977093B (en) Pyridino[3,4-b]pyrazine derivative and application thereof

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20050315

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20080917

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20081014

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20081210

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20090310

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

R150 Certificate of patent or registration of utility model

Ref document number: 4292291

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

EXPY Cancellation because of completion of term