JP5096673B2 - Semiconductor electrode and photoelectric conversion element - Google Patents
Semiconductor electrode and photoelectric conversion element Download PDFInfo
- Publication number
- JP5096673B2 JP5096673B2 JP2005343762A JP2005343762A JP5096673B2 JP 5096673 B2 JP5096673 B2 JP 5096673B2 JP 2005343762 A JP2005343762 A JP 2005343762A JP 2005343762 A JP2005343762 A JP 2005343762A JP 5096673 B2 JP5096673 B2 JP 5096673B2
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- dye
- photoelectric conversion
- semiconductor
- dyes
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- 229940043376 ammonium acetate Drugs 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
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- 150000002440 hydroxy compounds Chemical class 0.000 description 1
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- 239000011133 lead Substances 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Hybrid Cells (AREA)
- Indole Compounds (AREA)
- Photovoltaic Devices (AREA)
Description
本発明は、表面に導電性を有する基板と、その導電性表面上に被覆された半導体層と、
その半導体層の表面に吸着した2種以上の色素から構成されて成る半導体電極と、前記半導体電極を用いる光電変換素子に関するものである。
The present invention comprises a substrate having conductivity on the surface, a semiconductor layer coated on the conductive surface,
The present invention relates to a semiconductor electrode composed of two or more dyes adsorbed on the surface of the semiconductor layer, and a photoelectric conversion element using the semiconductor electrode.
大量の化石燃料の使用で引き起こされるCO2濃度増加による地球温暖化、更に人口増加に伴うエネルギー需要の増大は、人類の存亡にまで関わる問題と認識されている。そのため近年、無限で有害物質を発生しない太陽光の利用が精力的に検討されている。このクリーンエネルギー源である太陽光利用として現在実用化されているものは住宅用の単結晶シリコン、多結晶シリコン、アモルファスシリコンおよびテルル化カドミウムやセレン化インジウム銅等の無機系太陽電池が挙げられる。 Global warming due to the increase in CO 2 concentration caused by the use of a large amount of fossil fuel, and the increase in energy demand accompanying population increase are recognized as problems related to the existence of human beings. For this reason, in recent years, the use of sunlight that is infinite and does not generate harmful substances has been energetically studied. What is currently put into practical use as sunlight, which is a clean energy source, includes residential single crystal silicon, polycrystalline silicon, amorphous silicon, and inorganic solar cells such as cadmium telluride and indium copper selenide.
しかしながら、これらの無機系太陽電池にも欠点がある。例えばシリコン系では、非常に純度の高いものが要求され、当然精製の工程は複雑でプロセス数が多く、製造コストが高い。それ以外にも軽量化等の要求もあり、特に、ユーザーへのペイバックが長い点でも不利であり、普及には問題があった。 However, these inorganic solar cells also have drawbacks. For example, a silicon system is required to have a very high purity. Naturally, the purification process is complicated, the number of processes is large, and the manufacturing cost is high. In addition, there is a demand for weight reduction and the like, and in particular, it is disadvantageous in that payback to the user is long, and there is a problem in the spread.
その一方で、有機材料を使う太陽電池も多く提案されている。有機太陽電池としては、p型有機半導体と仕事関数の小さい金属を接合させるショットキー型光電変換素子、p型有機半導体とn型無機半導体、あるいはp型有機半導体と電子受容性有機化合物を接合させるヘテロ接合型光電変換素子等があり、利用される有機半導体は、クロロフィル、ペリレン等の合成色素や顔料、ポリアセチレン等の導電性高分子材料、またはそれらの複合材料等である。これらを真空蒸着法、キャスト法、またはディッピング法等により、薄膜化し電池材料が構成されている。有機材料は低コスト、大面積化が容易等の長所もあるが、変換効率は1%以下と低いものが多く、また耐久性も悪いという問題もあった。 On the other hand, many solar cells using organic materials have been proposed. As an organic solar cell, a Schottky photoelectric conversion element that joins a p-type organic semiconductor and a metal having a low work function, a p-type organic semiconductor and an n-type inorganic semiconductor, or a p-type organic semiconductor and an electron-accepting organic compound are joined. There are heterojunction photoelectric conversion elements and the like, and organic semiconductors used are synthetic dyes and pigments such as chlorophyll and perylene, conductive polymer materials such as polyacetylene, or composite materials thereof. These are thinned by a vacuum deposition method, a casting method, a dipping method, or the like to form a battery material. The organic material has advantages such as low cost and easy area enlargement, but there are many problems that the conversion efficiency is as low as 1% or less and the durability is poor.
こうした状況の中で、良好な特性を示す太陽電池がスイスのグレッツェル博士らによって報告された(非特許文献1参照)。この文献には電池作製に必要な材料および製造技術も開示されている。提案された電池は色素増感型太陽電池、あるいはグレッツェル型太陽電池と呼ばれ、ルテニウム錯体で分光増感された酸化チタン多孔質薄膜を作用電極とする湿式太陽電池である。この方式の利点は酸化チタン等の安価な酸化物半導体を高純度まで精製する必要がないために安価であること、更に利用できる光は可視光領域にまでわたっており、可視光成分の多い太陽光を有効に電気へ変換できることである。 Under such circumstances, a solar cell exhibiting good characteristics has been reported by Dr. Gretzell of Switzerland (see Non-Patent Document 1). This document also discloses materials and manufacturing techniques necessary for battery fabrication. The proposed battery is called a dye-sensitized solar cell or a Gretzel solar cell, and is a wet solar cell using a titanium oxide porous thin film spectrally sensitized with a ruthenium complex as a working electrode. The advantage of this method is that it is inexpensive because it is not necessary to purify an inexpensive oxide semiconductor such as titanium oxide to a high purity. Further, the available light extends to the visible light region, and the sun is rich in visible light components. It is that light can be effectively converted into electricity.
ただし、色素増感太陽電池には、実用化に向けてまだ解決すべき問題点がある。例えば、ルテニウム錯体のみならず、一般に単一の有機色素および有機金属錯体色素を用いた色素増感太陽電池では、これらの色素が光電変換に利用できる光の波長領域が太陽光あるいは蛍光灯等を光源とする光の波長領域に比べて狭いため、光源の波長成分を必ずしも十分に利用できていない点が挙げられる。従って、例えば、2種以上の色素を酸化チタン等の半導体表面に吸着させることで、このような問題点が解決される可能性がある。また、ルテニウム錯体は稀少金属のルテニウムを用いているために資源面での制約がある点、および色素が非常に高価である点が挙げられる。そのため、ルテニウム錯体を用いた色素増感太陽電池においては、ルテニウム錯体の一部を、量子効率が高く、かつ資源面での制約において有利な有機色素に置き換えることにより、これらの問題を解決出来る可能性がある。色素増感太陽電池用の有機色素としてはメロシアニン色素、シアニン色素、9−フェニルキサンテン系色素等が報告されている(例えば、特許文献1〜3参照)。しかしながら、これらの有機色素から選ばれる少なくとも2種以上を半導体層表面に吸着させても、またはこれらの有機色素から選ばれる少なくとも1種とルテニウム錯体色素等とを酸化チタン等の半導体層表面に吸着させても、半導体層表面に吸着した2種以上の色素によって相乗効果的に光電変換性能が向上するケースはほとんど無く、上述のような問題を十分に解決できていないのが現状であった。
本発明の目的は、光電変換特性に優れた光電変換素子を提供することにある。 The objective of this invention is providing the photoelectric conversion element excellent in the photoelectric conversion characteristic.
本発明者らは上記目的を達成すべく種々の増感色素を鋭意検討した結果、下記の施策によって目的の達成に至った。 As a result of intensive studies on various sensitizing dyes to achieve the above object, the present inventors have achieved the object by the following measures.
(イ)表面に導電性を有する基板、その導電性表面を被覆する半導体層及びその半導体層の表面に担持された2種以上の色素から構成されてなる半導体電極において、該色素のうち少なくとも1種が、有機溶剤に溶解した液中での吸収スペクトルの極大吸収波長を350nm以上、500nm以下に有する色素であり、他の色素の少なくとも1種が、極大吸収波長を500nm以上、700nm以下に有する色素であることを特徴とする半導体電極。 A substrate having an electrically conductive (i) surface in the semiconductor layer and a semiconductor electrode comprising consist supported more dyes on the surface of the semiconductor layer covering the electrically conductive surface, at least one of the dye The seed is a dye having a maximum absorption wavelength of an absorption spectrum in a solution dissolved in an organic solvent at 350 nm or more and 500 nm or less, and at least one of the other dyes has a maximum absorption wavelength at 500 nm or more and 700 nm or less. A semiconductor electrode characterized by being a dye.
有機溶剤に溶解した液中での吸収スペクトルの極大吸収波長を500nm以上、700nm以下に有する色素がルテニウム錯体である半導体電極。 Organic solvent dissolved a maximum absorption wavelength of the absorption spectrum in the liquid 500nm or more, semi-conductor electrode dye Ru der ruthenium complex having the 700nm below.
有機溶剤に溶解した液中での吸収スペクトルの極大吸収波長を350nm以上、500nm以下に有する色素が、下記一般式(1)と一般式(2)とで示される色素から選ばれる少なくとも1種である半導体電極。 The maximum absorption wavelength of the absorption spectrum in dissolved in organic solvent liquid 350nm or more, dyes having a 500nm or less is at least one selected from dyes represented de following general formula (1) General formula (2) der Ru semi conductor electrode.
(一般式(1)において、R1はアリール基を示し、置換基を有していてもよい。R2は窒素原子と、窒素原子に隣接するベンゼン環と結合して環状構造を形成する形成する連結基を示し、該環状構造が5員環である。R3は水素原子を示す。lは0を示す。炭素−炭素二重結合は、E型、Z型の何れであってもよい。R4は水素原子を示す。R5は酸素原子の置換基であって、水素原子を示す。) (In General Formula (1), R 1 represents an aryl group and may have a substituent. R 2 forms a ring structure by bonding to a nitrogen atom and a benzene ring adjacent to the nitrogen atom. the linking group which indicates, cyclic structure is a five-membered ring .R 3 is shown to .l hydrogen atom is 0 carbon -. carbon double bonds, be either E, Z-shaped which may be .R 4 is shown to .R 5 hydrogen atom a substituent oxygen atom, a water MotoHara child.)
(一般式(2)において、R6とR10は窒素原子と、窒素原子に隣接するベンゼン環と結合して環状構造を形成する連結基を示し、該環状構造が5員環である。R7とR11は水素原子を示す。mとnは0を示す。炭素−炭素二重結合は、E型、Z型の何れであってもよい。R8とR12は水素原子を示す。Ar1とAr2は1,4−フェニレン基を示し、L4は−SCH 2 CH 2 S−で示される二価の連結基を示し、pは1を示す。R9とR13は酸素原子の置換基であって、水素原子を示す。) In (formula (2), R 6 and R 10 is a nitrogen atom, bonded to the benzene ring adjacent to the nitrogen atom indicates a linking group which forms a cyclic structure, the cyclic structure is a 5-membered ring. R 7 and R 11 is 0 is shown to .m and n hydrogen atom carbon -. carbon double bond, E, good .R 8 and R 12 be either a Z-type hydrogen atoms the shown to .Ar 1 and Ar 2 child indicates 1,4-phenylene group, L 4 represents a divalent linking group represented by -SCH 2 CH 2 S-, p is an .R 9 showing a 1 R 13 is a substituent of an oxygen atom, a water MotoHara child.)
(ロ)半導体が、チタン、スズ、亜鉛、鉄、銅、タングステン、ジルコニウム、ハフニウム、ニオブ、タンタル、カドミウム、鉛、銀、アンチモン、ビスマス、モリブデン、アルミニウム、ガリウム、クロム、コバルト、ニッケル、から選ばれる金属カルコゲニドを少なくとも一種含むことを特徴とする上記(イ)記載の半導体電極。 ( B ) The semiconductor is selected from titanium, tin, zinc, iron, copper, tungsten, zirconium, hafnium, niobium, tantalum, cadmium, lead, silver, antimony, bismuth, molybdenum, aluminum, gallium, chromium, cobalt, nickel (a) above Symbol mounting of the semiconductor electrode to be metal chalcogenides comprising at least one kind.
(ハ)上記(イ)又は(ロ)記載の半導体電極を用いてなる光電変換素子。 ( C ) A photoelectric conversion element using the semiconductor electrode described in (a) or (b) above.
半導体層の表面に吸着した2種以上の色素から構成される半導体電極において、本発明で使用される一般式(1)あるいは一般式(2)で示される化合物から選ばれる色素の少なくとも1種を用いることにより、それぞれの色素を単独で用いた場合よりも優れた光電変換効率を示す光電変換素子を得ることが出来る。更に、前記一般式(1)あるいは一般式(2)で示される化合物から選ばれる色素と、ルテニウム錯体色素を用いた半導体電極を用いることにより、更に優れた変換効率を示す光電変換素子を得ることが出来た。2種以上の色素を用いる事により、このような相乗効果が得られる機構の詳細は解明されていない。しかしながら本発明者らはその相乗効果発現の原因として第一に、2種以上の色素の吸収スペクトルの相補性を挙げることができる。半導体のバンドギャップとの関係から、良好な光電変換効率を有する色素は、有機溶剤に溶解した液中での吸収スペクトルの極大吸収波長を500nm〜700nmに有する物が一般的であることが知られている。これらの色素の350nm〜500nmの吸収強度は極大吸収領域に比べて相対的に弱く、これらの色素と共に350nm〜500nmに吸収極大を有する色素を併用することにより350nm〜700nmの幅広い波長領域にわたって効率的に光電変換できる半導体電極を製造できることは容易に類推できることである。しかし、極大吸収波長の異なる複数の色素を併用した場合、異種色素間相互で生じる半導体への吸着阻害、あるいは異種色素を併用することによる光電変換効率の低い色素凝集体の半導体表面での発生のため、優れた光電変換効率を達成できる複数色素の実用例は非常に少ないのが実情である。本発明者らは、一般式(1)あるいは一般式(2)で示される化合物から選ばれる色素の少なくとも1種を用いることにより、350nm〜700nmの幅広い波長領域にわたって効率的に光電変換できる半導体電極を製造できることを見出した。 In the semiconductor electrode composed of two or more kinds of dyes adsorbed on the surface of the semiconductor layer, at least one kind of dye selected from the compounds represented by the general formula (1) or the general formula (2) used in the present invention is used. By using, the photoelectric conversion element which shows the photoelectric conversion efficiency superior to the case where each pigment | dye is used independently can be obtained. Furthermore, by using a semiconductor electrode using a dye selected from the compound represented by the general formula (1) or the general formula (2) and a ruthenium complex dye, a photoelectric conversion element having further excellent conversion efficiency is obtained. Was made. The details of the mechanism by which such a synergistic effect is obtained by using two or more dyes have not been elucidated. However, the present inventors can firstly mention the complementarity of the absorption spectra of two or more dyes as the cause of the synergistic effect. From the relationship with the semiconductor band gap, it is known that dyes having good photoelectric conversion efficiency are generally those having a maximum absorption wavelength of an absorption spectrum in a liquid dissolved in an organic solvent in the range of 500 nm to 700 nm. ing. The absorption intensity of these dyes at 350 nm to 500 nm is relatively weak compared to the maximum absorption region, and by combining these dyes with a dye having an absorption maximum at 350 nm to 500 nm, it is efficient over a wide wavelength range of 350 nm to 700 nm. It can be easily analogized that a semiconductor electrode capable of photoelectric conversion can be manufactured. However, when multiple dyes with different maximum absorption wavelengths are used in combination, inhibition of adsorption to semiconductors between different types of dyes, or generation of dye aggregates on the semiconductor surface with low photoelectric conversion efficiency by using different types of dyes together For this reason, there are very few practical examples of a plurality of dyes that can achieve excellent photoelectric conversion efficiency. The present inventors use a semiconductor electrode capable of efficiently performing photoelectric conversion over a wide wavelength region of 350 nm to 700 nm by using at least one dye selected from the compounds represented by the general formula (1) or the general formula (2). It has been found that
さらに、本発明者らはその相乗効果発現の原因として、以下に示す点を追加して挙げることができる。 Furthermore, the present inventors can add the following points as causes of the synergistic effects.
(a)本発明で用いられる色素が、微小領域において化学的または物理的性質の不均一な半導体層表面を隈無く被覆する能力に優れている事。その根拠としては、前記一般式(1)あるいは前記一般式(2)で示される色素が半導体層表面に吸着する際に、分子集合体の一形態であるJ凝集体を形成して半導体層表面に緻密に吸着する現象が挙げられる。J凝集体とは、少なくとも4個以上の色素分子が規則正しく配列会合した凝集体のことを表す。色素J凝集体の吸収スペクトルの極大吸収波長は、その色素の単分子の吸収スペクトルの極大吸収波長よりも略50nmから100nm長波長側にあるのが一般的である。 (A) The dye used in the present invention is excellent in the ability to cover the surface of a semiconductor layer having non-uniform chemical or physical properties in a minute region. The basis for this is that when the dye represented by the general formula (1) or the general formula (2) is adsorbed on the surface of the semiconductor layer, a J aggregate is formed as a form of a molecular assembly to form the surface of the semiconductor layer. And the phenomenon of dense adsorption. The J aggregate represents an aggregate in which at least four or more dye molecules are regularly aligned. In general, the maximum absorption wavelength of the absorption spectrum of the dye J aggregate is approximately 50 nm to 100 nm longer than the maximum absorption wavelength of the absorption spectrum of a single molecule of the dye.
(b)前記一般式(1)あるいは前記一般式(2)で示される色素と組み合わせて用いられる色素(例えばルテニウム錯体色素)が半導体層表面に吸着する場合に生じる色素未吸着の半導体層表面部位を、半導体層表面を被覆する能力に優れた前記一般式(1)あるいは前記一般式(2)で示される色素を用いて被覆できる事。 (B) The surface portion of the semiconductor layer that is not adsorbed to the dye, which is generated when the dye (for example, ruthenium complex dye) used in combination with the dye represented by the general formula (1) or (2) is adsorbed on the surface of the semiconductor layer. Can be coated using the dye represented by the general formula (1) or the general formula (2), which has an excellent ability to coat the surface of the semiconductor layer.
本発明に用いる一般式(1)で示される化合物について、更に詳細に説明する。一般式(1)で示される化合物のR1の具体的な例としては、メチル基、エチル基、イソプロピル基等のアルキル基、ベンジル基、1−ナフチルメチル基等のアラルキル基、ビニル基、シクロヘキセニル基等のアルケニル基、フェニル基、ナフチル基等のアリール基、フリル基、チエニル基、インドリル基等のヘテロ環残基を挙げることができるが、本発明において、R1はアリール基である。また、R1基は置換基を有していてもよく、その置換基の具体例としては、R1と同様のアルキル基、メトキシ基、エトキシ基、n−ヘキシルオキシ基等のアルコキシ基、メチルチオ基、n−ヘキシルチオ基等のアルキルチオ基、フェノキシ基、1−ナフチルオキシ基等のアリールオキシ基、フェニルチオ基等のアリールチオ基、塩素、臭素等のハロゲン原子、ジメチルアミノ基、ジフェニルアミノ基等のジ置換アミノ基、R1と同様のアリール基、R1と同様のヘテロ環、カルボキシル基、カルボキシメチル基のようなカルボキシアルキル基、スルホニルプロピル基のようなスルホニルアルキル基、リン酸基、ヒドロキサム酸基等の酸性基、シアノ基、ニトロ基、トリフルオロメチル基等の電子吸引性基を挙げることができる。R2は窒素原子と、窒素原子に隣接するベンゼン環と結合して環状構造を形成する連結基であり、更にR1とR2、R1と窒素原子に隣接するベンゼン環との間で環状構造を形成してもよい。その具体例を式(3)〜(19)に挙げることができるが、本発明において、R 2 は窒素原子と、窒素原子に隣接するベンゼン環と結合して環状構造を形成する形成する連結基を示し、該環状構造が5員環である。R3は水素原子、R1と同様のアルキル基、R1と同様のアルコキシ基、R1と同様のハロゲン原子を示し、置換基を有していてもよい。その置換基の具体例としては、R1と同様のアルキル基、メトキシ基、エトキシ基、n−ヘキシルオキシ基等のアルコキシ基、メチルチオ基、n−ヘキシルチオ基等のアルキルチオ基、フェノキシ基、1−ナフチルオキシ基等のアリールオキシ基、フェニルチオ基等のアリールチオ基、塩素、臭素等のハロゲン原子、ジメチルアミノ基、ジフェニルアミノ基等の二置換アミノ基、R1と同様のアリール基、R1と同様のヘテロ環、カルボキシル基、カルボキシメチル基等のカルボキシアルキル基、スルホニルプロピル基等のスルホニルアルキル基、リン酸基、ヒドロキサム酸等の酸性基、シアノ基、ニトロ基、トリフルオロメチル基等の電子吸引性基を挙げることができる。酸性基は4級アンモニウム塩、金属塩、エステル、アミドの形態であっても構わない。本発明において、R 3 は水素原子である。L1の具体例としては、1,2−ビニレン基、1,4−ブタジエニレン基等のアルケニレン基、1,4−フェニレン基、1,4−ナフチレン基等のアリーレン基、2,5−チエニレン基等のヘテロ環を1個以上有する二価の芳香族ヘテロ環残基を挙げることができる。本発明において、lは0である。R4は水素原子、R1と同様のアルキル基、R1と同様のアラルキル基、R1と同様のヘテロ環残基を示し、置換基を有していてもよい。その置換基の具体例としては、R1と同様のアルキル基、メトキシ基、エトキシ基、n−ヘキシルオキシ基等のアルコキシ基、メチルチオ基、n−ヘキシルチオ基等のアルキルチオ基、フェノキシ基、1−ナフチルオキシ基等のアリールオキシ基、フェニルチオ基等のアリールチオ基、塩素、臭素等のハロゲン原子、ジメチルアミノ基、ジフェニルアミノ基等の二置換アミノ基、R1と同様のアリール基、R1と同様のヘテロ環、カルボキシル基、カルボキシメチル基等のカルボキシアルキル基、スルホニルプロピル基等のスルホニルアルキル基、リン酸基、ヒドロキサム酸等の酸性基、シアノ基、ニトロ基、トリフルオロメチル基等の電子吸引性基を挙げることができる。酸性基は4級アンモニウム塩、金属塩、エステル、アミドの形態であっても構わない。本発明において、R 4 は水素原子である。R5の具体例としては、水素原子の他に、メチル基、エチル基等のアルキル基、アンモニウムイオン、テトラエチルアンモニウムイオン、テトラブチルアンモニウムイオン等の四級アンモニウム塩が挙げられるが、本発明において、R 5 は水素原子である。 The compound represented by the general formula (1) used in the present invention will be described in more detail. Specific examples of R 1 of the compound represented by the general formula (1) include alkyl groups such as methyl group, ethyl group and isopropyl group, aralkyl groups such as benzyl group and 1-naphthylmethyl group, vinyl group, cyclohexane Examples include alkenyl groups such as hexenyl groups, aryl groups such as phenyl groups and naphthyl groups, and heterocyclic residues such as furyl groups, thienyl groups, and indolyl groups. In the present invention, R 1 is an aryl group. The R 1 group may have a substituent. Specific examples of the substituent include the same alkyl group as R 1 , an alkoxy group such as a methoxy group, an ethoxy group, and an n-hexyloxy group, methylthio Group, alkylthio group such as n-hexylthio group, aryloxy group such as phenoxy group and 1-naphthyloxy group, arylthio group such as phenylthio group, halogen atom such as chlorine and bromine, dimethylamino group and diphenylamino group substituted amino group, the same aryl group as R 1, the same heterocycle with R 1, carboxyl group, carboxyalkyl carboxyalkyl group such as methyl group, sulfonyl propylsulfonyl alkyl groups such as groups, phosphate groups, hydroxamic acid And an electron-withdrawing group such as a cyano group, a nitro group, and a trifluoromethyl group. R 2 is a linking group that forms a cyclic structure by combining with a nitrogen atom and a benzene ring adjacent to the nitrogen atom, and is further cyclic between R 1 and R 2 , R 1 and the benzene ring adjacent to the nitrogen atom. A structure may be formed. Specific examples thereof can be mentioned in formulas (3) to (19) . In the present invention, R 2 is a linking group that forms a cyclic structure by bonding to a nitrogen atom and a benzene ring adjacent to the nitrogen atom. And the cyclic structure is a 5-membered ring . R 3 is a hydrogen atom, the same alkyl group as R 1, the same alkoxy group as R 1, shows the same halogen atom and R 1, which may have a substituent. Specific examples of the substituent include the same alkyl group as R 1 , an alkoxy group such as a methoxy group, an ethoxy group and an n-hexyloxy group, an alkylthio group such as a methylthio group and an n-hexylthio group, a phenoxy group, 1- Similarly aryloxy group such as naphthyloxy group, an arylthio group such as phenylthio group, a chlorine, a halogen atom such as bromine, dimethylamino group, disubstituted amino groups such as diphenylamino group, same aryl group as R 1, and R 1 Heterocycle, carboxyl group such as carboxyl group and carboxymethyl group, sulfonylalkyl group such as sulfonylpropyl group, acidic group such as phosphoric acid group and hydroxamic acid, electron withdrawing such as cyano group, nitro group and trifluoromethyl group Sex groups can be mentioned. The acidic group may be in the form of a quaternary ammonium salt, metal salt, ester or amide. In the present invention, R 3 is a hydrogen atom. Specific examples of L 1 include alkenylene groups such as 1,2-vinylene group and 1,4-butadienylene group, arylene groups such as 1,4-phenylene group and 1,4-naphthylene group, and 2,5-thienylene group. And divalent aromatic heterocyclic residues having one or more heterocyclic rings. In the present invention, l is 0. R 4 is a hydrogen atom, the same alkyl group as R 1, the same aralkyl groups as R 1, showed a similar heterocyclic residue and R 1, which may have a substituent. Specific examples of the substituent include the same alkyl group as R 1 , an alkoxy group such as a methoxy group, an ethoxy group and an n-hexyloxy group, an alkylthio group such as a methylthio group and an n-hexylthio group, a phenoxy group, 1- Similarly aryloxy group such as naphthyloxy group, an arylthio group such as phenylthio group, a chlorine, a halogen atom such as bromine, dimethylamino group, disubstituted amino groups such as diphenylamino group, same aryl group as R 1, and R 1 Heterocycle, carboxyl group such as carboxyl group and carboxymethyl group, sulfonylalkyl group such as sulfonylpropyl group, acidic group such as phosphoric acid group and hydroxamic acid, electron withdrawing such as cyano group, nitro group and trifluoromethyl group Sex groups can be mentioned. The acidic group may be in the form of a quaternary ammonium salt, metal salt, ester or amide. In the present invention, R 4 is a hydrogen atom. Specific examples of R 5 include, in addition to hydrogen atoms, alkyl groups such as methyl group and ethyl group, and quaternary ammonium salts such as ammonium ion, tetraethylammonium ion and tetrabutylammonium ion . R 5 is a hydrogen atom .
本発明に用いる一般式(2)で示される化合物について、更に詳細に説明する。一般式(2)で示される化合物のR6とR10は、窒素原子と、窒素原子に隣接するベンゼン環と結合して環状構造を形成する連結基である。その具体例を(20)〜(36)に挙げることができるが、本発明において、R 6 とR 10 は窒素原子と、窒素原子に隣接するベンゼン環と結合して環状構造を形成する形成する連結基を示し、該環状構造が5員環である。具体例(20)〜(36)中の置換基Arは、前記一般式(2)中のAr1、あるいはAr2を意味する。R7とR11は水素原子の他に、メチル基、エチル基、イソプロピル基等のアルキル基、メトキシ基、エトキシ基、n−ヘキシルオキシ基等のアルコキシ基、塩素、臭素等のハロゲン原子を示し、これらはさらに置換基を有していてもよい。その置換基の具体例としては、R7、R11と同様のアルキル基、R7、R11と同様のアルコキシ基、メチルチオ基、n−ヘキシルチオ基等のアルキルチオ基、フェノキシ基、1−ナフチルオキシ基等のアリールオキシ基、フェニルチオ基等のアリールチオ基、塩素、臭素等のハロゲン原子、ジメチルアミノ基、ジフェニルアミノ基等の二置換アミノ基、R7、R11と同様のアリール基、フリル基、チエニル基、インドリル基等のヘテロ環、カルボキシル基、カルボキシメチル基等のカルボキシアルキル基、スルホニルプロピル基等のスルホニルアルキル基、リン酸基、ヒドロキサム酸等の酸性基、シアノ基、ニトロ基、トリフルオロメチル基等の電子吸引性基を挙げることができる。酸性基は4級アンモニウム塩、金属塩、エステル、アミドの形態であっても構わない。本発明において、R 7 とR 11 は水素原子である。L2とL3の具体例としては、1,2−ビニレン基、1,4−ブタジエニレン基等のアルケニレン基、1,4−フェニレン基、1,4−ナフチレン基等のアリーレン基、2,5−チエニレン基等のヘテロ環を1個以上有する二価の芳香族ヘテロ環残基を挙げることができる。本発明において、mとnは0である。R8とR12は水素原子、R7、R11と同様のアルキル基、R7、R11と同様のアラルキル基、フリル基、チエニル基、インドリル基等のヘテロ環残基を示し、置換基を有していてもよい。その置換基の具体例としては、R7、R11と同様のアルキル基、メトキシ基、エトキシ基、n−ヘキシルオキシ基等のアルコキシ基、メチルチオ基、n−ヘキシルチオ基等のアルキルチオ基、フェノキシ基、1−ナフチルオキシ基等のアリールオキシ基、フェニルチオ基等のアリールチオ基、塩素、臭素等のハロゲン原子、ジメチルアミノ基、ジフェニルアミノ基等の二置換アミノ基、フェニル基、ナフチル基等のアリール基、フリル基、チエニル基、インドリル基等のヘテロ環、カルボキシル基、カルボキシメチル基等のカルボキシアルキル基、スルホニルプロピル基等のスルホニルアルキル基、リン酸基、ヒドロキサム酸等の酸性基、シアノ基、ニトロ基、トリフルオロメチル基等の電子吸引性基を挙げることができる。酸性基は4級アンモニウム塩、金属塩、エステル、アミドの形態であっても構わない。本発明において、R 8 とR 12 は水素原子である。R9とR13の具体例としては、水素原子の他に、メチル基、エチル基等のアルキル基、アンモニウムイオン、テトラエチルアンモニウムイオン、テトラブチルアンモニウムイオン等の四級アンモニウム塩が挙げられるが、本発明において、R 9 とR 13 は水素原子である。Ar1とAr2は1,4−フェニレン基、1,3−フェニレン基、2,6−ナフチレン基等のアリーレン基、2,5−チエニレン基等のヘテロ環を1個以上有する二価の芳香族ヘテロ環残基を挙げることができるが、本発明において、Ar 1 とAr 2 は1,4−フェニレン基である。L4は二価の連結基であって、具体例としては(37)〜(48)に示されるような連結基が挙げられるが、本発明において、L 4 は−SCH 2 CH 2 S−である。 The compound represented by the general formula (2) used in the present invention will be described in more detail. R 6 and R 10 of the compound represented by the general formula (2) are a linking group that forms a cyclic structure by bonding with a nitrogen atom and a benzene ring adjacent to the nitrogen atom. Specific examples thereof can be given in (20) to (36) . In the present invention, R 6 and R 10 are bonded to a nitrogen atom and a benzene ring adjacent to the nitrogen atom to form a cyclic structure. A linking group is shown, and the cyclic structure is a 5-membered ring . The substituent Ar in the specific examples (20) to (36) means Ar 1 or Ar 2 in the general formula (2). R 7 and R 11 represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group and an isopropyl group, an alkoxy group such as a methoxy group, an ethoxy group and an n-hexyloxy group, and a halogen atom such as chlorine and bromine. These may further have a substituent. Specific examples of the substituent, an alkyl group similar to R 7, R 11, same alkoxy group as R 7, R 11, methylthio group, n- hexylthio alkylthio group such as a group, a phenoxy group, 1-naphthyloxy Aryloxy groups such as phenylthio groups, arylthio groups such as phenylthio groups, halogen atoms such as chlorine and bromine, disubstituted amino groups such as dimethylamino groups and diphenylamino groups, aryl groups similar to R 7 and R 11 , furyl groups, thienyl group, a heterocyclic, carboxyl group such as an indolyl group, carboxyalkyl carboxyalkyl group such as a methyl group, sulfonyl propylsulfonyl alkyl group such as a group, phosphoric acid group, an acidic group such as a hydroxamic acid, a cyano group, a nitro group, a tri Mention may be made of electron-withdrawing groups such as fluoromethyl groups. The acidic group may be in the form of a quaternary ammonium salt, metal salt, ester or amide. In the present invention, R 7 and R 11 are hydrogen atoms. Specific examples of L 2 and L 3 include alkenylene groups such as 1,2-vinylene group and 1,4-butadienylene group, arylene groups such as 1,4-phenylene group and 1,4-naphthylene group, 2,5 -The divalent aromatic heterocyclic residue which has 1 or more heterocyclic rings, such as a thienylene group, can be mentioned. In the present invention, m and n are 0. R 8 and R 12 is a hydrogen atom, the same alkyl group as R 7, R 11, R 7 , R 11 and similar aralkyl group, a furyl group, a thienyl group, a heterocyclic residue such as an indolyl group, a substituted group You may have. Specific examples of the substituent include alkyl groups similar to R 7 and R 11 , alkoxy groups such as methoxy group, ethoxy group and n-hexyloxy group, alkylthio groups such as methylthio group and n-hexylthio group, and phenoxy groups. Aryloxy groups such as 1-naphthyloxy group, arylthio groups such as phenylthio group, halogen atoms such as chlorine and bromine, disubstituted amino groups such as dimethylamino group and diphenylamino group, aryl groups such as phenyl group and naphthyl group , Furyl group, thienyl group, indolyl group and other heterocycles, carboxyl group, carboxyalkyl group such as carboxymethyl group, sulfonylalkyl group such as sulfonylpropyl group, acidic group such as phosphate group, hydroxamic acid, cyano group, nitro group And an electron withdrawing group such as a trifluoromethyl group. The acidic group may be in the form of a quaternary ammonium salt, metal salt, ester or amide. In the present invention, R 8 and R 12 are hydrogen atoms. Specific examples of R 9 and R 13 are, in addition to the hydrogen atom, an alkyl group such as methyl group and ethyl group, an ammonium ion, tetraethyl ammonium ion, although quaternary ammonium salts such as tetrabutylammonium ion and the like, and the present In the invention, R 9 and R 13 are hydrogen atoms . Ar 1 and Ar 2 are divalent aromatics having one or more hetero rings such as 1,4-phenylene group, 1,3-phenylene group, arylene group such as 2,6-naphthylene group and 2,5-thienylene group. In the present invention, Ar 1 and Ar 2 are 1,4-phenylene groups . L 4 is a divalent linking group, and specific examples thereof include linking groups as shown in (37) to (48) . In the present invention, L 4 is —SCH 2 CH 2 S—. There is .
本発明に係わる、一般式(1)で示される化合物の具体例を(A−1)〜(A−18)に挙げる。(A−2)〜(A−4)、(A−16)、(A−17)は参考例である。 Specific examples of the compound represented by the general formula (1) according to the present invention are shown in (A-1) to (A-18). (A-2) to (A-4), (A-16), and (A-17) are reference examples.
本発明に係わる、一般式(2)で示される化合物の具体例を(B−1)〜(B−14)に挙げる。(B−1)〜(B−6)、(B−8)〜(B−14)は参考例である。 Specific examples of the compound represented by the general formula (2) according to the present invention are shown in (B-1) to (B-14). (B-1) to (B-6) and (B-8) to (B-14) are reference examples.
本発明において、一般式(1)あるいは一般式(2)で示される色素と組み合わせて用いられる色素について説明する。一般式(1)あるいは一般式(2)で示される色素と、組み合わせて用いられる色素の吸収極大波長は一致していても違っていても構わない。しかし、一般式(1)あるいは一般式(2)で示される色素と組み合わせて用いられる色素を用いた半導体電極を作用極とする光電変換素子の量子効率の入射光波長依存性は、一般式(1)あるいは一般式(2)で示される色素を用いた半導体電極を作用極とする光電変換素子の量子効率の入射光波長依存性と相補的な関係であると、より好ましい。より具体的には、一般式(1)あるいは一般式(2)で示される色素は、有機媒体に溶解した液中での吸収スペクトルの極大吸収波長を350nm以上で500nm以下の範囲に有するので、一般式(1)あるいは一般式(2)で示される色素と組み合わせて用いられる色素の有機媒体中での吸収スペクトルの極大吸収波長は500nmを超えた波長にある事が好ましい。 In the present invention, the dye used in combination with the dye represented by formula (1) or formula (2) will be described. The absorption maximum wavelength of the dye represented by the general formula (1) or (2) and the dye used in combination may be the same or different. However, the incident light wavelength dependency of the quantum efficiency of a photoelectric conversion element using a semiconductor electrode using a dye used in combination with the dye represented by the general formula (1) or (2) as a working electrode is expressed by the general formula ( It is more preferable that the relationship is complementary to the incident light wavelength dependency of the quantum efficiency of a photoelectric conversion element having a semiconductor electrode using a dye represented by 1) or the general formula (2) as a working electrode. More specifically, the dye represented by the general formula (1) or the general formula (2) has a maximum absorption wavelength of an absorption spectrum in a liquid dissolved in an organic medium in a range of 350 nm to 500 nm. The maximum absorption wavelength of the absorption spectrum in the organic medium of the dye used in combination with the dye represented by the general formula (1) or (2) is preferably at a wavelength exceeding 500 nm.
一般式(1)あるは一般式(2)で示される色素と組み合わせて用いられる色素の具体例としては、シアニン色素、メロシアニン色素、9−アリールキサンテン化合物、トリアリールメタン化合物、クマリン化合物、アクリジン化合物、アゾ化合物、フタロシアニン化合物、ポルフィリン化合物、有機金属錯体化合物等を挙げることができる。具体例を(C−1)〜(C−23)に挙げる。ただし、本発明の一般式(1)あるいは一般式(2)で示される色素と組み合わせて用いられる色素は、これらの例示化合物に限定されるものではない。 Specific examples of the dye used in combination with the dye represented by the general formula (1) or the general formula (2) include a cyanine dye, a merocyanine dye, a 9-arylxanthene compound, a triarylmethane compound, a coumarin compound, and an acridine compound. Azo compounds, phthalocyanine compounds, porphyrin compounds, organometallic complex compounds, and the like. Specific examples are given in (C-1) to (C-23). However, the dye used in combination with the dye represented by the general formula (1) or the general formula (2) of the present invention is not limited to these exemplified compounds.
これらの色素の中でも、本発明ではルテニウム錯体色素と、一般式(1)あるいは一般式(2)で示される色素とを組み合わせて用いており、より好ましい光電変換特性を得ることができる。ルテニウム錯体色素の具体例を(D−1)〜(D−10)に挙げる。ただし、本発明の一般式(1)あるいは一般式(2)で示される色素と組み合わせて用いられるルテニウム錯体色素は、これらの例示化合物に限定されるものではない。 Among these dyes, the present invention can be obtained ruthenium complex dye represented by the general formula (1) or use a combination of a dye represented by formula (2) Iteori, more preferred photoelectric conversion characteristics. Specific examples of the ruthenium complex dye are listed in (D-1) to (D-10). However, the ruthenium complex dye used in combination with the dye represented by the general formula (1) or the general formula (2) of the present invention is not limited to these exemplified compounds.
本発明に係わる色素の吸収スペクトルについては、メタノール、あるいはN,N−ジメチルホルムアミドに色素だけを溶解し、セル長1cmの石英セル中にサンプル溶液を入れ、可視・紫外分光光度計(日本分光製;V−570)を用いて350nmから700nmの波長範囲を測定して得た。色素濃度は、色素自身のモル吸光係数に応じて極大吸収波長における吸光度が1.0になる濃度に設定して測定を行った。 Regarding the absorption spectrum of the dye according to the present invention, only the dye is dissolved in methanol or N, N-dimethylformamide, and the sample solution is placed in a quartz cell having a cell length of 1 cm, and a visible / ultraviolet spectrophotometer (manufactured by JASCO). V-570) was used to measure the wavelength range from 350 nm to 700 nm. The dye concentration was measured by setting the concentration at which the absorbance at the maximum absorption wavelength was 1.0 according to the molar extinction coefficient of the dye itself.
本発明の光電変換素子は、導電性基板、導電性基板上に設置した色素によって増感された半導体層、電荷移動層及び対極からなる。半導体層は単層構成でも積層構成でもよく、目的に応じて設計される。また、導電性支持体の導電層と半導体層の境界、半導体層と電荷移動層の境界等、この素子における境界においては、各層の構成成分は相互に拡散、または混合していてもよい。 The photoelectric conversion element of the present invention comprises a conductive substrate, a semiconductor layer sensitized by a dye placed on the conductive substrate, a charge transfer layer, and a counter electrode. The semiconductor layer may be a single layer structure or a stacked structure, and is designed according to the purpose. In addition, at the boundary of this element such as the boundary between the conductive layer and the semiconductor layer of the conductive support, the boundary between the semiconductor layer and the charge transfer layer, the constituent components of each layer may be diffused or mixed with each other.
導電性基板は、金属のように基板そのものに導電性があるもの、または表面に導電剤を含む導電層を有するガラスあるいはプラスチック製の基板を用いることができる。後者の場合、導電剤としては白金、金、銀、銅、アルミニウム等の金属、炭素、あるいはインジウム−スズ複合酸化物(以降「ITO」と略記する)、フッ素をドーピングした酸化スズ等の金属酸化物(以降「FTO」と略記する)等が挙げられる。導電性基板は、光を10%以上透過する透明性を有していることが好ましく、50%以上透過することがより好ましい。この中でも、ITOやFTOからなる導電層をガラス上に堆積した導電性ガラスが特に好ましい。 As the conductive substrate, a substrate made of glass or plastic having a conductive layer containing a conductive agent on the surface can be used, such as a metal having a conductive property in itself. In the latter case, the conductive agent is a metal oxide such as platinum, gold, silver, copper, aluminum or the like, carbon or indium-tin composite oxide (hereinafter abbreviated as “ITO”), fluorine-doped tin oxide or the like. (Hereinafter abbreviated as “FTO”) and the like. The conductive substrate preferably has a transparency that transmits light of 10% or more, and more preferably transmits 50% or more. Among these, conductive glass in which a conductive layer made of ITO or FTO is deposited on glass is particularly preferable.
透明導電性基板の抵抗を下げる目的で、金属リード線を用いてもよい。金属リード線の材質はアルミニウム、銅、銀、金、白金、ニッケル等の金属が挙げられる。金属リード線は、透明基板に蒸着、スパッタリング、圧着等で設置し、その上にITOやFTOを設ける方法、あるいは透明導電層上に金属リード線を設置する。 A metal lead wire may be used for the purpose of reducing the resistance of the transparent conductive substrate. Examples of the material of the metal lead wire include metals such as aluminum, copper, silver, gold, platinum, and nickel. A metal lead wire is installed on a transparent substrate by vapor deposition, sputtering, pressure bonding, or the like, and a method of providing ITO or FTO thereon or a metal lead wire on a transparent conductive layer.
半導体としては、シリコン、ゲルマニウムのような単体半導体、あるいは金属のカルコゲニドに代表される化合物半導体、またはペロブスカイト構造を有する化合物等を使用することができる。金属のカルコゲニドとしてはチタン、スズ、亜鉛、鉄、タングステン、ジルコニウム、ハフニウム、ストロンチウム、インジウム、セリウム、イットリウム、ランタン、バナジウム、ニオブ、あるいはタンタルの酸化物、カドミウム、亜鉛、鉛、銀、アンチモン、ビスマスの硫化物、カドミウム、鉛のセレン化物、カドミウムのテルル化物等が挙げられる。他の化合物半導体としては亜鉛、ガリウム、インジウム、カドミウム、等のリン化物、ガリウム砒素、銅−インジウム−セレン化物、銅−インジウム−硫化物等が好ましい。また、ペロブスカイト構造を有する化合物としては、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸ナトリウム、チタン酸バリウム、ニオブ酸カリウム等が好ましい。 As the semiconductor, a single semiconductor such as silicon or germanium, a compound semiconductor typified by a metal chalcogenide, a compound having a perovskite structure, or the like can be used. Metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxides, cadmium, zinc, lead, silver, antimony, bismuth. Sulfide, cadmium, lead selenide, cadmium telluride and the like. Other compound semiconductors are preferably phosphides such as zinc, gallium, indium, cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like. As the compound having a perovskite structure, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate and the like are preferable.
本発明に用いられる半導体は、単結晶でも多結晶でもよい。変換効率としては単結晶が好ましいが、製造コスト、原材料確保等の点では多結晶が好ましく、その半導体の粒径は2nm以上、1μm以下であることが好ましい。 The semiconductor used in the present invention may be single crystal or polycrystalline. As the conversion efficiency, a single crystal is preferable, but a polycrystal is preferable in terms of manufacturing cost, securing raw materials, and the like, and the particle size of the semiconductor is preferably 2 nm or more and 1 μm or less.
導電性支持体上に半導体層を形成する方法としては、半導体微粒子の分散液またはコロイド溶液を導電性支持体上に塗布する方法、ゾル−ゲル法等がある。その分散液の作製方法としては、前述のゾル−ゲル法、乳鉢等で機械的に粉砕する方法、ミルを使って粉砕しながら分散する方法、あるいは半導体を合成する際に溶媒中で微粒子として析出させ、そのまま使用する方法等が挙げられる。 Examples of a method for forming a semiconductor layer on a conductive support include a method in which a dispersion or colloidal solution of semiconductor fine particles is applied on a conductive support, a sol-gel method, and the like. The dispersion can be prepared by the above-mentioned sol-gel method, a method of mechanically pulverizing with a mortar, etc., a method of dispersing while pulverizing using a mill, or a fine particle in a solvent when synthesizing a semiconductor. And a method of using it as it is.
機械的粉砕、あるいはミルを使用して粉砕して作製する分散液の場合、少なくとも半導体微粒子単独、あるいは半導体微粒子と樹脂の混合物を水あるいは有機溶剤に分散して形成される。使用される樹脂としては、スチレン、酢酸ビニル、アクリル酸エステル、メタクリル酸エステル等によるビニル化合物の重合体や共重合体、シリコーン樹脂、フェノキシ樹脂、ポリスルホン樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ポリエステル樹脂、セルロースエステル樹脂、セルロースエーテル樹脂、ウレタン樹脂、フェノール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリアリレート樹脂、ポリアミド樹脂、ポリイミド樹脂等が挙げられる。 In the case of a dispersion prepared by mechanical pulverization or pulverization using a mill, it is formed by dispersing at least semiconductor fine particles alone or a mixture of semiconductor fine particles and a resin in water or an organic solvent. Resins used include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, acrylic acid esters, methacrylic acid esters, silicone resins, phenoxy resins, polysulfone resins, polyvinyl butyral resins, polyvinyl formal resins, polyester resins. , Cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, polyamide resin, polyimide resin and the like.
半導体微粒子を分散する溶媒としては、水、メタノール、エタノール、あるいはイソプロピルアルコール等のアルコール系溶媒、アセトン、メチルエチルケトン、あるいはメチルイソブチルケトン等のケトン系溶媒、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチル等のエステル系溶媒、ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキソラン、あるいはジオキサン等のエーテル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、あるいはN−メチル−2−ピロリドン等のアミド系溶媒、ジクロロメタン、クロロホルム、ブロモホルム、ヨウ化メチル、ジクロロエタン、トリクロロエタン、トリクロロエチレン、クロロベンゼン、o−ジクロロベンゼン、フルオロベンゼン、ブロモベンゼン、ヨードベンゼン、あるいは1−クロロナフタレン等のハロゲン化炭化水素系溶媒、n−ペンタン、n−ヘキサン、n−オクタン、1,5−ヘキサジエン、シクロヘキサン、メチルシクロヘキサン、シクロヘキサジエン、ベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、エチルベンゼン、あるいはクメン等の炭化水素系溶媒を挙げることができる。これらは単独、あるいは2種以上の混合溶媒として用いることができる。 Solvents for dispersing the semiconductor fine particles include alcohol solvents such as water, methanol, ethanol, and isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl formate, ethyl acetate, and n-butyl acetate. Ester solvents, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or ether solvents such as dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, or amide solvents such as N-methyl-2-pyrrolidone , Dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodine Halogenated hydrocarbon solvents such as debenzene or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, Examples thereof include hydrocarbon solvents such as m-xylene, p-xylene, ethylbenzene, and cumene. These can be used alone or as a mixed solvent of two or more.
得られた分散液の塗布方法としては、ローラ法、ディップ法、エアナイフ法、ブレード法、ワイヤーバー法、スライドホッパ法、エクストルージョン法、カーテン法、スピン法、あるいはスプレー法を挙げることができる。 Examples of the method for applying the obtained dispersion include a roller method, a dip method, an air knife method, a blade method, a wire bar method , a slide hopper method, an extrusion method, a curtain method, a spin method, and a spray method.
更に半導体層は、単層であっても多層であってもよい。多層の場合、粒径の異なる半導体微粒子の分散液を多層塗布したり、種類の異なる半導体や、樹脂、添加剤の組成が異なる塗布層を多層塗布することもできる。また、一度の塗布で膜厚が不足する場合には多層塗布は有効な手段である。 Furthermore, the semiconductor layer may be a single layer or multiple layers. In the case of multiple layers, a dispersion of semiconductor fine particles having different particle diameters can be applied in multiple layers, or different types of semiconductors, and application layers having different compositions of resins and additives can be applied in multiple layers. In addition, when the film thickness is insufficient with a single coating, the multilayer coating is an effective means.
一般的に、半導体層の膜厚が増大するほど単位投影面積当たりの担持色素量も増えるため光の捕獲率が高くなるが、生成した電子の拡散距離も増えるために電荷の再結合も多くなってしまう。従って、半導体層の膜厚は0.1〜100μmが好ましく、1〜30μmがより好ましい。 In general, as the thickness of the semiconductor layer increases, the amount of supported dye increases per unit projected area and the light capture rate increases. However, the diffusion distance of the generated electrons also increases, and the recombination of charges also increases. End up. Therefore, the film thickness of the semiconductor layer is preferably 0.1 to 100 μm, and more preferably 1 to 30 μm.
半導体微粒子は導電性支持体上に塗布した後、加熱処理してもしなくともよいが、粒子同士の電子的コンタクト及び塗膜強度の向上や支持体との密着性向上の点から、加熱処理、マイクロ波照射、プレス処理あるいは電子線照射を行ってもよく、これらの処理は単独で行っても二種類以上行っても構わない。加熱処理の際、加熱温度は40〜700℃が好ましく、80〜600℃がより好ましい。また、加熱時間は5分〜50時間が好ましく、10分〜20時間がより好ましい。マイクロ波照射は、半導体電極の半導体層形成側から照射しても、裏側から照射しても構わない。照射時間には特に制限が無いが、1時間以内で行うことが好ましい。プレス処理は、100kg/cm2以上が好ましく、1000kg/cm2が更に好ましい。プレスする時間は特に制限が無いが、1時間以内で行うことが好ましい。 The semiconductor fine particles may be heat-treated after being coated on the conductive support, but from the viewpoint of improving the electronic contact between the particles and the strength of the coating film and the adhesion with the support, Microwave irradiation, press treatment, or electron beam irradiation may be performed, and these treatments may be performed alone or in combination of two or more. In the heat treatment, the heating temperature is preferably 40 to 700 ° C, more preferably 80 to 600 ° C. The heating time is preferably 5 minutes to 50 hours, and more preferably 10 minutes to 20 hours. The microwave irradiation may be performed from the semiconductor layer forming side of the semiconductor electrode or from the back side. Although there is no restriction | limiting in particular in irradiation time, It is preferable to carry out within 1 hour. The press treatment is preferably 100 kg / cm 2 or more, more preferably 1000 kg / cm 2 . There is no particular limitation on the pressing time, but it is preferably performed within 1 hour.
半導体微粒子は多くの色素を吸着できるように表面積の大きなものが好ましい。このため半導体層を支持体上に塗設した状態での表面積は、投影面積に対して10倍以上であることが好ましく、100倍以上であることがより好ましい。 The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. For this reason, it is preferable that the surface area in the state which coated the semiconductor layer on the support body is 10 times or more with respect to a projection area, and it is more preferable that it is 100 times or more.
半導体層に色素を吸着させる方法としては、色素溶液中あるいは色素分散液中に半導体微粒子を含有する作用電極を浸漬する方法、色素溶液あるいは分散液を半導体層に塗布して吸着させる方法を用いることができる。前者の場合、浸漬法、ディップ法、ローラ法、エアーナイフ法等を用いることができ、後者の場合は、ワイヤーバー法、スライドホッパー法、エクストルージョン法、カーテン法、スピン法、スプレー法等を用いることができる。しかしながら、色素の吸着平衡が確実に達成されるには、溶液による浸漬法が最も優れている。 As a method of adsorbing the dye to the semiconductor layer, a method of immersing a working electrode containing semiconductor fine particles in a dye solution or a dye dispersion, or a method of applying a dye solution or a dispersion to the semiconductor layer and adsorbing it is used. Can do. In the former case, dipping method, dipping method, roller method, air knife method, etc. can be used, and in the latter case, wire bar method, slide hopper method, extrusion method, curtain method, spin method, spray method, etc. Can be used. However, the immersion method using a solution is the best method for reliably achieving the adsorption equilibrium of the dye.
本発明において半導体層表面に2種以上の色素を吸着をするための手順としては、2種以上の混合溶液を用いて同時に吸着しても良いし、2種以上の色素の個別の溶液を用いて、交互に吸着しても良い。色素溶液の濃度は2種以上の色素混合溶液の場合であれ、個別の溶液であれ、0.01〜10.0mMの範囲で任意に調製して使用する事が可能で、0.1〜5.0mMであることがより好ましい。また、2種以上の色素を交互に吸着する場合は、吸着させる色素の順番は任意に設定できる。 In the present invention, as a procedure for adsorbing two or more kinds of dyes on the surface of the semiconductor layer, two or more kinds of mixed solutions may be adsorbed simultaneously, or individual solutions of two or more kinds of dyes may be used. Alternatively, they may be alternately adsorbed. The concentration of the dye solution can be arbitrarily prepared and used in the range of 0.01 to 10.0 mM, whether it is a mixture of two or more dyes or individual solutions. More preferably, it is 0.0 mM. Moreover, when adsorb | sucking 2 or more types of pigment | dyes alternately, the order of the pigment | dye to adsorb | suck can be set arbitrarily.
色素吸着の際には縮合剤を併用してもよい。縮合剤は、無機物表面に物理的あるいは化学的に色素を結合する際の触媒をするもの、または化学量論的に反応するものの何れでもよい。更に、縮合助剤としてチオール、あるいはヒドロキシ化合物を添加してもよい。 In the case of dye adsorption, a condensing agent may be used in combination. The condensing agent may be either a catalyst that physically or chemically binds the dye to the inorganic surface or a substance that reacts stoichiometrically. Furthermore, a thiol or a hydroxy compound may be added as a condensation aid.
色素を溶解、あるいは分散する溶媒は、水、メタノール、エタノール、あるいはイソプロピルアルコール等のアルコール系溶媒、アセトン、メチルエチルケトン、あるいはメチルイソブチルケトン等のケトン系溶媒、アセトニトリル、3−メトキシプロピオニトリル等のニトリル系溶媒、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチル等のエステル系溶媒、ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキソラン、あるいはジオキサン等のエーテル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、あるいはN−メチル−2−ピロリドン等のアミド系溶媒、ジクロロメタン、クロロホルム、ブロモホルム、ヨウ化メチル、ジクロロエタン、トリクロロエタン、トリクロロエチレン、クロロベンゼン、o−ジクロロベンゼン、フルオロベンゼン、ブロモベンゼン、ヨードベンゼン、あるいは1−クロロナフタレン等のハロゲン化炭化水素系溶媒、n−ペンタン、n−ヘキサン、n−オクタン、1,5−ヘキサジエン、シクロヘキサン、メチルシクロヘキサン、シクロヘキサジエン、ベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、エチルベンゼン、あるいはクメン等の炭化水素系溶媒を挙げることができ、これらは単独、あるいは2種以上の混合として用いることができる。 Solvents that dissolve or disperse the dye are alcohol solvents such as water, methanol, ethanol, and isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and nitriles such as acetonitrile and 3-methoxypropionitrile. Solvents, ester solvents such as ethyl formate, ethyl acetate, or n-butyl acetate, ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, N, N-dimethylformamide, N, N-dimethyl Amide solvents such as acetamide or N-methyl-2-pyrrolidone, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chloroben , O-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, or halogenated hydrocarbon solvents such as 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, Examples include hydrocarbon solvents such as methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene, and these are used alone or as a mixture of two or more. be able to.
色素を吸着する際の温度としては、−50℃以上、200℃以下が好ましい。また、このとき色素溶液を攪拌しながら行っても構わない。攪拌する場合の方法としては、スターラー、ボールミル、ペイントコンディショナー、サンドミル、アトライター、ディスパーザー、あるいは超音波分散等が挙げられるが、これらに限定されるものではない。吸着に要する時間は、5秒以上、1000時間以下が好ましく、10秒以上、500時間以下がより好ましく、1分以上、150時間以下が更に好ましい。 As temperature at the time of adsorb | sucking a pigment | dye, -50 degreeC or more and 200 degrees C or less are preferable. At this time, the dye solution may be stirred. Examples of the stirring method include, but are not limited to, a stirrer, a ball mill, a paint conditioner, a sand mill, an attritor, a disperser, and ultrasonic dispersion. The time required for adsorption is preferably 5 seconds or more and 1000 hours or less, more preferably 10 seconds or more and 500 hours or less, and further preferably 1 minute or more and 150 hours or less.
本発明では、色素を吸着する際に界面活性剤を併用しても構わない。界面活性剤としては、ステロイド系化合物、とりわけコール酸誘導体が好ましく、その具体例としては、(E−1)〜(E−10)に示すものが挙げられる。ステロイド系化合物の量は、色素1質量部に対して0.01〜1000質量部が好ましく、0.1〜100質量部がより好ましい。 In the present invention, a surfactant may be used in combination when adsorbing the dye. As the surfactant, steroidal compounds, particularly cholic acid derivatives, are preferable, and specific examples thereof include those shown in (E-1) to (E-10). 0.01-1000 mass parts is preferable with respect to 1 mass part of pigment | dyes, and, as for the quantity of a steroid type compound, 0.1-100 mass parts is more preferable.
本発明の光電変換素子の電荷移動層としては、酸化還元対を有機溶媒に溶解した電解液、酸化還元対を有機溶媒に溶解した液体をポリマーマトリックスに含浸したゲル電解質、酸化還元対を含有する溶融塩、固体電解質、有機正孔輸送材料等を用いることができる。 The charge transfer layer of the photoelectric conversion element of the present invention contains an electrolytic solution in which a redox couple is dissolved in an organic solvent, a gel electrolyte in which a liquid in which the redox couple is dissolved in an organic solvent is impregnated in a polymer matrix, and a redox couple Molten salts, solid electrolytes, organic hole transport materials, and the like can be used.
本発明で使用される電解液は、電解質、溶媒、及び添加物から構成されることが好ましい。好ましい電解質はヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化セシウム、ヨウ化カルシウム等の金属ヨウ化物−ヨウ素の組み合わせ、テトラアルキルアンモニウムヨ−ダイド、ピリジニウムヨーダイド、イミダゾリウムヨーダイド等の4級アンモニウム化合物のヨウ素塩−ヨウ素の組み合わせ、臭化リチウム、臭化ナトリウム、臭化カリウム、臭化セシウム、臭化カルシウム等の金属臭化物−臭素の組み合わせ、テトラアルキルアンモニウムブロマイド、ピリジニウムブロマイド等の4級アンモニウム化合物の臭素塩−臭素の組み合わせ、フェロシアン酸塩−フェリシアン酸塩、フェロセン−フェリシニウムイオン等の金属錯体、ポリ硫化ナトリウム、アルキルチオール−アルキルジスルフィド等のイオウ化合物、ビオロゲン色素、ヒドロキノン−キノン等が挙げられる。上述の電解質は単独の組み合わせであっても混合であってもよい。また、電解質として、室温で溶融状態の溶融塩を用いることもできる。この溶融塩を用いた場合は、特に溶媒を用いなくても構わない。 The electrolytic solution used in the present invention is preferably composed of an electrolyte, a solvent, and an additive. Preferred electrolytes include metal iodide-iodine combinations such as lithium iodide, sodium iodide, potassium iodide, cesium iodide, and calcium iodide, tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide, and the like. Iodine salts of quaternary ammonium compounds-iodine combinations, metal bromides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, calcium bromide-bromine combinations, quaternary compounds such as tetraalkylammonium bromide, pyridinium bromide Bromine-bromine combinations of ammonium compounds, metal complexes such as ferrocyanate-ferricyanate, ferrocene-ferricinium ion, sulfur compounds such as sodium polysulfide, alkylthiol-alkyldisulfide, viologen Dye, hydroquinone - quinones, and the like. The above-mentioned electrolytes may be a single combination or a mixture. Further, a molten salt in a molten state at room temperature can also be used as the electrolyte. When this molten salt is used, it is not necessary to use a solvent.
電解液における電解質濃度は、0.05〜20Mが好ましく、0.1〜15Mが更に好ましい。電解液に用いる溶媒としては、エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒、3−メチル−2−オキサゾリジノン等の複素環化合物、ジオキサン、ジエチルエーテル、エチレングリコールジアルキルエーテル等のエーテル系溶媒、メタノール、エタノール、ポリプロピレングリコールモノアルキルエーテル等のアルコール系溶媒、アセトニトリル、3−メトキシプロピオニトリル、ベンゾニトリル等のニトリル系溶媒、ジメチルスルホキシド、スルホラン等の非プロトン性極性溶媒等が好ましい。また、t−ブチルピリジン、2−ピコリン、2,6−ルチジン等の塩基性化合物を併用しても構わない。 The electrolyte concentration in the electrolytic solution is preferably 0.05 to 20M, and more preferably 0.1 to 15M. Solvents used for the electrolyte include carbonate solvents such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether solvents such as dioxane, diethyl ether and ethylene glycol dialkyl ether, methanol, ethanol Alcohol solvents such as polypropylene glycol monoalkyl ether, nitrile solvents such as acetonitrile, 3-methoxypropionitrile and benzonitrile, and aprotic polar solvents such as dimethyl sulfoxide and sulfolane are preferred. Further, basic compounds such as t-butylpyridine, 2-picoline, and 2,6-lutidine may be used in combination.
本発明では、電解質はポリマー添加、オイルゲル化剤添加、多官能モノマー類を含む重合、ポリマーの架橋反応等の手法によりゲル化させることもできる。ポリマー添加によりゲル化させる場合の好ましいポリマーとしては、ポリアクリロニトリル、ポリフッ化ビニリデン等を挙げることができる。オイルゲル化剤添加によりゲル化させる場合の好ましいゲル化剤としては、ジベンジルデン−D−ソルビトール、コレステロール誘導体、アミノ酸誘導体、トランス−(1R,2R)−1,2−シクロヘキサンジアミンのアルキルアミド誘導体、アルキル尿素誘導体、N−オクチル−D−グルコンアミドベンゾエート、双頭型アミノ酸誘導体、4級アンモニウム誘導体等を挙げることができる。 In the present invention, the electrolyte can be gelled by a technique such as addition of a polymer, addition of an oil gelling agent, polymerization including polyfunctional monomers, or a crosslinking reaction of the polymer. Preferable polymers in the case of gelation by polymer addition include polyacrylonitrile, polyvinylidene fluoride and the like. Preferred gelling agents for gelation by adding an oil gelling agent include dibenzylden-D-sorbitol, cholesterol derivatives, amino acid derivatives, alkylamide derivatives of trans- (1R, 2R) -1,2-cyclohexanediamine, alkylureas Derivatives, N-octyl-D-gluconamide benzoate, double-headed amino acid derivatives, quaternary ammonium derivatives and the like can be mentioned.
多官能モノマーによって重合する場合の好ましいモノマーとしては、ジビニルベンゼン、エチレングリコールジメタクリレート、エチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート等を挙げることができる。更に、アクリルアミド、メチルアクリレート等のアクリル酸やα−アルキルアクリル酸から誘導されるエステル類やアミド類、マレイン酸ジメチル、フマル酸ジエチル等のマレイン酸やフマル酸から誘導されるエステル類、ブタジエン、シクロペンタジエン等のジエン類、スチレン、p−クロロスチレン、スチレンスルホン酸ナトリウム等の芳香族ビニル化合物、ビニルエステル類、アクリロニトリル、メタクリロニトリル、含窒素複素環を有するビニル化合物、4級アンモニウム塩を有するビニル化合物、N−ビニルホルムアミド、ビニルスルホン酸、ビニリデンフルオライド、ビニルアルキルエーテル類、N−フェニルマレイミド等の単官能モノマーを含有してもよい。モノマー全量に占める多官能性モノマーは、0.5〜70質量%が好ましく、1.0〜50質量%がより好ましい。 Preferred monomers when polymerized by polyfunctional monomer include divinylbenzene, Echirengu recall dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate be able to. Furthermore, esters and amides derived from acrylic acid such as acrylamide and methyl acrylate and α-alkyl acrylic acid, esters derived from maleic acid and fumaric acid such as dimethyl maleate and diethyl fumarate, butadiene, cyclohexane and the like. Dienes such as pentadiene, aromatic vinyl compounds such as styrene, p-chlorostyrene and sodium styrene sulfonate, vinyl esters, acrylonitrile, methacrylonitrile, vinyl compounds having a nitrogen-containing heterocyclic ring, vinyl having a quaternary ammonium salt A monofunctional monomer such as a compound, N-vinylformamide, vinylsulfonic acid, vinylidene fluoride, vinyl alkyl ethers, N-phenylmaleimide may be contained. 0.5-70 mass% is preferable and the polyfunctional monomer which occupies for the monomer whole quantity has more preferable 1.0-50 mass%.
上述のモノマーは、ラジカル重合によって重合することができる。本発明で使用できるゲル電解質用モノマーは、加熱、光、電子線あるいは電気化学的にラジカル重合することができる。架橋高分子が加熱によって形成される場合に使用される重合開始剤は、2,2´−アゾビスイソブチロニトリル、2,2´−アゾビス(2,4−ジメチルバレロニトリル)、ジメチル−2,2´−アゾビス(2−メチルプロピオネート)等のアゾ系開始剤、ベンゾイルパーオキシド等の過酸化物系開始剤等が好ましい。これらの重合開始剤の添加量は、モノマー総量に対して、0.01〜20質量%が好ましく、0.1〜10質量%がより好ましい。 The above-mentioned monomers can be polymerized by radical polymerization. The monomer for gel electrolyte that can be used in the present invention can be radically polymerized by heating, light, electron beam or electrochemical. The polymerization initiator used when the crosslinked polymer is formed by heating is 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl-2. Azo initiators such as 2,2′-azobis (2-methylpropionate) and peroxide initiators such as benzoyl peroxide are preferable. The addition amount of these polymerization initiators is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total amount of monomers.
ポリマーの架橋反応により電解質をゲル化させる場合、架橋反応に必要な反応性基を含有するポリマー及び架橋剤を併用することが望ましい。架橋可能な反応性基に好ましい例としては、ピリジン、イミダゾール、チアゾール、オキサゾール、トリアゾール、モルフォリン、ピペリジン、ピペラジン等の含窒素複素環を挙げることができ、好ましい架橋剤は、ハロゲン化アルキル、ハロゲン化アラルキル、スルホン酸エステル、酸無水物、酸クロリド、イソシアネート等の窒素原子に対して求電子反応可能な2官能以上の試薬を挙げることができる。 When the electrolyte is gelled by a polymer crosslinking reaction, it is desirable to use a polymer containing a reactive group necessary for the crosslinking reaction and a crosslinking agent in combination. Preferable examples of the crosslinkable reactive group include nitrogen-containing heterocycles such as pyridine, imidazole, thiazole, oxazole, triazole, morpholine, piperidine, piperazine, etc. Preferred crosslinking agents include alkyl halides, halogens Bifunctional or higher functional reagents capable of electrophilic reaction with nitrogen atoms such as aralkyl fluoride, sulfonic acid ester, acid anhydride, acid chloride, and isocyanate can be exemplified.
無機固体化合物を電解質の代わりに用いる場合、ヨウ化銅、チオシアン化銅等をキャスト法、塗布法、スピンコート法、浸漬法、電解メッキ等の手法により電極内部に導入することができる。 When an inorganic solid compound is used instead of the electrolyte, copper iodide, copper thiocyanide, or the like can be introduced into the electrode by a casting method, a coating method, a spin coating method, a dipping method, electrolytic plating, or the like.
また、本発明では電解質の代わりに有機電荷輸送物質を用いることができる。電荷輸送物質には正孔輸送物質と電子輸送物質がある。前者の例としては、例えば特公昭34−5466号公報等に示されているオキサジアゾール類、特公昭45−555号公報等に示されているトリフェニルメタン類、特公昭52−4188号公報等に示されているピラゾリン類、特公昭55−42380号公報等に示されているヒドラゾン類、特開昭56−123544号公報等に示されているオキサジアゾール類、特開昭54−58445号公報に示されているテトラアリールベンジジン類、特開昭58−65440号公報、あるいは特開昭60−98437号公報に示されているスチルベン類等を挙げることができる。その中でも、本発明に使用される電荷輸送物質としては、特開昭60−24553号公報、特開平2−96767号公報、特開平2−183260号公報、並びに特開平2−226160号公報に示されているヒドラゾン類、特開平2−51162号公報、並びに特開平3−75660号公報に示されているスチルベン類が特に好ましい。また、これらは単独、あるいは2種以上の混合物として用いることができる。 In the present invention, an organic charge transport material can be used instead of the electrolyte. Charge transport materials include hole transport materials and electron transport materials. Examples of the former include, for example, oxadiazoles disclosed in Japanese Patent Publication No. 34-5466, triphenylmethanes disclosed in Japanese Patent Publication No. 45-555, and Japanese Patent Publication No. 52-4188. Pyrazolines shown in the above, hydrazones shown in JP-B-55-42380, oxadiazoles shown in JP-A-56-123544, etc., JP-A-54-58445 And tetrasylbenzidines disclosed in JP-A No. 58-65440, and stilbenes disclosed in JP-A No. 60-98437. Among them, examples of the charge transport material used in the present invention are shown in JP-A-60-24553, JP-A-2-96767, JP-A-2-183260, and JP-A-2-226160. Particularly preferred are the hydrazones described, and the stilbenes shown in JP-A-2-51162 and JP-A-3-75660. Moreover, these can be used individually or in mixture of 2 or more types.
一方、電子輸送物質としては、例えばクロラニル、テトラシアノエチレン、テトラシアノキノジメタン、2,4,7−トリニトロ−9−フルオレノン、2,4,5,7−テトラニトロ−9−フルオレノン、2,4,5,7−テトラニトロキサントン、2,4,8−トリニトロチオキサントン、1,3,7−トリニトロジベンゾチオフェン、あるいは1,3,7−トリニトロジベンゾチオフェン−5,5−ジオキシド等がある。これらの電子輸送物質は単独、あるいは2種以上の混合物として用いることができる。 On the other hand, examples of the electron transport material include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 1,3,7-trinitrodibenzothiophene, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, etc. . These electron transport materials can be used alone or as a mixture of two or more.
また、更に増感効果を増大させる増感剤として、ある種の電子吸引性化合物を添加することもできる。この電子吸引性化合物としては例えば、2,3−ジクロロ−1,4−ナフトキノン、1−ニトロアントラキノン、1−クロロ−5−ニトロアントラキノン、2−クロロアントラキノン、フェナントレンキノン等のキノン類、4−ニトロベンズアルデヒド等のアルデヒド類、9−ベンゾイルアントラセン、インダンジオン、3,5−ジニトロベンゾフェノン、あるいは3,3′,5,5′−テトラニトロベンゾフェノン等のケトン類、無水フタル酸、4−クロロナフタル酸無水物等の酸無水物、テレフタラルマロノニトリル、9−アントリルメチリデンマロノニトリル、4−ニトロベンザルマロノニトリル、あるいは4−(p−ニトロベンゾイルオキシ)ベンザルマロノニトリル等のシアノ化合物、3−ベンザルフタリド、3−(α−シアノ−p−ニトロベンザル)フタリド、あるいは3−(α−シアノ−p−ニトロベンザル)−4,5,6,7−テトラクロロフタリド等のフタリド類等を挙げることができる。 Further, as a sensitizer that further increases the sensitizing effect, a certain kind of electron-withdrawing compound can be added. Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, and phenanthrenequinone, 4-nitro Aldehydes such as benzaldehyde, ketones such as 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, or 3,3 ', 5,5'-tetranitrobenzophenone, phthalic anhydride, 4-chloronaphthalic anhydride Acid anhydrides such as terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile, 4-nitrobenzalmalononitrile, or cyano compounds such as 4- (p-nitrobenzoyloxy) benzalmalononitrile, 3-benzalphthalide , 3- (α-cyano- - Nitorobenzaru) phthalide, or 3- (alpha-cyano -p- Nitorobenzaru) -4,5,6,7 can be mentioned phthalides such as tetrachloro phthalide like.
これらの電荷輸送材料を用いて電荷移動層を形成する場合、樹脂を併用しても構わない。樹脂を併用する場合にはポリスチレン樹脂、ポリビニルアセタール樹脂、ポリスルホン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリフェニレンオキサイド樹脂、ポリアリレート樹脂、アクリル樹脂、メタクリル樹脂、フェノキシ樹脂等が挙げられる。これらの中でも、ポリスチレン樹脂、ポリビニルアセタール樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアリレート樹脂が好ましい。これらの樹脂は、単独あるいは共重合体として2種以上を混合しても構わない。 When forming a charge transfer layer using these charge transport materials, a resin may be used in combination. When resin is used in combination, polystyrene resin, polyvinyl acetal resin, polysulfone resin, polycarbonate resin, polyester resin, polyphenylene oxide resin, polyarylate resin, acrylic resin, methacrylic resin, phenoxy resin and the like can be mentioned. Among these, polystyrene resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, and polyarylate resin are preferable. These resins may be used alone or as a copolymer in combination of two or more.
電荷移動層の形成方法は大きく2通りの方法が挙げられる。1つは増感色素を担持した半導体微粒子含有層の上に、先に対極を貼り合わせ、その隙間に液状の電荷移動層を挟み込む方法、もう一つは、半導体微粒子含有層の上に直接電荷移動層を付与する方法である。後者の場合、対極はその後新たに付与することになる。 There are two main methods for forming the charge transfer layer. One is a method in which a counter electrode is first pasted on a semiconductor fine particle-containing layer carrying a sensitizing dye, and a liquid charge transfer layer is sandwiched between the opposite electrodes. This is a method of providing a moving layer. In the latter case, the counter electrode is newly added thereafter.
前者の場合、電荷移動層の挟み込み方法として、浸漬等による毛管現象を利用する常圧プロセスと常圧より低い圧力にして気相を液相に置換する真空プロセスが挙げられる。後者の場合、湿式の電荷移動層においては未乾燥のまま対極を付与し、エッジ部の液漏洩防止を施す必要がある。また、ゲル電解液の場合においては、湿式で塗布して重合等の方法により固体化する方法もある。その場合、乾燥、固定化した後に対極を付与してもよい。電解液の他、有機電荷輸送材料の溶解液やゲル電解質を付与する方法としては、半導体微粒子含有層や色素の付与と同様に、浸漬法、ローラ法、ディップ法、エアーナイフ法、エクストルージョン法、スライドホッパー法、ワイヤーバー法、スピン法、スプレー法、キャスト法、各種印刷法等が挙げられる。 In the former case, examples of the method for sandwiching the charge transfer layer include a normal pressure process using a capillary phenomenon due to immersion and a vacuum process in which the gas phase is replaced with a liquid phase at a pressure lower than normal pressure. In the latter case, in the wet charge transfer layer, it is necessary to provide a counter electrode without being dried to prevent liquid leakage at the edge portion. In the case of a gel electrolyte, there is a method in which it is applied in a wet manner and solidified by a method such as polymerization. In that case, you may provide a counter electrode after drying and fixing. In addition to the electrolyte solution, the organic charge transport material solution and the gel electrolyte can be applied in the same manner as the semiconductor fine particle-containing layer and the dye, as in the immersion method, roller method, dipping method, air knife method, and extrusion method. , Slide hopper method, wire bar method, spin method, spray method, casting method, various printing methods, and the like.
対極は通常前述の導電性基板と同様に導電性層を有する支持体を用いることもできるが、強度や密封性が十分に保たれるような構成では支持体は必ずしも必要ではない。対極に用いる材料の具体例としては、白金、金、銀、銅、アルミニウム、ロジウム、インジウム等の金属、炭素系化合物、ITO、FTO等の導電性金属酸化物等が挙げられる。対極の厚さには特に制限はない。 As the counter electrode, a support having a conductive layer can be used as in the case of the above-described conductive substrate. However, the support is not necessarily required in a configuration in which strength and sealability are sufficiently maintained. Specific examples of the material used for the counter electrode include metals such as platinum, gold, silver, copper, aluminum, rhodium and indium, carbon compounds, and conductive metal oxides such as ITO and FTO. There is no particular limitation on the thickness of the counter electrode.
半導体層に光が到達するためには、導電性基板と対極の少なくとも一方は実質的に透明でなければならない。本発明の光電変換素子においては、導電性基板が透明であり、太陽光を導電性基板側から入射させる方法が好ましい。この場合、対極には光を反射させる材料を使用することが好ましく、金属、導電性酸化物を蒸着したガラス、プラスチック、あるいは金属薄膜が好ましい。 In order for light to reach the semiconductor layer, at least one of the conductive substrate and the counter electrode must be substantially transparent. In the photoelectric conversion element of the present invention, a method in which the conductive substrate is transparent and sunlight is incident from the conductive substrate side is preferable. In this case, a material that reflects light is preferably used for the counter electrode, and a metal, glass, plastic, or metal thin film on which a conductive oxide is deposited is preferable.
対極の塗設については前述の通り、電荷移動層の上に付与する場合と半導体微粒子層上に付与する場合の2通りがある。何れの場合も対極材料の種類や電荷移動層の種類により、適宜、電荷移動層上または半導体微粒子含有層上に対極材料を塗布、ラミネート、蒸着、貼り合わせ等の手法により形成可能である。また、電荷移動層が固体の場合には、その上に直接、前述の導電性材料を塗布、蒸着、CVD等の手法で対極を形成することができる。 As described above, there are two types of coating of the counter electrode: when applied on the charge transfer layer and when applied on the semiconductor fine particle layer. In any case, the counter electrode material can be appropriately formed on the charge transfer layer or the semiconductor fine particle-containing layer by a technique such as coating, laminating, vapor deposition, or bonding depending on the type of the counter electrode material or the type of the charge transfer layer. When the charge transfer layer is solid, the counter electrode can be formed directly on the charge transfer layer by a technique such as coating, vapor deposition, or CVD.
(実施例)
以下実施例によって本発明を更に詳しく説明するが、本発明はこの実施例に限定されるものではない。なお、実施例中の部数や百分率は全て質量基準である。
(Example)
Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples. In addition, all the parts and percentages in the examples are based on mass.
合成例1 例示化合物(A−8)の合成
化合物(F−1)(1.0g)、シアノ酢酸(0.40g)、酢酸アンモニウム(0.13g)を酢酸4.7gに溶解し、120℃で加熱撹拌。30分後、加熱を停止すると直ぐに固化。室温まで冷却後、水(50ml)を加えて撹拌し、結晶を濾取。結晶をビーカーに移し、水(100ml)で2回洗浄し、次いで2−プロパノール(50ml)で2回洗浄して粗生成物を得た。これを、クロロホルム/メタノール=10/1(容量比)を用いたシリカゲルカラムクロマトグラフィーで精製して、例示化合物(A−8)を得た。メタノール中での吸収スペクトルデータ:λmax(吸収極大波長)=425nm、ε(モル吸収係数)=5.0×104mol−1・cm−1
Synthesis Example 1 Synthesis of Exemplified Compound (A- 8 ) Compound (F-1) (1.0 g), cyanoacetic acid (0.40 g) and ammonium acetate (0.13 g) were dissolved in 4.7 g of acetic acid, and 120 ° C. Stir with heat. After 30 minutes, solidify as soon as heating is stopped. After cooling to room temperature, water (50 ml) was added and stirred, and the crystals were collected by filtration. The crystals were transferred to a beaker and washed twice with water (100 ml) and then twice with 2-propanol (50 ml) to give the crude product. This was purified by silica gel column chromatography using chloroform / methanol = 10/1 (volume ratio) to obtain Illustrative Compound (A- 8 ). Absorption spectrum data in methanol: λmax (absorption maximum wavelength) = 425 nm, ε (molar absorption coefficient) = 5.0 × 10 4 mol −1 · cm −1
合成例2 例示化合物(B−7)の合成
化合物(F−2)(1.5g)、シアノ酢酸(1.1g)、ピペリジン(0.5g)をアセトニトリル200mlに溶解し、82℃で70時間加熱攪拌した。反応液を室温に冷却後、沈殿した油状物を取り出し、アセトニトリル20mlで洗浄した。これをクロロホルム/メタノール=5/1(容量比)を用いたシリカゲルカラムクロマトグラフィーで精製して、例示化合物(B−7)のピペリジン塩を得た。さらにこれをクロロホルム300mlに溶解し、1%塩酸100mlで2回洗浄し、次いで水100mlで3回洗浄し、無水硫酸マグネシウムで乾燥後クロロホルムを減圧留去して、例示化合物(B−7)を得た。DMF中での吸収スペクトルデータ:λmax(吸収極大波長)=390nm、ε(モル吸収係数)=7.1×104mol-1・cm-1
Synthesis Example 2 Synthesis of Exemplary Compound (B-7) Compound (F-2) (1.5 g), cyanoacetic acid (1.1 g), and piperidine (0.5 g) were dissolved in 200 ml of acetonitrile, and the mixture was heated at 82 ° C. for 70 hours. Stir with heating. After cooling the reaction solution to room temperature, the precipitated oil was taken out and washed with 20 ml of acetonitrile. This was purified by silica gel column chromatography using chloroform / methanol = 5/1 (volume ratio) to obtain a piperidine salt of exemplary compound (B-7). Further, this was dissolved in 300 ml of chloroform, washed twice with 100 ml of 1% hydrochloric acid, then washed three times with 100 ml of water, dried over anhydrous magnesium sulfate, and then chloroform was distilled off under reduced pressure to give Example Compound (B-7). Obtained. Absorption spectrum data in DMF: λmax (absorption maximum wavelength) = 390 nm, ε (molar absorption coefficient) = 7.1 × 10 4 mol −1 · cm −1
酸化チタン膜の作製
酸化チタン(日本エアロジル社製P−25)2g、アセチルアセトン0.2g、界面活性剤(アルドリッチ社製Triton X−100)0.3gを水6.5gと共にペイントコンディショナー(レッドデビル社製)で6時間分散処理を施した。更に、この分散液4.0gに対して濃硝酸0.2ml、エタノール0.4ml、ポリエチレングリコール(#20,000)1.2gを加えてペーストを作製した。このペーストをFTOガラス基板上に膜厚5μmになるように塗布し、室温で乾燥後、100℃で1時間、更に500℃で1時間焼成して酸化チタン膜を作製した。
Preparation of Titanium Oxide Film Paint Conditioner (Red Devil) 2 g of titanium oxide (P-25 manufactured by Nippon Aerosil Co., Ltd.), 0.2 g of acetylacetone, and 0.3 g of surfactant (Triton X-100 manufactured by Aldrich) together with 6.5 g of water For 6 hours. Further, 0.2 g of concentrated nitric acid, 0.4 ml of ethanol, and 1.2 g of polyethylene glycol (# 20,000) were added to 4.0 g of this dispersion to prepare a paste. This paste was applied on an FTO glass substrate so as to have a film thickness of 5 μm, dried at room temperature, and then baked at 100 ° C. for 1 hour and further at 500 ° C. for 1 hour to produce a titanium oxide film.
色素溶液1の作製
例示化合物(A−8)をt−ブチルアルコール/アセトニトリル(1/1)の混合溶液に溶解し、例示化合物(A−8)の濃度が0.5mMの色素溶液1を作製した。
Preparation of Dye Solution 1 Exemplified Compound (A- 8 ) is dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1) to prepare Dye Solution 1 having a concentration of Exemplified Compound (A- 8 ) of 0.5 mM. did.
色素溶液2の作製
例示化合物(D−1)と(E−1)をt−ブチルアルコール/アセトニトリル(1/1)の混合溶液に溶解し、例示化合物(D−1)の濃度が0.5mM、例示化合物(E−1)の濃度が1.0mMの色素溶液2を作製した。
Preparation of dye solution 2 Exemplified compounds (D-1) and (E-1) were dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1), and the concentration of the exemplified compound (D-1) was 0.5 mM. A dye solution 2 having a concentration of exemplary compound (E-1) of 1.0 mM was prepared.
先に作製した酸化チタン膜を、色素溶液1に室温下で90分間浸漬して例示化合物(A−8)の吸着処理をした。次いで、この例示化合物(A−8)を吸着処理した酸化チタン膜を、色素溶液2に室温下で90分間浸漬して例示化合物(D−1)の吸着処理をして、2種以上の色素を吸着した半導体電極を作製した。 The previously prepared titanium oxide film was immersed in the dye solution 1 at room temperature for 90 minutes to perform adsorption treatment of the exemplary compound (A- 8 ). Next, the titanium oxide film on which the exemplified compound (A- 8 ) is adsorbed is immersed in the dye solution 2 at room temperature for 90 minutes to adsorb the exemplified compound (D-1), thereby obtaining two or more kinds of dyes. The semiconductor electrode which adsorb | sucked was produced.
色素を吸着した半導体電極と対極とを対向配置した間隙に電解液を注入して、半導体電極を作用極とする光電変換素子を作製した。なお、対極にはチタニウム板上にスパッタリングによって形成した白金膜を、電解液にはヨウ化リチウム0.1M、ヨウ素0.05M、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾリウム0.5Mの3−メトキシプロピオニトリル溶液を使用した。この光電変換素子に、作用極側からソーラーシミュレータ光源(東洋テクニカ製;Solartron SI−1280B)による疑似太陽光(AM1.5、照射強度100mW/cm2)を照射した。その結果得られた光電変換特性を表1に示した。また、この光電変換素子に、作用極側から波長300〜900nmの単色光を5nm刻みで照射して、量子効率の入射光波長依存性を測定した。その結果を図1に示した。 An electrolytic solution was injected into a gap in which a semiconductor electrode adsorbing a dye and a counter electrode were arranged to face each other, to produce a photoelectric conversion element using the semiconductor electrode as a working electrode. The counter electrode is a platinum film formed on a titanium plate by sputtering, and the electrolyte solution is 0.1M lithium iodide, 0.05M iodine, 1,2-dimethyl-3-n-propylimidazolium iodide,. using 3-methoxy propionic nitrile solution 5M. This photoelectric conversion element was irradiated with simulated sunlight (AM1.5, irradiation intensity: 100 mW / cm 2 ) from a solar simulator light source (manufactured by Toyo Technica; Solartron SI-1280B) from the working electrode side. The photoelectric conversion characteristics obtained as a result are shown in Table 1. Moreover, this photoelectric conversion element was irradiated with monochromatic light having a wavelength of 300 to 900 nm from the working electrode side in increments of 5 nm, and the dependence of the quantum efficiency on the incident light wavelength was measured. The results are shown in FIG.
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液2に室温下で90分間浸漬して例示化合物(D−1)の吸着処理をした。次いで、この例示化合物(D−1)を吸着処理した酸化チタン膜を、色素溶液1に室温下で90分間浸漬して例示化合物(A−8)の吸着処理をして、2種以上の色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表1に示した。 The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 2 at room temperature for 90 minutes to perform the adsorption treatment of the exemplary compound (D-1). Next, the titanium oxide film on which the exemplary compound (D-1) is adsorbed is immersed in the dye solution 1 at room temperature for 90 minutes to adsorb the exemplary compound (A- 8 ), and two or more types of dyes are absorbed. The semiconductor electrode which adsorb | sucked was produced. Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 1.
色素溶液3の作製
例示化合物(A−8)、例示化合物(D−1)および例示化合物(E−1)をt−ブチルアルコール/アセトニトリル(1/1)の混合溶液に溶解し、例示化合物(A−8)の濃度が0.5mM、例示化合物(D−1)の濃度が0.5mM、および例示化合物(E−1)の濃度が1.0mMの色素溶液3を作製した。
Preparation of dye solution 3 Exemplified compound (A- 8 ), exemplified compound (D-1) and exemplified compound (E-1) were dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1), and exemplified compound ( A dye solution 3 having a concentration of A- 8 ) of 0.5 mM, a concentration of exemplary compound (D-1) of 0.5 mM, and a concentration of exemplary compound (E-1) of 1.0 mM was prepared.
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液3に、室温下で3時間浸漬して例示化合物(A−8)と例示化合物(D−1)の吸着処理をして、2種以上の色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表1に示した。 The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 3 at room temperature for 3 hours to adsorb the exemplified compound (A- 8 ) and the exemplified compound (D-1), A semiconductor electrode adsorbing two or more dyes was prepared. Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 1.
(比較例1)
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液1に、室温下で3時間浸漬して例示化合物(A−8)の吸着処理を行い、色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表1に示した。また、この光電変換素子に、作用極側から波長300〜900nmの単色光を5nm刻みで照射して、量子効率の入射光波長依存性を測定した。その結果を図1に示した。
(Comparative Example 1)
The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 1 at room temperature for 3 hours to perform the adsorption treatment of the exemplified compound (A- 8 ) to produce a semiconductor electrode adsorbing the dye. . Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 1. Moreover, this photoelectric conversion element was irradiated with monochromatic light having a wavelength of 300 to 900 nm from the working electrode side in increments of 5 nm, and the dependence of the quantum efficiency on the incident light wavelength was measured. The results are shown in FIG.
(比較例2)
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液2に、室温下で3時間浸漬して例示化合物(D−1)の吸着処理をして、色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表1に示した。また、この光電変換素子に、作用極側から波長300〜900nmの単色光を5nm刻みで照射して、量子効率の入射光波長依存性を測定した。その結果を図1に示した。
(Comparative Example 2)
A titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 2 at room temperature for 3 hours to adsorb the exemplified compound (D-1) to produce a semiconductor electrode adsorbed with the dye. did. Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 1. Moreover, this photoelectric conversion element was irradiated with monochromatic light having a wavelength of 300 to 900 nm from the working electrode side in increments of 5 nm, and the dependence of the quantum efficiency on the incident light wavelength was measured. The results are shown in FIG.
色素溶液4の作製
例示化合物(B−7)をt−ブチルアルコール/アセトニトリル(1/1)の混合溶液に溶解し、例示化合物(B−7)の濃度が0.5mMの色素溶液4を作製した。
Preparation of Dye Solution 4 Exemplified Compound (B-7) is dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1) to prepare Dye Solution 4 having a concentration of Exemplified Compound (B-7) of 0.5 mM. did.
色素溶液5の作製
例示化合物(D−3)と(E−1)をt−ブチルアルコール/アセトニトリル(1/1)の混合溶液に溶解し、例示化合物(D−3)の濃度が0.5mM、例示化合物(E−1)の濃度が1.0mMの色素溶液2を作製した。
Preparation of Dye Solution 5 Exemplary compound (D-3) and (E-1) are dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1), and the concentration of exemplary compound (D-3) is 0.5 mM. A dye solution 2 having a concentration of exemplary compound (E-1) of 1.0 mM was prepared.
先に作製した酸化チタン膜を、色素溶液4に室温下で90分間浸漬して例示化合物(B−7)の吸着処理をした。次いで、この例示化合物(B−7)を吸着処理した酸化チタン膜を、色素溶液5に室温下で90分間浸漬して例示化合物(D−3)の吸着処理をして、2種以上の色素を吸着した半導体電極を作製した。 The previously prepared titanium oxide film was immersed in the dye solution 4 at room temperature for 90 minutes to perform adsorption treatment of the exemplary compound (B-7). Next, the titanium oxide film on which the exemplified compound (B-7) is adsorbed is immersed in the dye solution 5 at room temperature for 90 minutes to adsorb the exemplified compound (D-3), and then two or more kinds of dyes are adsorbed. The semiconductor electrode which adsorb | sucked was produced.
色素を吸着した半導体電極と対極とを対向配置した間隙に電解液を注入して、半導体電極を作用極とする光電変換素子を作製した。なお、対極にはチタニウム板上にスパッタリングによって形成した白金膜を、電解液にはヨウ化リチウム0.1M、ヨウ素0.05M、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾリウム0.5Mの3−メトキシプロピオニトリル溶液を使用した。この光電変換素子に、作用極側からソーラーシミュレータ光源による疑似太陽光(AM1.5、照射強度100mW/cm2)を照射した。その結果得られた光電変換特性を表2に示した。
An electrolytic solution was injected into a gap in which a semiconductor electrode adsorbing a dye and a counter electrode were arranged to face each other, to produce a photoelectric conversion element using the semiconductor electrode as a working electrode. The counter electrode is a platinum film formed on a titanium plate by sputtering, and the electrolyte solution is 0.1M lithium iodide, 0.05M iodine, 1,2-dimethyl-3-n-propylimidazolium iodide,. using 3-methoxy propionic nitrile solution 5M. This photoelectric conversion element was irradiated with artificial sunlight (AM1.5,
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液5に室温下で90分間浸漬して例示化合物(D−3)の吸着処理をした。次いで、この例示化合物(D−3)を吸着処理した酸化チタン膜を、色素溶液4に室温下で90分間浸漬して例示化合物(B−7)の吸着処理をして、2種以上の色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表2に示した。 The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 5 at room temperature for 90 minutes to perform the adsorption treatment of the exemplary compound (D-3). Next, the titanium oxide film on which the exemplified compound (D-3) is adsorbed is immersed in the dye solution 4 at room temperature for 90 minutes to adsorb the exemplified compound (B-7), and two or more kinds of dyes The semiconductor electrode which adsorb | sucked was produced. Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 2.
色素溶液6の作製
例示化合物(B−7)、例示化合物(D−3)および例示化合物(E−1)をt−ブチルアルコール/アセトニトリル(1/1)の混合溶液に溶解し、例示化合物(B−7)の濃度が0.5mM、例示化合物(D−3)の濃度が0.5mM、および例示化合物(E−1)の濃度が1.0mMの色素溶液6を作製した。
Preparation of dye solution 6 Exemplified compound (B-7), exemplified compound (D-3) and exemplified compound (E-1) were dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1), and exemplified compound ( A dye solution 6 having a concentration of B-7) of 0.5 mM, an exemplary compound (D-3) of 0.5 mM, and an exemplary compound (E-1) of 1.0 mM was prepared.
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液6に、室温下で3時間浸漬して例示化合物(B−7)と例示化合物(D−3)の吸着処理をして、2種以上の色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表2に示した。 The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 6 at room temperature for 3 hours to adsorb the exemplified compound (B-7) and the exemplified compound (D-3), A semiconductor electrode adsorbing two or more dyes was prepared. Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 2.
(比較例3)
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液4に、室温下で3時間浸漬して例示化合物(B−7)の吸着処理を行い、色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表2に示した。
(Comparative Example 3)
The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 4 at room temperature for 3 hours to perform adsorption treatment of the exemplified compound (B-7) to produce a semiconductor electrode adsorbing the dye. . Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 2.
(比較例4)
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液5に、室温下で3時間浸漬して例示化合物(D−3)の吸着処理をして、色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表2に示した。
(Comparative Example 4)
A titanium oxide film produced in the same manner as in Example 1 was immersed in the dye solution 5 at room temperature for 3 hours to adsorb the exemplified compound (D-3) to produce a semiconductor electrode adsorbed with the dye. did. Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 2.
(比較例5)
色素溶液7の作製
例示化合物(C−22)をt−ブチルアルコール/アセトニトリル(1/1)の混合溶液に溶解し、例示化合物(C−22)の濃度が0.5mMの色素溶液7を作製した。
(Comparative Example 5)
Preparation of Dye Solution 7 Exemplified Compound (C-22) was dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1) to prepare Dye Solution 7 with a concentration of Exemplified Compound (C-22) of 0.5 mM. did.
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液7に室温下で90分間浸漬して例示化合物(C−22)の吸着処理をした。次いで、この例示化合物(C−22)を吸着処理した酸化チタン膜を、色素溶液2に室温下で90分間浸漬して例示化合物(D−1)の吸着処理をして、2種以上の色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表3に示した。 The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 7 at room temperature for 90 minutes to perform the adsorption treatment of the exemplary compound (C-22). Next, the titanium oxide film on which the exemplary compound (C-22) is adsorbed is immersed in the dye solution 2 at room temperature for 90 minutes to adsorb the exemplary compound (D-1), thereby obtaining two or more types of dyes. The semiconductor electrode which adsorb | sucked was produced. Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 3.
(比較例6) (Comparative Example 6)
色素溶液8の作製
例示化合物(C−22)、例示化合物(D−1)および例示化合物(E−1)をt−ブチルアルコール/アセトニトリル(1/1)の混合溶液に溶解し、例示化合物(C−22)の濃度が0.5mM、例示化合物(D−1)の濃度が0.5mM、および例示化合物(E−1)の濃度が1.0mMの色素溶液8を作製した。
Preparation of dye solution 8 Exemplified compound (C-22), exemplified compound (D-1) and exemplified compound (E-1) were dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1), and exemplified compound ( A dye solution 8 having a concentration of C-22) of 0.5 mM, a concentration of exemplary compound (D-1) of 0.5 mM, and a concentration of exemplary compound (E-1) of 1.0 mM was prepared.
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液8に、室温下で3時間浸漬して例示化合物(C−22)と例示化合物(D−1)の吸着処理をして、2種以上の色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表3に示した。 The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 8 at room temperature for 3 hours to adsorb the exemplified compound (C-22) and the exemplified compound (D-1). A semiconductor electrode adsorbing two or more dyes was prepared. Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 3.
(比較例7)
実施例1と同様の方法で作製した酸化チタン膜を、色素溶液7に、室温下で3時間浸漬して例示化合物(C−22)の吸着処理を行い、色素を吸着した半導体電極を作製した。この半導体電極を作用極として、実施例1と同様の方法で光電変換素子を作製し、光電変換特性を測定した。その結果得られた光電変換特性を表3に示した。
(Comparative Example 7)
The titanium oxide film produced by the same method as in Example 1 was immersed in the dye solution 7 at room temperature for 3 hours to perform the adsorption treatment of the exemplified compound (C-22) to produce a semiconductor electrode adsorbing the dye. . Using this semiconductor electrode as a working electrode, a photoelectric conversion element was produced in the same manner as in Example 1, and the photoelectric conversion characteristics were measured. The photoelectric conversion characteristics obtained as a result are shown in Table 3.
尚、例示化合物(C−22)のメタノール中での吸収スペクトルの極大吸収波長は532nmであった。 In addition, the maximum absorption wavelength of the absorption spectrum in methanol of exemplary compound (C-22) was 532 nm.
表1、表2に示す様に、導電性基板上に被覆された半導体層の表面に吸着した2種以上の色素のうち少なくとも1種が一般式(1)あるいは一般式(2)で示される化合物で構成される半導体膜を用いた光電変換素子は、それぞれの化合物をを単独で吸着した半導体膜を用いた光電変換素子に比べて良好な光電変換特性を示した。本発明の2種以上の色素の併用による相乗効果は明らかである。本発明により、量子効率の入射光波長依存性に優れた、高効率の光電変換素子を提供する事が可能となった。 As shown in Tables 1 and 2, at least one of the two or more dyes adsorbed on the surface of the semiconductor layer coated on the conductive substrate is represented by General Formula (1) or General Formula (2). A photoelectric conversion element using a semiconductor film composed of a compound showed better photoelectric conversion characteristics than a photoelectric conversion element using a semiconductor film in which each compound was adsorbed alone. The synergistic effect of the combined use of two or more dyes of the present invention is clear. According to the present invention, it has become possible to provide a high-efficiency photoelectric conversion element excellent in the incident light wavelength dependency of quantum efficiency.
表3に示す様に、本発明の記載以外の色素の組み合わせで構成される半導体膜を用いた光電変換素子は、それぞれの化合物を単独で吸着した半導体膜を用いた光電変換素子と比べて光電変換効率に劣ることが明らかである。 As shown in Table 3, a photoelectric conversion element using a semiconductor film composed of a combination of dyes other than those described in the present invention is more photoelectrical than a photoelectric conversion element using a semiconductor film adsorbing each compound alone. It is clear that the conversion efficiency is inferior.
本発明の活用例として、光電変換効率に優れた色素増感型太陽電池が挙げられる。 As an application example of the present invention, a dye-sensitized solar cell excellent in photoelectric conversion efficiency can be mentioned.
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