JP5369238B2 - Material for photoelectric conversion element, method for producing photoelectric conversion element, and photoelectric conversion element - Google Patents
Material for photoelectric conversion element, method for producing photoelectric conversion element, and photoelectric conversion element Download PDFInfo
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- JP5369238B2 JP5369238B2 JP2012548669A JP2012548669A JP5369238B2 JP 5369238 B2 JP5369238 B2 JP 5369238B2 JP 2012548669 A JP2012548669 A JP 2012548669A JP 2012548669 A JP2012548669 A JP 2012548669A JP 5369238 B2 JP5369238 B2 JP 5369238B2
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- photoelectric conversion
- conversion element
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/652—Cyanine dyes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
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Description
本発明は、エネルギー変換効率の高い光電変換素子を、安定的かつ簡便に製造することができる光電変換素子用材料、該光電変換素子用材料を用いた光電変換素子の製造方法、及び、該光電変換素子用材料を用いてなる光電変換素子に関する。 The present invention provides a photoelectric conversion element material capable of stably and simply producing a photoelectric conversion element having high energy conversion efficiency, a method for producing a photoelectric conversion element using the photoelectric conversion element material, and the photoelectric conversion element. The present invention relates to a photoelectric conversion element using a conversion element material.
従来から、有機半導体層と無機半導体層とを積層し、この積層体の両側に電極を設けた光電変換素子が開発されている。このような構造の光電変換素子では、光励起により有機半導体層で光キャリア（電子−ホール対）が生成し、電子が無機半導体層を、ホールが有機半導体層を移動することで、電界が生じる。しかしながら、有機半導体層のうち、光キャリア生成に活性な領域は無機半導体層との接合界面付近の数十ｎｍ程度と非常に狭く、この活性な領域以外の有機半導体層は光キャリア生成に寄与できないため、光電変換素子として、エネルギー変換効率が低くなってしまうという欠点があった。 Conventionally, a photoelectric conversion element in which an organic semiconductor layer and an inorganic semiconductor layer are stacked and electrodes are provided on both sides of the stacked body has been developed. In the photoelectric conversion element having such a structure, photocarriers (electron-hole pairs) are generated in the organic semiconductor layer by photoexcitation, and an electric field is generated by electrons moving through the inorganic semiconductor layer and holes moving through the organic semiconductor layer. However, in the organic semiconductor layer, the active region for generating photocarriers is very narrow, about several tens of nanometers near the junction interface with the inorganic semiconductor layer, and organic semiconductor layers other than this active region cannot contribute to the generation of photocarriers. Therefore, the photoelectric conversion element has a drawback that the energy conversion efficiency is lowered.
この問題を解決する目的で、有機半導体と、無機半導体とを混合して複合化した複合膜を用いることが検討されている。
例えば、特許文献１には、有機半導体と無機半導体を共蒸着によって複合化した共蒸着薄膜と、この薄膜を挟んでその両面に設けられ、この複合薄膜に内蔵電界を与えるための半導体もしくは金属、又はそれら双方からなる電極部とを備えた有機・無機複合薄膜太陽電池が記載されている。特許文献１には、同文献に記載の有機・無機複合薄膜においては、ｐｎ接合（有機／無機半導体接合）が膜全体に張り巡らされた構造のため、膜全体が光キャリア生成に対して活性に働き、膜で吸収された光すべてがキャリア生成に寄与するため、大きな光電流が得られる効果がある旨が記載されている。In order to solve this problem, it has been studied to use a composite film in which an organic semiconductor and an inorganic semiconductor are mixed to form a composite.
For example, Patent Document 1 discloses a co-deposited thin film in which an organic semiconductor and an inorganic semiconductor are combined by co-evaporation, and a semiconductor or metal for providing a built-in electric field to the composite thin film provided on both sides of the thin film, Or the organic-inorganic composite thin film solar cell provided with the electrode part which consists of both of them is described. In Patent Document 1, the organic / inorganic composite thin film described in the same document has a structure in which a pn junction (organic / inorganic semiconductor junction) is stretched over the entire film, so that the entire film is active against photocarrier generation. It is described that since all the light absorbed by the film contributes to carrier generation, a large photocurrent can be obtained.
また、有機半導体に対して無機半導体を密充填させて、エネルギー変換効率を向上させる試みもなされている。
例えば、特許文献２には、有機電子供与体と化合物半導体結晶とを含有する活性層を二つの電極の間に設けた有機太陽電池において、前記活性層は有機電子供与体と化合物半導体結晶とを混合して分散してなり、且つ、化合物半導体結晶が平均粒径が異なる二種類のロッド状の結晶を含み、この二種類のロッド状結晶の平均粒径及び含有比率を所定範囲内とする有機太陽電池が記載されている。特許文献２には、活性層中における化合物半導体結晶の充填率を増大することができ、これにより変換効率の高い太陽電池を得ることができる旨が記載されている。Attempts have also been made to improve energy conversion efficiency by closely packing an inorganic semiconductor with an organic semiconductor.
For example, in Patent Document 2, in an organic solar cell in which an active layer containing an organic electron donor and a compound semiconductor crystal is provided between two electrodes, the active layer includes an organic electron donor and a compound semiconductor crystal. An organic compound that is mixed and dispersed, and the compound semiconductor crystal includes two types of rod-shaped crystals having different average particle sizes, and the average particle size and content ratio of the two types of rod-shaped crystals are within a predetermined range. A solar cell is described. Patent Document 2 describes that the filling rate of the compound semiconductor crystal in the active layer can be increased, and thereby a solar cell with high conversion efficiency can be obtained.
しかしながら、特許文献１又は２に記載の光電変換素子であっても未だエネルギー変換効率はかなり低く、実用化に耐えうる有機太陽電池の開発のためには更なるエネルギー変換効率の改善が不可欠である。 However, even in the photoelectric conversion element described in Patent Document 1 or 2, the energy conversion efficiency is still very low, and further improvement of the energy conversion efficiency is indispensable for the development of an organic solar cell that can withstand practical use. .
本発明者は、有機半導体化合物中に、平均粒子径がｎｍオーダーの無機半導体化合物微粒子を分散させることにより、有機半導体化合物中に無機半導体化合物を密充填させれば高いエネルギー変換効率を実現できると考えた。しかしながら、有機半導体化合物と無機半導体化合物とは親和性が低く、無機半導体化合物微粒子が凝集してしまうことから、期待したような高いエネルギー変換効率を実現することはできなかった。無機半導体化合物微粒子を凝集させることなく微分散させる方法として分散剤の使用も検討したが、分散剤を加えることにより更にエネルギー変換効率が低下してしまうという問題があった。 The present inventor can realize high energy conversion efficiency by dispersing inorganic semiconductor compound fine particles having an average particle diameter of the order of nm in the organic semiconductor compound so that the inorganic semiconductor compound is closely packed in the organic semiconductor compound. Thought. However, the organic semiconductor compound and the inorganic semiconductor compound have low affinity, and the inorganic semiconductor compound fine particles are aggregated. Therefore, the high energy conversion efficiency as expected could not be realized. The use of a dispersant as a method of finely dispersing inorganic semiconductor compound fine particles without agglomeration was also examined, but there was a problem that the energy conversion efficiency was further reduced by adding the dispersant.
本発明は、エネルギー変換効率の高い光電変換素子を、安定的かつ簡便に製造することができる光電変換素子用材料、該光電変換素子用材料を用いた光電変換素子の製造方法、及び、該光電変換素子用材料を用いてなる光電変換素子を提供することを目的とする。 The present invention provides a photoelectric conversion element material capable of stably and simply producing a photoelectric conversion element having high energy conversion efficiency, a method for producing a photoelectric conversion element using the photoelectric conversion element material, and the photoelectric conversion element. It aims at providing the photoelectric conversion element which uses the material for conversion elements.
本発明は、有機半導体化合物、無機半導体化合物微粒子、及び、有機溶媒を含有し、前記有機半導体化合物は、極性基を有する光電変換素子用材料である。
以下に本発明を詳述する。The present invention contains an organic semiconductor compound, inorganic semiconductor compound fine particles, and an organic solvent, and the organic semiconductor compound is a material for a photoelectric conversion element having a polar group.
The present invention is described in detail below.
本発明者は、鋭意検討の結果、極性基を有する有機半導体化合物を用いることにより、平均粒子径がｎｍオーダーであっても無機半導体化合物微粒子を凝集させることなく微分散させることが可能であることを見出した。これは、有機半導体化合物が極性基を有することにより、有機半導体化合物と無機半導体化合物微粒子との親和性が向上し、有機半導体化合物自体が一種の分散剤として機能し得るためであると考えられる。このようにして光電変換素子用材料中に無機半導体化合物微粒子を微分散させることにより、高いエネルギー変換効率を実現した光電変換素子を製造できる。 As a result of intensive studies, the present inventor is able to finely disperse the inorganic semiconductor compound fine particles without aggregating even if the average particle diameter is on the order of nm by using an organic semiconductor compound having a polar group. I found. This is probably because the organic semiconductor compound has a polar group, whereby the affinity between the organic semiconductor compound and the inorganic semiconductor compound fine particles is improved, and the organic semiconductor compound itself can function as a kind of dispersant. Thus, the photoelectric conversion element which implement | achieved high energy conversion efficiency can be manufactured by finely dispersing inorganic semiconductor compound fine particles in the material for photoelectric conversion elements.
本発明の光電変換素子用材料は、有機半導体化合物、無機半導体化合物微粒子、及び、有機溶媒を含有する。
上記有機半導体化合物は、極性基を有する。上記有機半導体化合物が極性基を有することにより有機半導体化合物と無機半導体化合物微粒子との親和性が向上し、光電変換素子用材料中に無機半導体化合物微粒子を微分散させることができる。The photoelectric conversion element material of the present invention contains an organic semiconductor compound, inorganic semiconductor compound fine particles, and an organic solvent.
The organic semiconductor compound has a polar group. When the organic semiconductor compound has a polar group, the affinity between the organic semiconductor compound and the inorganic semiconductor compound fine particles is improved, and the inorganic semiconductor compound fine particles can be finely dispersed in the photoelectric conversion element material.
上記極性基は、例えば、カルボキシル基、エステル基、カルボニル基、アミノ基、水酸基、スルホン酸基、チオール基、シアノ基、フルオロ基、クロロ基、ブロモ基等が挙げられる。なかでも、合成のしやすさから、カルボキシル基、エステル基、カルボニル基、水酸基が好適である。 Examples of the polar group include a carboxyl group, an ester group, a carbonyl group, an amino group, a hydroxyl group, a sulfonic acid group, a thiol group, a cyano group, a fluoro group, a chloro group, and a bromo group. Of these, a carboxyl group, an ester group, a carbonyl group, and a hydroxyl group are preferable because of ease of synthesis.
上記有機半導体化合物は、共役するドナーとアクセプターとを有する（ドナー−アクセプター構造を有する、ともいう）ことが好ましい。上記有機半導体化合物が更に共役するドナーとアクセプターとを有することにより、高いエネルギー変換効率を実現した光電変換素子を製造できる。このような有機半導体化合物として、例えば、極性基を有し、かつ、１分子内に共役するドナーとアクセプターとを有する低分子化合物、極性基を有し、かつ、共役するドナーとなるセグメントとアクセプターとなるセグメントとを有する導電性高分子化合物等が挙げられる。
上記有機半導体化合物が低分子化合物であると、有機溶媒に分散しやすいので有機溶媒の選択肢が広くなり、塗工等により簡便に光電変換素子を製造することができる。上記有機半導体化合物が高分子化合物であると、有機半導体化合物がバインダーとしての機能を発揮し得ることから、製膜性に優れ、また、光吸収波長に関して調整しやすい。The organic semiconductor compound preferably has a conjugated donor and acceptor (also referred to as having a donor-acceptor structure). By having the donor and acceptor which the said organic-semiconductor compound further conjugates, the photoelectric conversion element which implement | achieved high energy conversion efficiency can be manufactured. As such an organic semiconductor compound, for example, a low molecular compound having a polar group and having a donor and an acceptor conjugated in one molecule, a segment and an acceptor having a polar group and serving as a conjugated donor And a conductive polymer compound having a segment.
When the organic semiconductor compound is a low molecular compound, the organic semiconductor compound is easily dispersed in an organic solvent, so that the choice of the organic solvent is widened, and a photoelectric conversion element can be easily produced by coating or the like. When the organic semiconductor compound is a polymer compound, the organic semiconductor compound can exhibit a function as a binder, so that the film forming property is excellent and the light absorption wavelength can be easily adjusted.
上記ドナーとアクセプターとは、それぞれに対して電子供与性をもつ骨格と電子吸引性をもつ骨格とを意味する。即ち、ドナーは、アクセプターに対して相対的にＨＯＭＯ、ＬＵＭＯ準位がともに高い値を有する。逆に、アクセプターは、ドナーに対して相対的にＨＯＭＯ、ＬＵＭＯ準位がともに低い値を有する。
また、上記ドナーとアクセプターとが共役するとは、ドナー部位とアクセプター部位とが共役結合を介して結合していることを意味する。The donor and acceptor mean a skeleton having an electron donating property and a skeleton having an electron withdrawing property, respectively. That is, the donor has a high value in both the HOMO and LUMO levels relative to the acceptor. On the contrary, the acceptor has a low value for both the HOMO and LUMO levels relative to the donor.
Moreover, that the donor and the acceptor are conjugated means that the donor site and the acceptor site are bonded via a conjugated bond.
上記極性基を有し、かつ、１分子内に共役するドナーとアクセプターとを有する低分子化合物においてドナーとして機能し得る構造は、例えば、チオフェン、フルオレン、カルバゾール、フェニレンビニレン、クマリン、インドリン等の骨格が挙げられる。なかでも、導電性に優れ、高いエネルギー変換効率を得やすいことから、チオフェン骨格が好適である。
上記チオフェン骨格としては、例えば、アルキルチオフェン、アルコキシチオフェン、チエノチオフェン、ジチエノチオフェン、エチレンジオキシチオフェン、シクロペンタジチオフェン、ジチエノシロール等の骨格が挙げられる。The structure capable of functioning as a donor in a low molecular compound having a polar group and having a donor and an acceptor conjugated in one molecule is, for example, a skeleton such as thiophene, fluorene, carbazole, phenylene vinylene, coumarin, and indoline. Is mentioned. Among these, a thiophene skeleton is preferable because of its excellent conductivity and high energy conversion efficiency.
Examples of the thiophene skeleton include skeletons such as alkylthiophene, alkoxythiophene, thienothiophene, dithienothiophene, ethylenedioxythiophene, cyclopentadithiophene, and dithienosilole.
上記極性基を有し、かつ、１分子内に共役するドナーとアクセプターとを有する低分子化合物においてアクセプターとして機能し得る構造は、ドナーとして機能する構造に比べて相対的に小さい値のＨＯＭＯ、ＬＵＭＯ準位を有するものであれば特に限定されないが、例えば、チエノチオフェン、ジチエノチオフェン、ベンゾチアジアゾール、ベンゾビスチアジアゾール、チエノピラジン等の骨格が好ましい。 A structure that can function as an acceptor in a low-molecular compound having a polar group and having a donor and an acceptor conjugated in one molecule has a relatively small value of HOMO and LUMO compared to a structure that functions as a donor. Although it will not specifically limit if it has a level, For example, frame | skeletons, such as thienothiophene, dithienothiophene, benzothiadiazole, benzobisthiadiazole, thienopyrazine, are preferable.
上記ドナーとアクセプターとは、低分子化合物の１分子内にあって共役していればよい。即ち、上記ドナーとアクセプターとは隣接していてもよく、共役する範囲であれば炭素数２以上の分岐していてもよいアルキル基、アリーレン基等を介在していてもよい。 The donor and acceptor may be conjugated within one molecule of the low molecular compound. That is, the donor and the acceptor may be adjacent to each other, and may have a branched alkyl group having 2 or more carbon atoms, an arylene group, or the like as long as they are conjugated.
上記極性基を有し、かつ、１分子内に共役するドナーとアクセプターとを有する低分子化合物は、分子内に複素環状骨格を有することが好ましい。複素環状骨格を有することにより分子同士の配向性が向上し、電荷移動度が向上する。更に配向性を向上させるには、硫黄元素を含有する複素環状骨格を有することがより好ましく、硫黄元素を含有する複素環状骨格を２つ以上有することが更に好ましい。 The low molecular compound having a polar group and having a donor and an acceptor conjugated in one molecule preferably has a heterocyclic skeleton in the molecule. By having a heterocyclic skeleton, orientation between molecules is improved and charge mobility is improved. In order to further improve the orientation, it is more preferable to have a heterocyclic skeleton containing a sulfur element, and it is more preferable to have two or more heterocyclic skeletons containing a sulfur element.
上記極性基を有し、かつ、１分子内に共役するドナーとアクセプターとを有する低分子化合物は、具体的には例えば、下記式（１）、下記式（２）又は下記式（３）で表される有機半導体化合物が挙げられる。 Specific examples of the low molecular compound having the polar group and having a donor and an acceptor conjugated in one molecule are represented by the following formula (1), the following formula (2), or the following formula (3). The organic-semiconductor compound represented is mentioned.
上記式（１）で表される有機半導体化合物は、極性基としてカルボキシル基を有し、かつ、クマリン誘導体がドナーとして、シアノ基含有チオフェン誘導体構造がアクセプターとして共役している構造を有する。
上記式（１）で表される有機半導体化合物の市販品は、例えば、林原生物化学研究所社製のＮＫＸ−２５８７が挙げられる。The organic semiconductor compound represented by the above formula (1) has a carboxyl group as a polar group, a coumarin derivative as a donor, and a cyano group-containing thiophene derivative structure as a acceptor.
As for the commercial item of the organic-semiconductor compound represented by the said Formula (1), NKX-2587 by Hayashibara Biochemical Research Institute company is mentioned, for example.
上記式（２）で表される有機半導体化合物は、極性基としてカルボニル基とカルボキシル基とを有し、かつ、インドリン誘導体構造がドナーとして、チアゾール誘導体がアクセプターとして共役している構造を有する。
上記式（２）で表される有機半導体化合物の市販品は、例えば、三菱製紙社製のＤ−１４９が挙げられる。The organic semiconductor compound represented by the above formula (2) has a carbonyl group and a carboxyl group as polar groups, a structure in which an indoline derivative structure is conjugated as a donor, and a thiazole derivative is conjugated as an acceptor.
As for the commercial item of the organic-semiconductor compound represented by the said Formula (2), D-149 by Mitsubishi Paper Industries is mentioned, for example.
上記式（３）で表される有機半導体化合物は、極性基としてカルボキシル基を有し、かつ、カルバゾール構造がドナーとして、シアノ基含有チオフェン誘導体構造がアクセプターとして共役している構造を有する。
上記式（３）で表される有機半導体化合物の市販品は、例えば、綜研化学社製のＳＫ−ＩＩが挙げられる。The organic semiconductor compound represented by the above formula (3) has a carboxyl group as a polar group, a carbazole structure as a donor, and a cyano group-containing thiophene derivative structure as a acceptor.
Examples of commercially available organic semiconductor compounds represented by the above formula (3) include SK-II manufactured by Soken Chemical Co., Ltd.
上記極性基を有し、かつ、共役するドナーとなるセグメントとアクセプターとなるセグメントとを有する導電性高分子化合物は、ドナーとなるセグメントとアクセプターとなるセグメントとを繰り返し単位として構成される高分子化合物である。上記有機半導体化合物をこのような構造とすることにより、幅広い範囲の波長の光を吸収できるエネルギー変換効率の極めて高い光電変換素子を製造することができる。
なお、導電性高分子化合物が極性基を有するとは、導電性高分子化合物が側鎖に極性基を含有する官能基を有することを意味する。The conductive polymer compound having a polar group and a conjugated donor segment and an acceptor segment is a polymer compound composed of a donor segment and an acceptor segment as a repeating unit. It is. By setting the organic semiconductor compound to such a structure, a photoelectric conversion element with extremely high energy conversion efficiency capable of absorbing light in a wide range of wavelengths can be manufactured.
In addition, that a conductive polymer compound has a polar group means that a conductive polymer compound has a functional group containing a polar group in a side chain.
上記ドナーとなるセグメントと上記アクセプターとなるセグメントとの比率（ドナーとなるセグメント：アクセプターとなるセグメント）は、７：１〜１：２であることが好ましい。上記範囲よりもドナーとなるセグメントの割合が多くなると、長波長の光の吸収が低下してしまうことがある。上記範囲よりもアクセプターとなるセグメントの割合が多くなると、電荷移動度が低下し、光電変換素子の性能が低下することがある。上記ドナーとなるセグメントと上記アクセプターとなるセグメントとの比率のより好ましい下限は５：１、より好ましい上限は１：１である。 The ratio of the donor segment to the acceptor segment (the donor segment: acceptor segment) is preferably 7: 1 to 1: 2. If the proportion of the segment serving as a donor is larger than the above range, the absorption of light having a long wavelength may be reduced. If the proportion of the segment serving as an acceptor is larger than the above range, the charge mobility may be lowered, and the performance of the photoelectric conversion element may be lowered. A more preferred lower limit of the ratio of the donor segment and the acceptor segment is 5: 1, and a more preferred upper limit is 1: 1.
また、高いエネルギー変換効率を得やすいことから、上記ドナーとなるセグメントと上記アクセプターとなるセグメントとは、交互に並んでいることが好ましい。 Moreover, since it is easy to obtain high energy conversion efficiency, it is preferable that the segment serving as the donor and the segment serving as the acceptor are alternately arranged.
上記ドナーとなるセグメントは、複素環状骨格を有することが好ましい。複素環状骨格を有することにより、セグメント同士の配向性が向上して電荷移動度が向上するため、高いエネルギー変換効率を得やすい。更に配向性を向上させるには、上記ドナーとなるセグメントは、硫黄元素を含有する複素環状骨格を有することがより好ましい。 The segment serving as a donor preferably has a heterocyclic skeleton. By having a heterocyclic skeleton, the orientation between the segments is improved and the charge mobility is improved, so that high energy conversion efficiency is easily obtained. In order to further improve the orientation, it is more preferable that the segment serving as the donor has a heterocyclic skeleton containing a sulfur element.
上記ドナーとなるセグメントとして、具体的には例えば、下記式（ａ）〜（ｇ）で表されるセグメント等が挙げられる。なかでも、電荷移動度に優れ、高いエネルギー変換効率を得やすいことから、下記式（ａ）、（ｂ）、（ｃ）、（ｄ）で表されるセグメントが好ましい。 Specific examples of the segment serving as the donor include segments represented by the following formulas (a) to (g). Among these, the segments represented by the following formulas (a), (b), (c), and (d) are preferable because they are excellent in charge mobility and easily obtain high energy conversion efficiency.
式（ａ）〜（ｇ）中、Ｒ１〜Ｒ１４は水素原子又は置換基を示す。
上記置換基は、上述したような極性基を含有する官能基であってもよいし、非極性基であってもよい。上記非極性基として、例えば、炭素数１〜１６のアルキル基、アリール基、アルコキシ基、アルケニル基、アルキニル基、アラルキル基、ヘテロアリール基等が挙げられる。In formulas (a) to (g), R 1 to R 14 represent a hydrogen atom or a substituent.
The substituent may be a functional group containing a polar group as described above, or may be a nonpolar group. Examples of the nonpolar group include an alkyl group having 1 to 16 carbon atoms, an aryl group, an alkoxy group, an alkenyl group, an alkynyl group, an aralkyl group, and a heteroaryl group.
上記アクセプターとなるセグメントもまた、セグメント同士の配向性が向上して電荷移動度が向上することから、複素環状骨格を有することが好ましい。更に配向性を向上させるには、上記アクセプターとなるセグメントは、硫黄元素及び／又は窒素元素を含有する複素環状骨格を有することがより好ましい。 The segment serving as the acceptor also preferably has a heterocyclic skeleton because the orientation between the segments is improved and the charge mobility is improved. In order to further improve the orientation, it is more preferable that the segment serving as the acceptor has a heterocyclic skeleton containing a sulfur element and / or a nitrogen element.
上記アクセプターとなるセグメントとして、具体的には例えば、下記式（ｈ）〜（ｒ）で表されるセグメント等が挙げられる。なかでも、電荷移動度に優れ、高いエネルギー変換効率を得やすいことから、下記式（ｈ）、（ｉ）、（ｊ）、（ｑ）で表されるセグメントが好ましい。 Specific examples of the segment serving as the acceptor include segments represented by the following formulas (h) to (r). Among these, the segments represented by the following formulas (h), (i), (j), and (q) are preferable because they are excellent in charge mobility and easily obtain high energy conversion efficiency.
式（ｈ）〜（ｒ）中、Ｒ１５〜Ｒ３５は水素原子又は置換基を示す。
上記置換基は、上述したような極性基を含有する官能基であってもよいし、非極性基であってもよい。上記非極性基として、例えば、炭素数１〜１６のアルキル基、アリール基、アルコキシ基、アルケニル基 、アルキニル基、ヘテロアリール基等が挙げられる。In formulas (h) to (r), R 15 to R 35 represent a hydrogen atom or a substituent.
The substituent may be a functional group containing a polar group as described above, or may be a nonpolar group. As said nonpolar group, a C1-C16 alkyl group, an aryl group, an alkoxy group, an alkenyl group, an alkynyl group, heteroaryl group etc. are mentioned, for example.
なお、上記ドナーとなるセグメントと上記アクセプターとなるセグメントとの組み合わせのうち、少なくとも一方のセグメント上に、上述したような極性基を含有する官能基が存在する。また、上記式（ｑ）中、Ｒ３２、Ｒ３３は水素原子又は置換基を示すが、Ｒ３２、Ｒ３３のうち少なくとも一方は極性基を有する官能基であることが好ましい。In addition, the functional group containing the polar group as described above is present on at least one of the combinations of the donor segment and the acceptor segment. In the formula (q), R 32 and R 33 each represent a hydrogen atom or a substituent, but at least one of R 32 and R 33 is preferably a functional group having a polar group.
上記ドナーとなるセグメントと上記アクセプターとなるセグメントとの組み合わせは特に限定されないが、導電性に優れ、高いエネルギー変換効率を得やすいことから、上記式（ｃ）で表されるセグメントと上記式（ｑ）で表されるセグメントとの組み合わせ、上記式（ａ）で表されるセグメントと上記式（ｈ）で表されるセグメントとの組み合わせ、上記式（ｄ）で表されるセグメントと上記式（ｉ）で表されるセグメントとの組み合わせが好ましい。 The combination of the segment serving as the donor and the segment serving as the acceptor is not particularly limited, but is excellent in conductivity and easily obtains high energy conversion efficiency. Therefore, the segment represented by the above formula (c) and the above formula (q ), A combination of the segment represented by the above formula (a) and the segment represented by the above formula (h), a segment represented by the above formula (d) and the above formula (i). A combination with a segment represented by
上記極性基を有し、かつ、共役するドナーとなるセグメントとアクセプターとなるセグメントとを有する導電性高分子化合物は、数平均分子量の好ましい下限が３０００、好ましい上限が１００００００である。上記数平均分子量が３０００未満であると、有機半導体化合物の電荷移動度が低くなり、エネルギー変換効率が低下することがあり、１００００００を超えると、有機半導体化合物の溶剤溶解性が低下し、製膜性が悪くなることがある。上記数平均分子量のより好ましい下限は５０００、より好ましい上限は７０００００である。
なお、数平均分子量は、ゲルパーミエーションクロマトグラフィーを用いて、クロロホルム中４０℃にて測定し、標準ポリスチレンを基準にして算出することができる。The conductive polymer compound having the polar group and having a conjugated donor segment and an acceptor segment has a preferred number average molecular weight of 3000 and a preferred upper limit of 1000000. When the number average molecular weight is less than 3000, the charge mobility of the organic semiconductor compound is lowered and energy conversion efficiency may be lowered. When the number average molecular weight is more than 1000000, the solvent solubility of the organic semiconductor compound is lowered and film formation is performed. May be worse. The more preferable lower limit of the number average molecular weight is 5000, and the more preferable upper limit is 700,000.
In addition, a number average molecular weight can be calculated on the basis of standard polystyrene by measuring at 40 degreeC in chloroform using a gel permeation chromatography.
上記極性基を有し、かつ、共役するドナーとなるセグメントとアクセプターとなるセグメントとを有する導電性高分子化合物を製造する方法は特に限定されず、例えば、上記ドナーとなるセグメントを構成するモノマーと、上記アクセプターとなるセグメントを構成するモノマーとを共重合する方法等が挙げられる。 A method for producing a conductive polymer compound having the polar group and having a conjugated donor segment and an acceptor segment is not particularly limited. For example, the monomer constituting the donor segment and And a method of copolymerizing with a monomer constituting the segment serving as the acceptor.
上記有機半導体化合物は、上述したようなドナー−アクセプター構造を有することが好ましいが、ドナー−アクセプター構造を有していなくてもよい。
ドナー−アクセプター構造を有さない場合、上記有機半導体化合物は、低分子化合物であるよりも導電性高分子化合物であることが好ましい。The organic semiconductor compound preferably has a donor-acceptor structure as described above, but may not have a donor-acceptor structure.
When it does not have a donor-acceptor structure, the organic semiconductor compound is preferably a conductive polymer compound rather than a low molecular compound.
上記極性基を有し、かつ、ドナー−アクセプター構造を有さない導電性高分子化合物は、電荷移動度が高く、高いエネルギー変換効率が得られることから、チオフェン環、チアゾール環、チアジアゾール環、カルバゾール環、ピロール環等の硫黄元素又は窒素元素を含有する複素環状骨格を有することが好ましい。 Since the conductive polymer compound having the polar group and having no donor-acceptor structure has high charge mobility and high energy conversion efficiency, the thiophene ring, thiazole ring, thiadiazole ring, carbazole It preferably has a heterocyclic skeleton containing a sulfur element such as a ring or a pyrrole ring or a nitrogen element.
上記極性基を有し、かつ、ドナー−アクセプター構造を有さない導電性高分子化合物は、具体的には例えば、下記式（４）、下記式（５）又は下記式（６）で表される繰り返し単位を有する高分子化合物が挙げられる。 The conductive polymer compound having the polar group and having no donor-acceptor structure is specifically represented by, for example, the following formula (4), the following formula (5), or the following formula (6). And a high molecular compound having a repeating unit.
式中、ｎは整数を表す。
上記式（４）で表される繰り返し単位は、極性基としてエステル基を有するポリチオフェン構造を有する。
上記式（４）で表される繰り返し単位を有する高分子化合物の市販品は、例えば、Ｒｉｅｋｅ ｍｅｔａｌｓ社製４０２３が挙げられる。In the formula, n represents an integer.
The repeating unit represented by the above formula (4) has a polythiophene structure having an ester group as a polar group.
As for the commercial item of the high molecular compound which has a repeating unit represented by the said Formula (4), 4023 by Rieke metals is mentioned, for example.
上記式（５）で表される繰り返し単位は、極性基としてカルボキシル基を有するポリチオフェン構造を有する。
上記式（５）で表される繰り返し単位を有する高分子化合物の市販品は、例えば、Ｒｉｅｋｅ ｍｅｔａｌｓ社製４０３０が挙げられる。The repeating unit represented by the above formula (5) has a polythiophene structure having a carboxyl group as a polar group.
As for the commercial item of the high molecular compound which has a repeating unit represented by the said Formula (5), 4030 by Rieke metals is mentioned, for example.
上記式（６）で表される繰り返し単位は、極性基としてポリエーテル基を有するポリフェニレンビニレン構造を有する。
上記式（６）で表される繰り返し単位を有する高分子化合物の市販品は、例えば、アルドリッチ社製ＭＤＭＯ−ＰＰＶが挙げられる。The repeating unit represented by the above formula (6) has a polyphenylene vinylene structure having a polyether group as a polar group.
As for the commercial item of the high molecular compound which has a repeating unit represented by the said Formula (6), MDMO-PPV by Aldrich is mentioned, for example.
上記極性基を有し、かつ、ドナー−アクセプター構造を有さない導電性高分子化合物は、重量平均分子量の好ましい下限が３０００、好ましい上限が１００００００である。上記重量平均分子量が３０００未満であると、有機半導体化合物の電荷移動度が低くなり、エネルギー変換効率が低下することがあり、１００００００を超えると、有機半導体化合物の溶剤溶解性が低下し、製膜性が悪くなることがある。上記重量平均分子量のより好ましい下限は５０００、より好ましい上限は７０００００である。 The conductive polymer compound having a polar group and not having a donor-acceptor structure has a preferable lower limit of the weight average molecular weight of 3000 and a preferable upper limit of 1000000. When the weight average molecular weight is less than 3000, the charge mobility of the organic semiconductor compound is lowered, and the energy conversion efficiency may be lowered. When the weight average molecular weight is more than 1000000, the solvent solubility of the organic semiconductor compound is lowered, and film formation May be worse. The minimum with said more preferable weight average molecular weight is 5000, and a more preferable upper limit is 700,000.
上記極性基を有し、かつ、ドナー−アクセプター構造を有さない導電性高分子化合物を調製する方法は特に限定されず、例えば、極性基を有するモノマーを用いて重合する方法等が挙げられる。 The method for preparing the conductive polymer compound having the polar group and not having the donor-acceptor structure is not particularly limited, and examples thereof include a method of polymerizing using a monomer having a polar group.
上記有機半導体化合物の配合量は特に限定されないが、無機半導体化合物微粒子１００重量部に対して好ましい下限は１重量部、好ましい上限は５００重量部である。上記有機半導体化合物の配合量が１重量部未満であると、ホールが電極まで移動できなくなることがあり、５００重量部を超えると、電子が電極まで移動できなくなることがある。上記有機半導体化合物の配合量のより好ましい下限は１０重量部、より好ましい上限は２００重量部である。 Although the compounding quantity of the said organic-semiconductor compound is not specifically limited, A preferable minimum is 1 weight part with respect to 100 weight part of inorganic semiconductor compound fine particles, and a preferable upper limit is 500 weight part. When the compounding amount of the organic semiconductor compound is less than 1 part by weight, holes may not be able to move to the electrode, and when it exceeds 500 parts by weight, electrons may not be able to move to the electrode. A more preferred lower limit of the amount of the organic semiconductor compound is 10 parts by weight, and a more preferred upper limit is 200 parts by weight.
上記無機半導体化合物微粒子は特に限定されず、例えば、酸化チタン、酸化亜鉛、酸化スズ、酸化インジウム、酸化ガリウム、酸化タングステン、酸化ケイ素、酸化アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、硫化カドミウム、酸化バナジウム等からなるものが挙げられる。また、上記無機半導体化合物微粒子として、例えば、ＩｎＰ、ＩｎＡｓ、ＧａＰ、ＧａＡｓ等の周期表１３族元素と１５族元素との化合物、ＣｄＳｅ、ＣｄＴｅ、ＺｎＳ等の周期表１２族元素と１６族元素との化合物等からなるものも挙げられる。これらの無機半導体化合物微粒子は、単独で用いられてもよく、２種以上が併用されてもよい。なかでも、電子移動度の高い活性層を形成できることから、亜鉛、スズ、ガリウム、インジウムの酸化物又は硫化物を主成分とする無機半導体化合物微粒子が好適であり、酸化亜鉛からなる無機半導体化合物微粒子がより好適である。 The inorganic semiconductor compound fine particles are not particularly limited. For example, titanium oxide, zinc oxide, tin oxide, indium oxide, gallium oxide, tungsten oxide, silicon oxide, aluminum oxide, barium titanate, strontium titanate, cadmium sulfide, vanadium oxide. The thing which consists of etc. is mentioned. Further, as the inorganic semiconductor compound fine particles, for example, compounds of Group 13 elements and Group 15 elements of periodic table such as InP, InAs, GaP, GaAs, etc., Group 12 elements and Group 16 elements of periodic table such as CdSe, CdTe, ZnS, and the like The thing which consists of these compounds etc. is mentioned. These inorganic semiconductor compound fine particles may be used alone or in combination of two or more. In particular, since an active layer with high electron mobility can be formed, inorganic semiconductor compound fine particles containing zinc, tin, gallium, indium oxide or sulfide as the main component are suitable, and inorganic semiconductor compound fine particles made of zinc oxide are preferred. Is more preferred.
上記無機半導体化合物微粒子は、平均粒子径の好ましい下限が１ｎｍ、好ましい上限が３０ｎｍである。上記無機半導体化合物微粒子の平均粒子径が１ｎｍ未満であると、得られる光電変換素子において上記無機半導体化合物微粒子同士の粒界数が多くなり、電子移動の妨げが増すことがある。上記無機半導体化合物微粒子の平均粒子径が３０ｎｍを超えると、得られる光電変換素子において、上記有機半導体化合物で生成した光キャリアが効率よく上記無機半導体化合物微粒子との接合界面にまで伝達されないことがある。上記無機半導体化合物微粒子の平均粒子径のより好ましい下限は３ｎｍ、より好ましい上限は２０ｎｍである。
上記無機半導体化合物微粒子の形状は特に限定されず、例えば、ロッド状、球状等が挙げられる。The inorganic semiconductor compound fine particles have a preferable lower limit of the average particle diameter of 1 nm and a preferable upper limit of 30 nm. When the average particle diameter of the inorganic semiconductor compound fine particles is less than 1 nm, the number of grain boundaries between the inorganic semiconductor compound fine particles in the resulting photoelectric conversion element increases, and the hindrance to electron transfer may increase. When the average particle diameter of the inorganic semiconductor compound fine particles exceeds 30 nm, in the resulting photoelectric conversion element, the photocarrier generated by the organic semiconductor compound may not be efficiently transmitted to the bonding interface with the inorganic semiconductor compound fine particles. . The more preferable lower limit of the average particle diameter of the inorganic semiconductor compound fine particles is 3 nm, and the more preferable upper limit is 20 nm.
The shape of the inorganic semiconductor compound fine particles is not particularly limited, and examples thereof include a rod shape and a spherical shape.
上記有機溶媒は特に限定されないが、例えば、クロロベンゼン、クロロホルム、メチルエチルケトン、トルエン、酢酸エチル、エタノール、キシレン等が好ましい。 Although the said organic solvent is not specifically limited, For example, chlorobenzene, chloroform, methyl ethyl ketone, toluene, ethyl acetate, ethanol, xylene etc. are preferable.
上記有機溶媒の配合量は特に限定されないが、上記有機半導体化合物１重量部に対する好ましい下限が２０重量部、好ましい上限が１０００重量部である。上記有機溶媒の配合量が２０重量部未満であると、光電変換素子用材料の粘度が高すぎ、安定的かつ簡便に光電変換素子を形成することができないことがある。上記有機溶媒の配合量が１０００重量部を超えると、光電変換素子用材料の粘度が低すぎ、充分な厚みを有する光電変換素子を形成することができないことがある。上記有機溶媒の配合量のより好ましい下限は５０重量部、より好ましい上限は５００重量部である。 Although the compounding quantity of the said organic solvent is not specifically limited, The preferable minimum with respect to 1 weight part of said organic-semiconductor compounds is 20 weight part, and a preferable upper limit is 1000 weight part. When the blending amount of the organic solvent is less than 20 parts by weight, the viscosity of the photoelectric conversion element material is too high, and the photoelectric conversion element may not be formed stably and simply. When the blending amount of the organic solvent exceeds 1000 parts by weight, the viscosity of the photoelectric conversion element material may be too low to form a photoelectric conversion element having a sufficient thickness. The more preferable lower limit of the amount of the organic solvent is 50 parts by weight, and the more preferable upper limit is 500 parts by weight.
本発明の光電変換素子用材料を製造する方法は特に限定されず、例えば、上記有機半導体化合物と上記無機半導体化合物微粒子とを、超音波分散機等を用いて上記有機溶媒に分散及び溶解させる方法等が挙げられる。 The method for producing the photoelectric conversion element material of the present invention is not particularly limited. For example, the organic semiconductor compound and the inorganic semiconductor compound fine particles are dispersed and dissolved in the organic solvent using an ultrasonic disperser or the like. Etc.
本発明の光電変換素子用材料を用いることにより、エネルギー変換効率の高い光電変換素子を、安定的かつ簡便に形成することができる。
本発明の光電変換素子用材料を用いてなる活性層が、一組の電極間に挟持された構造を有する光電変換素子もまた、本発明の１つである。By using the photoelectric conversion element material of the present invention, a photoelectric conversion element with high energy conversion efficiency can be stably and easily formed.
A photoelectric conversion element having a structure in which an active layer made of the photoelectric conversion element material of the present invention is sandwiched between a pair of electrodes is also one aspect of the present invention.
本発明の光電変換素子においては、有機半導体化合物と無機半導体化合物微粒子とが極めて良好に分散した状態にあり、両者の接合界面の面積が大きく、光キャリア生成に対して活性な領域が大きい。従って、本発明の光電変換素子は、エネルギー変換効率が高い。 In the photoelectric conversion element of the present invention, the organic semiconductor compound and the inorganic semiconductor compound fine particles are in a very well dispersed state, the area of the junction interface between them is large, and the active region for photocarrier generation is large. Therefore, the photoelectric conversion element of the present invention has high energy conversion efficiency.
本発明の光電変換素子を製造する方法は特に限定されず、例えば、電極を有する基板上に、本発明の光電変換素子用材料を塗布する工程と、光電変換素子用材料を乾燥させて、活性層を形成する工程とを有する方法が挙げられる。このような光電変換素子の製造方法もまた、本発明の１つである。本発明の光電変換素子の製造方法では、活性層を形成する工程の後、更に、該活性層上に、電極を形成する工程を行ってもよい。 The method for producing the photoelectric conversion element of the present invention is not particularly limited. For example, the step of applying the photoelectric conversion element material of the present invention on a substrate having electrodes, and drying the photoelectric conversion element material to activate the photoelectric conversion element And a step of forming a layer. Such a method for producing a photoelectric conversion element is also one aspect of the present invention. In the method for producing a photoelectric conversion element of the present invention, after the step of forming the active layer, a step of forming an electrode on the active layer may be further performed.
本発明の光電変換素子用材料を塗布する方法は特に限定されないが、例えば、スピンコート法等の印刷法が挙げられる。上記有機半導体化合物と上記無機半導体化合物との分散性が高いことに加えて、活性層の形成方法として印刷法を採用できることから、本発明の光電変換素子用材料を用いることにより、活性層を安定的かつ簡便に形成することができ、光電変換素子の製造コストを削減することができる。 The method for applying the photoelectric conversion element material of the present invention is not particularly limited, and examples thereof include a printing method such as a spin coating method. In addition to the high dispersibility of the organic semiconductor compound and the inorganic semiconductor compound, a printing method can be adopted as a method for forming the active layer, so that the active layer can be stabilized by using the photoelectric conversion element material of the present invention. And the manufacturing cost of the photoelectric conversion element can be reduced.
本発明によれば、エネルギー変換効率の高い光電変換素子を、安定的かつ簡便に製造することができる光電変換素子用材料、該光電変換素子用材料を用いた光電変換素子の製造方法、及び、該光電変換素子用材料を用いてなる光電変換素子を提供することができる。 According to the present invention, a photoelectric conversion element that can stably and easily produce a photoelectric conversion element having high energy conversion efficiency, a method for producing a photoelectric conversion element using the photoelectric conversion element material, and A photoelectric conversion element using the photoelectric conversion element material can be provided.
以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるものではない。 Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
有機半導体化合物として、極性基を有し、かつ、１分子内に共役するドナーとアクセプターとを有する低分子化合物であるＮＫＸ−２５８７（林原生物化学研究所社製）を用いた。
有機半導体化合物１０重量部と、無機半導体化合物として平均粒子径が５ｎｍの酸化亜鉛粒子を３０重量部とを、エタノール３０００重量部とピリジン５００重量部との混合溶媒中に分散させて、光電変換素子用材料を得た。Example 1
As the organic semiconductor compound, NKX-2587 (manufactured by Hayashibara Biochemical Research Institute), which is a low molecular compound having a polar group and having a donor and an acceptor conjugated in one molecule, was used.
10 parts by weight of an organic semiconductor compound and 30 parts by weight of zinc oxide particles having an average particle diameter of 5 nm as an inorganic semiconductor compound are dispersed in a mixed solvent of 3000 parts by weight of ethanol and 500 parts by weight of pyridine to produce a photoelectric conversion element Material was obtained.
ガラス基板上に陽極として厚み２４０ｎｍのＩＴＯ膜を形成し、アセトン、メタノール及びイソプロピルアルコールをこの順に用いて各１０分間超音波洗浄した後、乾燥させた。このＩＴＯ膜の表面上にホール輸送層としてポリエチレンジオキサイドチオフェン：ポリスチレンスルフォネート（ＰＥＤＯＴ：ＰＳＳ）をスピンコート法により１００ｎｍの厚みに成膜した。次いで、このホール輸送層の表面上に上記で得られた光電変換素子用材料をスピンコート法により５０ｎｍの厚みに成膜して、活性層を形成した。更に、この活性層の表面上に陰極として真空蒸着により厚み１００ｎｍのアルミニウム膜を形成し、光電変換素子を得た。 An ITO film having a thickness of 240 nm was formed as an anode on a glass substrate, and was ultrasonically cleaned for 10 minutes each using acetone, methanol and isopropyl alcohol in this order, and then dried. On the surface of this ITO film, polyethylene dioxide thiophene: polystyrene sulfonate (PEDOT: PSS) was formed as a hole transport layer to a thickness of 100 nm by spin coating. Next, the photoelectric conversion element material obtained above was deposited on the surface of the hole transport layer to a thickness of 50 nm by spin coating to form an active layer. Further, an aluminum film having a thickness of 100 nm was formed as a cathode on the surface of the active layer by vacuum vapor deposition to obtain a photoelectric conversion element.
（実施例２）
有機半導体化合物として、極性基を有し、かつ、１分子内に共役するドナーとアクセプターとを有する低分子化合物であるＤ−１４９（三菱製紙社製）を用い、溶媒としてクロロホルム３０００重量部とｏ−ジクロロベンゼン１０００重量部との混合溶媒を用いた以外は実施例１と同様にして、光電変換素子を得た。(Example 2)
As an organic semiconductor compound, D-149 (manufactured by Mitsubishi Paper Industries Co., Ltd.), which is a low molecular compound having a polar group and having a donor and an acceptor conjugated in one molecule, is used. -A photoelectric conversion element was obtained in the same manner as in Example 1 except that a mixed solvent with 1000 parts by weight of dichlorobenzene was used.
（実施例３）
有機半導体化合物として、極性基を有し、かつ、１分子内に共役するドナーとアクセプターとを有する低分子化合物であるＳＫ−ＩＩ（綜研化学社製）を用い、溶媒としてクロロホルムを用いた以外は実施例１と同様にして、光電変換素子を得た。(Example 3)
As an organic semiconductor compound, except that SK-II (manufactured by Soken Chemical Co., Ltd.), which is a low molecular compound having a polar group and having a donor and an acceptor conjugated in one molecule, is used, and chloroform is used as a solvent. In the same manner as in Example 1, a photoelectric conversion element was obtained.
（実施例４）
（有機半導体化合物の合成）
撹拌機を備え付け、窒素置換を行った５０ｍＬ容のシュレンク管に、３，６−ジ（２−チエニル）−２，５−ジヒドロピロロ［３，４−ｃ］ピロール−１，４−ジオンを２５０ｍｇ（０．３２ｍｍｏｌ）、Ｎ−ブロモスクシンイミド１７１ｍｇ（０．９６ｍｍｏｌ）、ジクロロメタン１０ｍＬを仕込んだ。次いで、窒素雰囲気下、室温で４８時間反応させた。反応終了後、これに水を加えて分液操作によって有機層を抽出した。有機層に硫酸マグネシウムを加え乾燥後、減圧下にて濃縮した。その後、クロロホルム、ヘキサンを１：１の比率で混合した展開溶媒を用いて、アミン修飾シリカゲルによるクロマトグラフィーにより、式（ｑ）で表される骨格を有するモノマー（Ａ）を得た。次に、撹拌機を備え付け、窒素置換を行った２５ｍＬ容のシュレンク管に、式（ｑ）で表される骨格を有するモノマー（Ａ）を５９．８ｍｇ（０．０６３ｍｍｏｌ）、式（ｃ）で表されるチオフェン骨格を有するモノマーとして２，５−チオフェンジボロン酸１１．０ｍｇ（０．０６４ｍｍｏｌ）、Ａｌｉｑｕａｔ３３６を５９．２μＬ、トルエン５９．２μＬ、トリフェニルホスフィン（ＰＰｈ３）１．６ｍｇ（６．２μｍｏｌ）を仕込んだ。この混合物に、サンプル瓶に用意した、リン酸カリウム（Ｋ３ＰＯ４）６７．４ｍｇ（０．３２ｍｍｏｌ）を溶解させた蒸留水０．１２ｍＬとトルエン１．１ｍＬとの混合溶液を加え、５分間窒素バブリングを行った。次に、トリス（ジベンジリデンアセトン）二パラジウム（０）（Ｐｄ２（ｄｂａ）３）２．４ｍｇ（２．６μｍｏｌ）を加え、窒素雰囲気下で１１５℃まで昇温し、同温度で７２時間反応させた。その後、反応液を室温まで冷却し、メタノール５００ｍＬに注ぎ、ポリマーを析出させた。
析出したポリマーをろ別した後にクロロホルム２５ｍＬに再び溶かし、アンモニア水２５ｍＬを加え３時間攪拌した。その後、分液操作によって有機層を取り出した。この有機層にエチレンジアミン四酢酸（ＥＤＴＡ）を７５ｍｇ加え室温で１６時間攪拌した後、水２５ｍＬを加え１２時間撹拌した。次に、再度分液によって有機層を取り出し、溶媒を減圧留去した。その後、乾燥した固体を約１ｍＬのクロロホルムに溶解させ、再びメタノール５００ｍＬに注ぎ、ポリマーを析出させた。析出したポリマーをろ別した後にメタノール、水及びヘキサンで順次洗浄した後、減圧乾燥して黒青色の導電性高分子化合物を得た（固体、３２．４ｍｇ）。Example 4
(Synthesis of organic semiconductor compounds)
A 50 mL Schlenk tube equipped with a stirrer and purged with nitrogen was charged with 250 mg of 3,6-di (2-thienyl) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione. (0.32 mmol), 171 mg (0.96 mmol) of N-bromosuccinimide, and 10 mL of dichloromethane were charged. Subsequently, it was made to react at room temperature for 48 hours under nitrogen atmosphere. After completion of the reaction, water was added thereto and the organic layer was extracted by a liquid separation operation. Magnesium sulfate was added to the organic layer, dried, and concentrated under reduced pressure. Thereafter, a monomer (A) having a skeleton represented by the formula (q) was obtained by chromatography on amine-modified silica gel using a developing solvent in which chloroform and hexane were mixed at a ratio of 1: 1. Next, 59.8 mg (0.063 mmol) of the monomer (A) having a skeleton represented by the formula (q) was added to a 25 mL Schlenk tube equipped with a stirrer and purged with nitrogen by the formula (c). As a monomer having a thiophene skeleton, 11.0 mg (0.064 mmol) of 2,5-thiophene diboronic acid, 59.2 μL of Aliquat 336, 59.2 μL of toluene, 1.6 mg of triphenylphosphine (PPh 3 ) (6. 2 μmol) was charged. To this mixture was added a mixed solution of 0.12 mL of distilled water and 1.1 mL of toluene prepared by dissolving 67.4 mg (0.32 mmol) of potassium phosphate (K 3 PO 4 ) prepared in a sample bottle for 5 minutes. Nitrogen bubbling was performed. Next, 2.4 mg (2.6 μmol) of tris (dibenzylideneacetone) dipalladium (0) (Pd 2 (dba) 3 ) was added, the temperature was raised to 115 ° C. under a nitrogen atmosphere, and the reaction was continued at the same temperature for 72 hours. I let you. Thereafter, the reaction solution was cooled to room temperature and poured into 500 mL of methanol to precipitate a polymer.
The precipitated polymer was filtered off and dissolved again in chloroform (25 mL). Aqueous ammonia (25 mL) was added and the mixture was stirred for 3 hours. Thereafter, the organic layer was taken out by a liquid separation operation. To this organic layer, 75 mg of ethylenediaminetetraacetic acid (EDTA) was added and stirred at room temperature for 16 hours, and then 25 mL of water was added and stirred for 12 hours. Next, the organic layer was taken out again by liquid separation, and the solvent was distilled off under reduced pressure. Thereafter, the dried solid was dissolved in about 1 mL of chloroform and poured again into 500 mL of methanol to precipitate a polymer. The precipitated polymer was separated by filtration, washed successively with methanol, water and hexane, and dried under reduced pressure to obtain a black-blue conductive polymer compound (solid, 32.4 mg).
得られた導電性高分子化合物は、共役する、式（ｃ）で表されるセグメント（Ｒ５及びＲ６は水素原子）と式（ｑ）で表されるセグメント（Ｒ３２及びＲ３３はエステル基を含有する官能基）とを有しており、式（ｃ）で表されるセグメントと式（ｑ）で表されるセグメントとの比率は３：１であった。
得られた導電性高分子化合物の収率は、使用したジケトピロロピロール誘導体に対して６０％であった。また、得られた導電性高分子化合物の数平均分子量は４０００、重量平均分子量は８１００であった。なお、数平均分子量及び重量平均分子量は、ゲルパーミエーションクロマトグラフィー（東ソー社製、商品名ＨＬＣ−８０２０）を用いて、クロロホルム中４０℃にて測定し、標準ポリスチレンを基準にして算出した。The obtained conductive polymer compound is conjugated, a segment represented by formula (c) (R 5 and R 6 are hydrogen atoms) and a segment represented by formula (q) (R 32 and R 33 are esters) The ratio of the segment represented by the formula (c) and the segment represented by the formula (q) was 3: 1.
The yield of the obtained conductive polymer compound was 60% based on the diketopyrrolopyrrole derivative used. Moreover, the number average molecular weight of the obtained conductive polymer compound was 4000, and the weight average molecular weight was 8100. In addition, the number average molecular weight and the weight average molecular weight were measured at 40 ° C. in chloroform using gel permeation chromatography (trade name HLC-8020, manufactured by Tosoh Corporation), and calculated based on standard polystyrene.
（光電変換素子の製造）
有機半導体化合物として、上記で得られた導電性高分子化合物を用い、溶媒としてクロロホルム１７００重量部とピリジン３００重量部との混合溶媒を用いた以外は実施例１と同様にして、光電変換素子を得た。(Manufacture of photoelectric conversion elements)
A photoelectric conversion element was prepared in the same manner as in Example 1 except that the conductive polymer compound obtained above was used as the organic semiconductor compound, and a mixed solvent of 1700 parts by weight of chloroform and 300 parts by weight of pyridine was used as the solvent. Obtained.
（実施例５）
有機半導体化合物として、極性基を有し、かつ、共役するドナーとなるセグメントとアクセプターとなるセグメントとを有する導電性高分子化合物であるカルボニル基含有導電性高分子化合物（ＰＢＤＴＴＴ‐ＣＦ、１−ｍｅｔａｌｓ社製）を用い、溶媒としてクロロホルム２０００重量部を用いた以外は実施例１と同様にして、光電変換素子を得た。(Example 5)
As an organic semiconductor compound, a carbonyl group-containing conductive polymer compound (PBDTTTT-CF, 1-metals) which is a conductive polymer compound having a polar group and having a conjugated donor segment and an acceptor segment. A photoelectric conversion element was obtained in the same manner as in Example 1 except that 2000 parts by weight of chloroform was used as a solvent.
（実施例６）
有機半導体化合物として、極性基を有し、かつ、ドナー−アクセプター構造を有さない導電性高分子化合物であるポリ（３−カルボキシチオフェン）（Ｒｉｅｋｅ ｍｅｔａｌｓ社製）を用い、溶媒としてエタノール１５００重量部とピリジン５００重量部との混合溶媒を用いた以外は実施例１と同様にして、光電変換素子を得た。(Example 6)
As an organic semiconductor compound, poly (3-carboxythiophene) (manufactured by Rieke metals), which is a conductive polymer compound having a polar group and not having a donor-acceptor structure, is used, and 1500 parts by weight of ethanol as a solvent A photoelectric conversion element was obtained in the same manner as in Example 1 except that a mixed solvent of pyridine and 500 parts by weight of pyridine was used.
（実施例７）
有機半導体化合物として、極性基を有し、かつ、ドナー−アクセプター構造を有さない導電性高分子化合物であるカルボキシル基含有ポリチオフェン化合物（Ｒｉｅｋｅ ｍｅｔａｌｓ社製、４０３０）を用い、溶媒としてエタノール２０００重量部とピリジン５００重量部との混合溶媒を用い、活性層を１００ｎｍの厚みに成膜した以外は実施例１と同様にして、光電変換素子を得た。(Example 7)
As the organic semiconductor compound, a carboxyl group-containing polythiophene compound (4030, manufactured by Rieke Metals), which is a conductive polymer compound having a polar group and having no donor-acceptor structure, is used, and 2000 parts by weight of ethanol as a solvent. A photoelectric conversion element was obtained in the same manner as in Example 1 except that a mixed solvent of pyridine and 500 parts by weight of pyridine was used and the active layer was formed to a thickness of 100 nm.
（実施例８）
有機半導体化合物として、極性基を有し、かつ、ドナー−アクセプター構造を有さない導電性高分子化合物であるポリエーテル基含有ポリフェニレンビニレン化合物（アルドリッチ社製、ＭＤＭＯ−ＰＰＶ）を用い、溶媒としてクロロベンゼン２０００重量部を用い、活性層を１００ｎｍの厚みに成膜した以外は実施例１と同様にして、光電変換素子を得た。(Example 8)
A polyether group-containing polyphenylene vinylene compound (MDMO-PPV, manufactured by Aldrich), which is a conductive polymer compound having a polar group and not having a donor-acceptor structure, is used as an organic semiconductor compound, and chlorobenzene is used as a solvent. A photoelectric conversion element was obtained in the same manner as in Example 1 except that 2000 parts by weight was used and the active layer was formed to a thickness of 100 nm.
（実施例９）
有機半導体化合物として、極性基を有し、かつ、ドナー−アクセプター構造を有さない導電性高分子化合物であるエステル基含有ポリチオフェン化合物（Ｒｉｅｋｅ Ｍｅｔａｌｓ社製、４０２０）を用い、溶媒としてクロロホルム２０００重量部を用い、活性層を１００ｎｍの厚みに成膜した以外は実施例１と同様にして、光電変換素子を得た。Example 9
As an organic semiconductor compound, an ester group-containing polythiophene compound (Rieke Metals, 4020), which is a conductive polymer compound having a polar group and not having a donor-acceptor structure, is used, and 2000 parts by weight of chloroform as a solvent. And a photoelectric conversion element was obtained in the same manner as in Example 1 except that the active layer was formed to a thickness of 100 nm.
（比較例１）
有機半導体化合物として、下記式（７）で表されるＦ８ＢＴ（アルドリッチ社製）を用い、溶媒としてクロロホルムを用いた以外は実施例１と同様にして、光電変換素子を得た。
なお、下記式（７）で表されるＦ８ＢＴは、共役するドナーとアクセプターとを有するものの、極性基は有しない導電性高分子化合物である。(Comparative Example 1)
A photoelectric conversion element was obtained in the same manner as in Example 1 except that F8BT (manufactured by Aldrich) represented by the following formula (7) was used as the organic semiconductor compound, and chloroform was used as the solvent.
Note that F8BT represented by the following formula (7) is a conductive polymer compound that has a conjugated donor and an acceptor but does not have a polar group.
（比較例２）
有機半導体化合物として、Ｐ３ＯＴ（アルドリッチ社製）を用い、溶媒としてクロロホルム１５００重量部とクロロベンゼン５００重量部との混合溶媒を用いた以外は実施例１と同様にして、光電変換素子を得た。
なお、Ｐ３ＯＴは、極性基を有さず、ドナー性部位もアクセプター性部位も有しない導電性高分子化合物である。(Comparative Example 2)
A photoelectric conversion element was obtained in the same manner as in Example 1 except that P3OT (manufactured by Aldrich) was used as the organic semiconductor compound and a mixed solvent of 1500 parts by weight of chloroform and 500 parts by weight of chlorobenzene was used as the solvent.
Note that P3OT is a conductive polymer compound that does not have a polar group and has neither a donor site nor an acceptor site.
（比較例３）
有機半導体化合物として、ポリチオフェン化合物であるＰ３ＨＴ（アルドリッチ社製）を用い、溶媒としてクロロホルム２０００重量部を用い、活性層を１００ｎｍの厚みに成膜した以外は実施例１と同様にして、光電変換素子を得た。
なお、Ｐ３ＨＴは、極性基を有さず、ドナー性部位もアクセプター性部位も有しない導電性高分子化合物である。(Comparative Example 3)
A photoelectric conversion element was obtained in the same manner as in Example 1 except that P3HT (manufactured by Aldrich) as a polythiophene compound was used as the organic semiconductor compound, 2000 parts by weight of chloroform was used as the solvent, and the active layer was formed to a thickness of 100 nm. Got.
Note that P3HT is a conductive polymer compound that does not have a polar group and has neither a donor site nor an acceptor site.
（比較例４）
有機半導体化合物として、シリコンナフタロシアニン誘導体（シリコン２，３−ナフタロシアニンビス（トリヘキシルシリルオキシド）、アルドリッチ社製）を用い、溶媒としてクロロホルム２０００重量部を用い、活性層を１００ｎｍの厚みに成膜した以外は実施例１と同様にして、光電変換素子を得た。
なお、シリコンナフタロシアニン誘導体は、極性基を有さず、ドナー性部位もアクセプター性部位も有しない低分子化合物である。(Comparative Example 4)
A silicon naphthalocyanine derivative (silicon 2,3-naphthalocyanine bis (trihexylsilyloxide), manufactured by Aldrich) is used as an organic semiconductor compound, and 2000 parts by weight of chloroform is used as a solvent, and an active layer is formed to a thickness of 100 nm. A photoelectric conversion element was obtained in the same manner as in Example 1 except that.
Note that a silicon naphthalocyanine derivative is a low molecular compound having no polar group and having neither a donor site nor an acceptor site.
（評価１）
実施例及び比較例で得られた光電変換素子用材料を、ガラス基板上に３０００ｒｐｍでスピンコートした。得られたガラス基板上の塗布膜を、光学顕微鏡（キーエンス社製、ＶＨＸ−５００Ｆ、倍率１０００倍）を用いて観察した。塗布膜に相分離による模様が観察された場合を×、塗布膜が均一で相分離による模様が観察されなかった場合を○とし、分散性を評価した。更に、実施例及び比較例で得られた光電変換素子用材料を、ガラス基板上に１０００ｒｐｍでスピンコートし、得られたガラス基板上の塗布膜を同様にして観察して、塗布膜が均一で相分離による模様が観察されなかった場合を◎とした。結果を表１に示した。(Evaluation 1)
The photoelectric conversion element materials obtained in Examples and Comparative Examples were spin-coated on a glass substrate at 3000 rpm. The coating film on the obtained glass substrate was observed using an optical microscope (manufactured by Keyence Corporation, VHX-500F, magnification 1000 times). The case where a pattern due to phase separation was observed in the coating film was evaluated as x, and the case where the coating film was uniform and the pattern due to phase separation was not observed was evaluated as ◯. Further, the photoelectric conversion element materials obtained in Examples and Comparative Examples were spin-coated on a glass substrate at 1000 rpm, and the coating film on the obtained glass substrate was observed in the same manner, and the coating film was uniform. The case where no pattern due to phase separation was observed was marked with ◎. The results are shown in Table 1.
（評価２）
実施例及び比較例で得られた光電変換素子用材料を、ＰＥＴ基板上に３０００ｒｐｍでスピンコートした。ＰＥＴ基板を折り曲げたときに塗布膜に亀裂が入った場合を×、亀裂が入らなかった場合を○として、製膜性を評価した。結果を表１に示した。(Evaluation 2)
The photoelectric conversion element materials obtained in Examples and Comparative Examples were spin-coated on a PET substrate at 3000 rpm. When the PET substrate was bent, the film-forming property was evaluated with a case where the coating film was cracked as x and a case where the crack was not cracked as ◯. The results are shown in Table 1.
（評価３）
実施例及び比較例で得られた光電変換素子用材料を、ガラス基板上に２０００ｒｐｍでスピンコートした。得られたガラス基板上の塗布膜の吸光度を、分光光度計（日立ハイテク社製、型式Ｕ−３０００）を用いて測定し、波長８００ｎｍでの吸光度を求めた。波長８００ｎｍでの吸光度が０．３以上であった場合を○、０．３未満であった場合を×として、長波長光の吸収を評価した。結果を表１に示した。(Evaluation 3)
The photoelectric conversion element materials obtained in Examples and Comparative Examples were spin-coated on a glass substrate at 2000 rpm. The absorbance of the coating film on the obtained glass substrate was measured using a spectrophotometer (manufactured by Hitachi High-Tech, model U-3000), and the absorbance at a wavelength of 800 nm was determined. Absorption at a wavelength of 800 nm was 0.3 or more, and the case of less than 0.3 was x, and the absorption of long wavelength light was evaluated. The results are shown in Table 1.
（評価４）
実施例及び比較例で得られた光電変換素子の電極間に、電源（ＫＥＹＴＨＬＥＹ社製、２３６モデル）を接続し、１００ｍＷ／ｃｍ２の強度のソーラーシミュレータ（山下電装社製）を用いて光電変換素子のエネルギー変換効率を測定した。比較例１で得られた光電変換素子のエネルギー変換効率を１．００として規格化した。規格化した値が１以下であった場合を×、１より大きく２以下であった場合を△、２より大きく４以下であった場合を○、４より大きかった場合を◎として、エネルギー変換効率を評価した。結果を表１に示した。(Evaluation 4)
A power source (manufactured by KEYTHLEY, 236 model) is connected between the electrodes of the photoelectric conversion elements obtained in Examples and Comparative Examples, and photoelectric conversion is performed using a solar simulator (manufactured by Yamashita Denso Co., Ltd.) having an intensity of 100 mW / cm 2. The energy conversion efficiency of the device was measured. The photoelectric conversion element obtained in Comparative Example 1 was normalized by setting the energy conversion efficiency to 1.00. When the normalized value is 1 or less, x is greater than 1 and 2 or less, Δ is greater than 2 and 4 or less, ○ is greater than 4, and ◎ is energy conversion efficiency. Evaluated. The results are shown in Table 1.
（総合評価）
上記評価１〜４の◎を２点、○を１点、△及び×を０点として、合計点を求めた。合計点が３点以上であった場合を○、３点未満であった場合を×として、総合評価を行った。結果を表１に示した。(Comprehensive evaluation)
In the above evaluations 1 to 4, the total score was obtained with 2 points, 1 point, and 0 points as Δ and ×. When the total score was 3 points or more, the case of less than 3 points was evaluated as x, and the overall evaluation was performed. The results are shown in Table 1.
本発明によれば、エネルギー変換効率の高い光電変換素子を、安定的かつ簡便に製造することができる光電変換素子用材料、該光電変換素子用材料を用いた光電変換素子の製造方法、及び、該光電変換素子用材料を用いてなる光電変換素子を提供することができる。 According to the present invention, a photoelectric conversion element that can stably and easily produce a photoelectric conversion element having high energy conversion efficiency, a method for producing a photoelectric conversion element using the photoelectric conversion element material, and A photoelectric conversion element using the photoelectric conversion element material can be provided.
Claims (14)
有機半導体化合物、平均粒子径が１〜３０ｎｍである無機半導体化合物微粒子、及び、有機溶媒を含有し、前記有機半導体化合物は、極性基を有するものであることを特徴とする光電変換素子用材料。 A material for a photoelectric conversion element used for forming an active layer of an organic solar cell including an organic semiconductor compound and an inorganic semiconductor compound on a substrate having an electrode,
The organic semiconductor compound, an inorganic semiconductor compound fine particles having an average particle diameter of 1 to 30 nm, and contains an organic solvent, the organic semiconductor compound, a material for a photoelectric conversion device which is characterized in that those having a polar group.
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