JP2018043943A - Novel squarylium derivative and organic thin film solar battery using the same - Google Patents
Novel squarylium derivative and organic thin film solar battery using the same Download PDFInfo
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- JP2018043943A JP2018043943A JP2016179255A JP2016179255A JP2018043943A JP 2018043943 A JP2018043943 A JP 2018043943A JP 2016179255 A JP2016179255 A JP 2016179255A JP 2016179255 A JP2016179255 A JP 2016179255A JP 2018043943 A JP2018043943 A JP 2018043943A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/549—Organic PV cells
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Abstract
Description
本発明は、新規なスクアリリウム誘導体、及びそれを用いた有機薄膜太陽電池素子に関する。 The present invention relates to a novel squarylium derivative and an organic thin film solar cell element using the same.
近年、有機薄膜太陽電池は、軽量で自由に曲げられるという特徴をもち、製造コスト面でも有利であることから、シリコン系無機太陽電池に代わって、実用化・市場投入段階に入りつつある。有機薄膜太陽電池には蒸着型及び塗布型があるが、特に塗布型の有機薄膜太陽電池は、蒸着型の有機薄膜太陽電池に比べて製造コストが安く、大量生産に向いている。しかしながら、有機薄膜太陽電池は、その光電エネルギー変換効率が10%程度であり、シリコン系無機太陽電池と比較して、効率や信頼性の点で未だ改善の余地があり、盛んに研究開発が行われている。 In recent years, organic thin film solar cells are lightweight and can be bent freely, and are advantageous in terms of manufacturing cost. Therefore, instead of silicon-based inorganic solar cells, they are entering the stage of commercialization and market introduction. Organic thin film solar cells include a vapor deposition type and a coating type. Particularly, a coating type organic thin film solar cell has a lower manufacturing cost and is suitable for mass production than a vapor deposition type organic thin film solar cell. However, organic thin-film solar cells have a photoelectric energy conversion efficiency of about 10%, and there is still room for improvement in terms of efficiency and reliability compared to silicon-based inorganic solar cells. It has been broken.
太陽光は、そのエネルギーの50%以上を、650nmより長波長の近赤外・赤外領域に持つ。そのため、光電変換効率の飛躍的な向上には、この波長領域を効率良く吸収し、電気エネルギーとして取り出すことが必須である。有機薄膜太陽電池素子はドナー材料とアクセプター材料を用いて作製される。一般にアクセプター材料で用いられているフラーレン誘導体は逆電子移動が遅く、対称性が高いという利点があるが、これらは近赤外領域付近に強い吸収を持たないため、有機薄膜太陽電池の高効率化には、長波長領域の吸収を持つドナー材料の開発が非常に重要となる。また、有機薄膜太陽電池の高効率化には、ドナー材料と、アクセプター材料とのエネルギー準位の関係が重要である。ドナー材料で太陽光を吸収して発生した励起子(エキシトン)からアクセプター材料に電荷移動させるには、一般にドナー材料の最低非占有分子軌道(lowest unoccupied molecular orbital:LUMO)準位がアクセプター材料のLUMO準位よりも0.3eV以上浅いことが好ましいとされている。塗布型有機薄膜太陽電池では、アクセプター材料として、通常溶解性が高い[6,6]−フェニルC71酪酸メチル(PC71BM)が使用される。PC71BMのLUMO準位は4.0eVであるから、ドナー材料には3.7eV程度のLUMO準位が求められる。 Sunlight has 50% or more of its energy in the near infrared / infrared region having a wavelength longer than 650 nm. Therefore, to dramatically improve the photoelectric conversion efficiency, it is essential to efficiently absorb this wavelength region and take it out as electric energy. The organic thin film solar cell element is manufactured using a donor material and an acceptor material. In general, fullerene derivatives used in acceptor materials have the advantage of slow reverse electron transfer and high symmetry, but they do not have strong absorption near the near infrared region, so the efficiency of organic thin-film solar cells is improved. For this purpose, it is very important to develop a donor material having absorption in the long wavelength region. In addition, the relationship between the energy levels of the donor material and the acceptor material is important for increasing the efficiency of the organic thin film solar cell. In general, the lowest unoccupied molecular orbital (LUMO) level of the donor material is the LUMO of the acceptor material in order to transfer charge from the exciton (exciton) generated by absorbing sunlight in the donor material to the acceptor material. It is preferable that the depth is shallower by 0.3 eV or more than the level. In the coating type organic thin film solar cell, [6,6] -phenyl C71 methyl butyrate (PC 71 BM) having high solubility is usually used as an acceptor material. Since the LUMO level of PC 71 BM is 4.0 eV, the donor material is required to have a LUMO level of about 3.7 eV.
塗布型有機薄膜太陽電池に使用されるドナー材料は、当然ながら、溶媒によく溶ける必要がある。ドナー材料は大きく分けて高分子型と低分子型の2つが知られている。高分子型材料は、そのエネルギー変換効率が12%程度まで向上しているが、高分子型材料は、精製が難しく、高純度化が困難で、製造ロット間の特性変化が大きく品質を保つことが難しい。一方、低分子型材料は、分子量分布を持たず、精製が容易で信頼性が高い、又は、製造ロット間の品質が変わらず、ロットによりエネルギー変換効率に影響を与えない等の特徴を持つ。しかしながら、低分子型材料は、現時点で移動度も10-5cm2/Vs程度と低く、エネルギー変換効率も、アクセプターにフラーレンを用いてようやく10%を上回る程度である。また、低分子型材料のうち、高効率を達成している材料は、一般に溶解性が低く、塗布型有機薄膜太陽電池を作製する際に、オルトジクロロベンゼン(ODCB)、クロロホルム等、ハロゲン系の溶媒を使用しなければならず、環境面で問題がある。そのため、塗布型有機薄膜太陽電池の高性能化と実用性向上には、近赤外光の吸収能と高い移動度を持ち、非ハロゲン系の溶媒等にも高い溶解性を示す新しい低分子材料の開発が求められている。 Needless to say, the donor material used in the coating type organic thin film solar cell needs to be well dissolved in a solvent. Donor materials are roughly classified into two types, a high molecular type and a low molecular type. Polymer type materials have improved energy conversion efficiency to about 12%, but polymer type materials are difficult to purify and highly purified, and the quality changes greatly between production lots to maintain quality. Is difficult. On the other hand, the low molecular weight material has characteristics such as no molecular weight distribution, easy purification and high reliability, or quality between production lots does not change, and energy conversion efficiency is not affected by lots. However, the low molecular weight material has a mobility as low as about 10 −5 cm 2 / Vs at the present time, and the energy conversion efficiency finally exceeds 10% by using fullerene as an acceptor. Further, among the low molecular weight materials, materials that have achieved high efficiency are generally low in solubility, and halogen-based materials such as orthodichlorobenzene (ODCB), chloroform, etc. are used in the production of coated organic thin film solar cells. Solvents must be used and are environmentally problematic. Therefore, a new low molecular weight material that has high absorption capability and high mobility for near-infrared light, and high solubility in non-halogen solvents, etc., to improve the performance and practicality of coated organic thin-film solar cells. Development is required.
スクアリリウム誘導体は、非ハロゲン系溶媒に対しても高い溶解性を示し、近赤外領域に強い吸収を持ち、かつ、逆電子移動が遅く、高い対称性を持つ構造であることから、ドナー材料として研究開発が行われており、すでに多数報告されている(非特許文献1〜3)。
As a donor material, squarylium derivatives are highly soluble in non-halogen solvents, have strong absorption in the near infrared region, have slow reverse electron transfer, and high symmetry. Research and development has been conducted, and many reports have already been reported (Non-Patent
スクアリリウム誘導体は、脱水縮合反応により高収率で比較的容易に合成できて環境に優しく、また、種々の置換基の導入も可能である。塗布成膜によるBHJ(bulk heterojunction)型の素子で、例えば、S−ASQとPC71BMとを用いた混合BHJ素子(S−ASQ/PC71BM(1:7(質量比))では、PCE(power conversion efficiency)が5.52%を達成している。ただし、これらの誘導体のエネルギー変換効率は、以前のものに比べれば向上しているものの、未だ低い値に留まっている。また、これらのスクアリリウム誘導体を用いた有機薄膜太陽電池は、そのVOC(開放電圧)、JSC(短絡電流密度)の値が他の材料に比べて高いものの、FF(曲線因子)が低いという問題があった。
前記S−ASQにおいて、例えば、π共役系を拡張することで、可視〜近赤外領域の光を吸収できるようになると考えられる。また、π共役系を拡張することで、正孔移動度が向上すれば、自在に動き回るπ電子に由来する種々の光学的・電気化学的機能を向上できると考えられる。 In the S-ASQ, for example, it is considered that light in the visible to near infrared region can be absorbed by extending the π-conjugated system. Moreover, it is considered that if the hole mobility is improved by extending the π-conjugated system, various optical and electrochemical functions derived from freely moving π electrons can be improved.
本発明では、高効率な素子を提供するために有用な新規スクアリリウム誘導体を提供すべく、ASQ構造に着目し、その末端置換基を改良して、エネルギー準位を変化させずに、薄膜状態での移動度を向上させ、さらにFF(曲線因子)を改善してエネルギー変換効率を向上させることを課題としている。また、得られたスクアリリウム誘導体を用いた有機薄膜太陽電池を提供することを課題としている。 In the present invention, in order to provide a novel squarylium derivative useful for providing a high-efficiency device, focusing on the ASQ structure, the terminal substituent is improved, and without changing the energy level, in a thin film state. It is an object to improve the energy conversion efficiency by improving the FF (curve factor). Another object of the present invention is to provide an organic thin film solar cell using the obtained squarylium derivative.
本発明は以下の事項からなる。
本発明のスクアリリウム誘導体は、下記一般式(1)で表されることを特徴とする。
The squarylium derivative of the present invention is represented by the following general formula (1).
一般式(1)中、R1〜R6はそれぞれ独立に脂肪族基又は芳香族基を示し、R2及びR3が脂肪族基の場合、R2及びR3は連結して環を形成してもよく、R5及びR6が脂肪族基の場合、R5及びR6は連結して環を形成してもよく、Xは、フェニル基、又は、下記構造式で表される置換基を示し、Arは芳香族基を示す。 In general formula (1), R 1 to R 6 each independently represents an aliphatic group or an aromatic group, and when R 2 and R 3 are aliphatic groups, R 2 and R 3 are linked to form a ring. When R 5 and R 6 are aliphatic groups, R 5 and R 6 may be linked to form a ring, and X is a phenyl group or a substituent represented by the following structural formula Represents a group, and Ar represents an aromatic group.
前記一般式(1)中、Arはチオフェニレン基を示すことが好ましい。
前記一般式(1)中、Arはチオフェニレン基を示し、かつ、R1〜R6はそれぞれ独立に炭素原子数1〜20の脂肪族基を示すことが好ましい。脂肪族基は直鎖であっても、分岐を有していてもよい。
本発明の有機薄膜太陽電池は、上記スクアリリウム誘導体を用いたものであることを特徴とする。
In the general formula (1), Ar preferably represents a thiophenylene group.
In the general formula (1), Ar represents a thiophenylene group, and R 1 to R 6 preferably each independently represent an aliphatic group having 1 to 20 carbon atoms. The aliphatic group may be linear or branched.
The organic thin film solar cell of the present invention is characterized by using the above squarylium derivative.
本発明のスクアリリウム誘導体は、従来より既知のS−ASQの末端の置換基の一方に、芳香族縮合環であるベンゾ[1,2−b:4,5−b’]ジチオフェン(BDT)の橋掛け構造を介して、フェニル基、又はスクアリリウム誘導体構造を付加することにより、分子内のπ共役が拡張され、正孔移動度が向上し、また、最高占有分子軌道(highest occupied molecular orbital;HOMO)が深くなり、安定性が向上する。 The squarylium derivative of the present invention has a bridge of benzo [1,2-b: 4,5-b ′] dithiophene (BDT), which is an aromatic condensed ring, on one of the conventionally known substituents at the end of S-ASQ. By adding a phenyl group or a squarylium derivative structure through a hanging structure, the π conjugation in the molecule is expanded, the hole mobility is improved, and the highest occupied molecular orbital (HOMO) Deepens and improves stability.
また、本発明のスクアリリウム誘導体は、π共役が拡張されることにより、固体薄膜における吸収波長を750nmの近赤外領域まで拡張できるとともに、適切な電子物性を持つことができる。特に、D−BDT−ASQでは、平面かつ非対称な二量体構造を有するため、成膜時のフェイスオン(face−on)配向性が高くなり、正孔移動度を向上させるとともに、550〜700nmの領域で強い吸収を示す。 In addition, the squarylium derivative of the present invention can expand the absorption wavelength in the solid thin film to the near-infrared region of 750 nm by extending the π conjugation, and can have appropriate electronic properties. In particular, since D-BDT-ASQ has a planar and asymmetric dimer structure, the face-on orientation during film formation is increased, hole mobility is improved, and 550 to 700 nm. Strong absorption is shown in the region.
よって、本発明によれば、上記一般式(1)で表されるスクアリリウム誘導体を用いることにより、得られる素子は、薄膜状態でのキャリア移動度が向上してFFの値が改善され、結果としてエネルギー変換効率が向上した、高効率な有機薄膜太陽電池を提供することができる。 Therefore, according to the present invention, by using the squarylium derivative represented by the general formula (1), the resulting device has improved carrier mobility in a thin film state and improved FF value. A highly efficient organic thin-film solar cell with improved energy conversion efficiency can be provided.
以下、本発明について、詳細に説明する。
[スクアリリウム誘導体]
本発明のスクアリリウム誘導体は、下記一般式(1)で表される。
[Squarylium derivatives]
The squarylium derivative of the present invention is represented by the following general formula (1).
一般式(1)中、R1〜R6はそれぞれ独立に1価の脂肪族基又は1価の芳香族基である。
脂肪族基は、芳香族基以外の基を広く含みうるが、具体的には、炭素原子数が1〜20の直鎖又は分岐状の脂肪族基を指す。また、本発明の効果を損なわない範囲内で、脂肪族基を構成する水素原子の一部が、例えば、窒素原子、硫黄原子、酸素原子、リン原子若しくはケイ素原子又はこれらを含む置換基で置換されていてもよい。
炭素原子数1〜20の脂肪族基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、エチルヘキシル基、及びドデシル基等が挙げられる。これらのうち、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、ヘキシル基、オクチル基、及びエチルヘキシル基等がより好ましく、ブチル基及びエチルヘキシル基等が特に好ましい。
芳香族基は、単環のアリール基又はヘテロアリール基でもよいし、多環(縮合環)のアリール基又はヘテロアリール基でもよい。また、前記芳香族基における芳香環上の水素原子の一部が、例えば、メチル基、イソプロピル基及びイソブチル基等で置換されていてもよい。
上記芳香族基は、炭素原子数が6〜50の芳香族基であることが好ましい。
炭素数6〜50の芳香族基としては、例えば、フェニル基、ピリジル基、チオフェニル基、ビフェニル基、ナフチル基、トリフェニレニル基、ターフェニル基、クオーターフェニル基、アントラセニル基、ベンゾチオフェニル基、ベンゾフラニル基、ジベンゾチオフェニル基、及びジベンゾフラニル基等が挙げられる。これらのうち、フェニル基、ピリジル基、チオフェニル基、ビフェニル基、ベンゾチオフェニル基、及びベンゾフラニル基等がより好ましい。
R2及びR3が脂肪族基の場合、R2及びR3は連結して4員環、5員環又は6員環を形成してもよく、R5及びR6が脂肪族基の場合、R5及びR6は連結して4員環、5員環又は6員環を形成してもよい。
In the general formula (1), R 1 to R 6 are each independently a monovalent aliphatic group or a monovalent aromatic group.
The aliphatic group may widely include groups other than aromatic groups, and specifically refers to a linear or branched aliphatic group having 1 to 20 carbon atoms. Further, within a range not impairing the effects of the present invention, a part of the hydrogen atoms constituting the aliphatic group is substituted with, for example, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, a silicon atom, or a substituent containing these. May be.
Examples of the aliphatic group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. Group, octyl group, ethylhexyl group, dodecyl group and the like. Of these, isopropyl group, butyl group, isobutyl group, sec-butyl group, hexyl group, octyl group, and ethylhexyl group are more preferable, and butyl group and ethylhexyl group are particularly preferable.
The aromatic group may be a monocyclic aryl group or heteroaryl group, or may be a polycyclic (fused ring) aryl group or heteroaryl group. Moreover, some hydrogen atoms on the aromatic ring in the aromatic group may be substituted with, for example, a methyl group, an isopropyl group, an isobutyl group, or the like.
The aromatic group is preferably an aromatic group having 6 to 50 carbon atoms.
Examples of the aromatic group having 6 to 50 carbon atoms include phenyl group, pyridyl group, thiophenyl group, biphenyl group, naphthyl group, triphenylenyl group, terphenyl group, quarterphenyl group, anthracenyl group, benzothiophenyl group, and benzofuranyl group. , Dibenzothiophenyl group, and dibenzofuranyl group. Of these, a phenyl group, a pyridyl group, a thiophenyl group, a biphenyl group, a benzothiophenyl group, a benzofuranyl group, and the like are more preferable.
When R 2 and R 3 are aliphatic groups, R 2 and R 3 may be linked to form a 4-membered ring, 5-membered ring or 6-membered ring, and when R 5 and R 6 are aliphatic groups , R 5 and R 6 may be linked to form a 4-membered, 5-membered or 6-membered ring.
Xは、フェニル基、又は、下記構造式で表される1価の置換基を示す。
具体的には、上記一般式(1)で表される化合物は、以下の構造式で表される化合物BDT−ASQ又はD−BDT−ASQであることが好ましい。
上記一般式(1)で表されるスクアリリウム誘導体は、従来のS−ASQの末端の置換基の一方に、芳香族縮合環であるベンゾ[1,2−b:4,5−b’]ジチオフェン(BDT)の橋掛け構造を介して、フェニル基、又はスクアリリウム誘導体を付加した構造を有することにより、深いHOMO及び近赤外領域における広い吸収を持つことができ、また、長鎖分岐構造の脂肪族炭化水素基を有することにより、有機溶媒への溶解性が向上し、例えば、スクアリリウム誘導体の末端の置換基がいずれも芳香族基である場合や、末端置換基の一方が芳香族基であり、他方が直鎖状の脂肪族基である場合と比較して、近赤外領域におけるモル吸光係数と有機溶媒への溶解性が向上する。
[スクアリリウム誘導体の製造方法]
本発明のスクアリリウム誘導体は、例えば、以下に示す方法により製造することができる。BDT−ASQの製造方法を一例に示す。
3−((5−ブロモ−1−ブチル−3,3−ジメチルインドリン−2−イリデン)メチル)4−エトキシシクロブタ−3−エン−1,2−ジオン及び4,8−ビス[5−(2−エチルヘキシル)チオフェン−2−イル]−2,6−ビス(トリメチルスタニル)ベンゾ[1,2−b:4,5−b’]ジチオフェンを、Pd(PPh3)4の存在下、トルエン溶液中で36時間加熱還流した後、得られる反応混合物をシリカゲルカラムクロマトグラフィーにより精製して、化合物1a及び1bをそれぞれ収率29%及び36%で得る。得られた化合物1a及び1bのうち、化合物1aをアセトンに溶解させ、6M塩酸を8mL滴下し、5時間加熱還流することにより、収率82%で化合物2aを得る。次いで、化合物2a及び5−(1,3,3a,8b−テトラヒドロシクロペンタ[b]インドール−4(2H)−イル)ベンゼン−1,3−ジオールを、トルエン及びn−ブタノールの1:1混合溶液中で、36時間、140℃で反応させることにより、暗赤色固体であるBDT−ASQを得る(収率70%)。
ただし、上記一般式(1)で表されるスクアリリウム誘導体は、上記した方法に限られず、種々の公知の方法で製造することができる。
[Method for producing squarylium derivative]
The squarylium derivative of the present invention can be produced, for example, by the method shown below. A method for producing BDT-ASQ is shown as an example.
3-((5-Bromo-1-butyl-3,3-dimethylindoline-2-ylidene) methyl) 4-ethoxycyclobut-3-ene-1,2-dione and 4,8-bis [5- ( 2-ethylhexyl) thiophen-2-yl] -2,6-bis (trimethylstannyl) benzo [1,2-b: 4,5-b ′] dithiophene in toluene in the presence of Pd (PPh 3 ) 4 After heating to reflux for 36 hours in solution, the resulting reaction mixture is purified by silica gel column chromatography to give compounds 1a and 1b in 29% and 36% yield, respectively. Of the obtained compounds 1a and 1b, compound 1a is dissolved in acetone, 8 mL of 6M hydrochloric acid is dropped, and the mixture is heated to reflux for 5 hours to obtain compound 2a in a yield of 82%. Compound 2a and 5- (1,3,3a, 8b-tetrahydrocyclopenta [b] indol-4 (2H) -yl) benzene-1,3-diol are then mixed in a 1: 1 mixture of toluene and n-butanol. BDT-ASQ, a dark red solid, is obtained by reacting in solution at 140 ° C. for 36 hours (yield 70%).
However, the squarylium derivative represented by the general formula (1) is not limited to the above-described method, and can be produced by various known methods.
[有機薄膜太陽電池及びその製造方法]
本発明の有機薄膜太陽電池素子(以下「太陽電池素子」ともいう。)は、一対の電極(陽極2、陰極6)間に、ドナー及びアクセプターの界面構造を含む活性層が積層された素子構造を有する。ドナー材料とアクセプター材料とが相互に入り組んだ界面において、電荷(電子、正孔)が生成される。典型的には、図1に示すように、基板1、陽極2、正孔輸送層3、活性層4、電子輸送層5及び陰極6が順次積層された素子構造を有する。
以下、本発明の太陽電池素子の構成を説明する。
[Organic thin film solar cell and manufacturing method thereof]
The organic thin film solar cell element of the present invention (hereinafter also referred to as “solar cell element”) has an element structure in which an active layer including an interface structure of a donor and an acceptor is laminated between a pair of electrodes (
Hereinafter, the configuration of the solar cell element of the present invention will be described.
<太陽電池素子の構成>
本発明の太陽電池素子の構成は、図1の例に限定されず、陽極と陰極との間に順次、1)陽極バッファ層(図示せず)/正孔輸送層/活性層、2)陽極バッファ層(図示せず)/活性層/電子輸送層、3)陽極バッファ層(図示せず)/正孔輸送層/活性層/電子輸送層、4)陽極バッファ層(図示せず)/正孔輸送性化合物、活性化合物および電子輸送性化合物を含む層、5)陽極バッファ層(図示せず)/正孔輸送性化合物及び活性化合物を含む層、6)陽極バッファ層(図示せず)/活性化合物及び電子輸送性化合物を含む層、7)陽極バッファ層(図示せず)/正孔電子輸送性化合物および活性化合物を含む層、8)陽極バッファ層(図示せず)/活性層/正孔ブロック層(図示せず)/電子輸送層を設けた構成等が挙げられる。また、図1に示した活性層は一層であるが、二層以上であってもよい。
<Configuration of solar cell element>
The configuration of the solar cell element of the present invention is not limited to the example shown in FIG. 1, and 1) an anode buffer layer (not shown) / hole transport layer / active layer, and 2) an anode sequentially between the anode and the cathode. Buffer layer (not shown) / active layer / electron transport layer, 3) anode buffer layer (not shown) / hole transport layer / active layer / electron transport layer, 4) anode buffer layer (not shown) / positive Layer containing hole transporting compound, active compound and electron transporting compound, 5) Anode buffer layer (not shown) / Layer containing hole transporting compound and active compound, 6) Anode buffer layer (not shown) / Layer containing active compound and electron transporting compound, 7) Anode buffer layer (not shown) / layer containing hole electron transporting compound and active compound, 8) Anode buffer layer (not shown) / active layer / positive The structure etc. which provided the hole block layer (not shown) / electron carrying layer are mentioned. Further, the active layer shown in FIG. 1 is a single layer, but may be two or more layers.
<陽極>
前記陽極には、−5〜80℃の温度範囲で、面抵抗が、通常1000Ω(オーム)以下、好ましくは100Ω以下の材料が用いられる。
太陽電池素子の陽極側から光を取り出す場合(ボトムエミッション)には、陽極は可視光線に対して透明(380〜680nmの光に対する平均透過率が50%以上)であることが必要であるため、陽極の材料には、酸化インジウム錫(ITO)及びインジウム−亜鉛酸化物(IZO)等が用いられる。これらのうち、入手容易性の観点から、ITOが好ましい。
<Anode>
For the anode, a material having a surface resistance of usually 1000Ω (ohms) or less, preferably 100Ω or less in a temperature range of −5 to 80 ° C. is used.
When extracting light from the anode side of the solar cell element (bottom emission), the anode needs to be transparent to visible light (average transmittance for light of 380 to 680 nm is 50% or more). For the material of the anode, indium tin oxide (ITO), indium-zinc oxide (IZO), or the like is used. Of these, ITO is preferable from the viewpoint of availability.
また、素子の陰極側から光を取り出す場合(トップエミッション)には、陽極の光透過度は制限されないため、陽極の材料には、ITO及びIZOの他に、ステンレスや、銅、銀、金、白金、タングステン、チタン、タンタル若しくはニオブの単体、又はこれらの合金が用いられる。 In addition, when light is extracted from the cathode side of the device (top emission), the light transmittance of the anode is not limited. Therefore, in addition to ITO and IZO, the anode material includes stainless steel, copper, silver, gold, Platinum, tungsten, titanium, tantalum, niobium, or an alloy thereof is used.
陽極の厚さは、ボトムエミッションの場合には、高い光透過率を実現するために、通常2〜300nmであり、トップエミッションの場合には、通常2nm〜2mmである。 In the case of bottom emission, the thickness of the anode is usually 2 to 300 nm in order to realize high light transmittance, and in the case of top emission, it is usually 2 nm to 2 mm.
<陽極バッファ層>
陽極バッファ層は、陽極上に、陽極バッファ層用材料を塗布し、さらに加熱することによって形成される。
この塗布操作においては、スピンコート法、キャスト法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ディップコート法、スプレーコート法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、及びインクジェットプリント法等の公知の塗布法を適用することができる。
<Anode buffer layer>
The anode buffer layer is formed by applying an anode buffer layer material on the anode and further heating.
In this coating operation, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, In addition, a known coating method such as an ink jet printing method can be applied.
また、陽極バッファ層用材料には、活性層形成の際に陽極バッファ層が溶解するのを防ぐ観点から、通常は、有機溶剤に対する耐性の高い材料が用いられる。
陽極バッファ層の厚さは、バッファ層としての効果を充分に発揮させ、また、太陽電池素子の駆動電圧の上昇を防ぐ観点から、通常5〜50nm、好ましくは10〜30nmである。
Further, as the material for the anode buffer layer, a material having high resistance to an organic solvent is usually used from the viewpoint of preventing the anode buffer layer from being dissolved during the formation of the active layer.
The thickness of the anode buffer layer is usually 5 to 50 nm, preferably 10 to 30 nm, from the viewpoint of sufficiently exhibiting the effect as the buffer layer and preventing an increase in the driving voltage of the solar cell element.
<活性層、正孔輸送層、電子輸送層>
太陽電池素子における活性層は、活性層、正孔輸送層、及び電子輸送層で構成される。
前記活性層には、上記一般式(1)で表されるスクアリリウム誘導体が用いられる。前記スクアリリウム誘導体は、通常アクセプター材料を混合して用いられる。前記スクアリリウム誘導体をドナー材料とし、アクセプター材料とともに、活性層4を形成することにより、高効率の有機薄膜太陽電池を提供することができる。
前記アクセプター材料には、公知の材料が適宜選択して用いられるが、電子輸送性があり、HOMOのエネルギー準位が深い化合物が好ましく、具体的には、フラーレン(C60、C70等)又はその誘導体(PC71BM等)体が好適に用いられる。
<Active layer, hole transport layer, electron transport layer>
The active layer in the solar cell element includes an active layer, a hole transport layer, and an electron transport layer.
The squarylium derivative represented by the general formula (1) is used for the active layer. The squarylium derivative is usually used in combination with an acceptor material. By using the squarylium derivative as a donor material and forming the active layer 4 together with an acceptor material, a highly efficient organic thin-film solar cell can be provided.
As the acceptor material, a known material is appropriately selected and used, but a compound having an electron transporting property and a deep HOMO energy level is preferable. Specifically, fullerene (C60, C70, etc.) or a derivative thereof. (PC 71 BM etc.) is preferably used.
前記活性層は、活性層のキャリア輸送性を補う目的で、図1に示すように、正孔輸送層と電子輸送層との間に挿入してもよいし、活性層中に、前記アクセプター材料とともに、正孔輸送性化合物や電子輸送性化合物を分散させて用いてもよい。 The active layer may be inserted between the hole transport layer and the electron transport layer as shown in FIG. 1 for the purpose of supplementing the carrier transport property of the active layer, and the acceptor material may be inserted in the active layer. In addition, a hole transporting compound or an electron transporting compound may be dispersed and used.
正孔輸送性化合物としては、例えば、酸化モリブデン(VI)(MoO3)、酸化バナジウム(V2O5)、酸化タングステン(WO3)、及び酸化ルテニウム(RuO2)等の金属酸化物;ヘキサアザトリフェニレンヘキサカルボニル(HATCN)、及び2,3,5,6−テトラフルオロ−7,7,8,8−テトラシアノ−キノジメタン(F4TCNQ)等の低分子材料;並びに該低分子材料に重合性官能基を導入して高分子化したもの等が挙げられる。 Examples of the hole transporting compound include metal oxides such as molybdenum oxide (VI) (MoO 3 ), vanadium oxide (V 2 O 5 ), tungsten oxide (WO 3 ), and ruthenium oxide (RuO 2 ); Low molecular weight materials such as azatriphenylene hexacarbonyl (HATCN) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ); and polymerizable functional groups in the low molecular weight material And the like which are polymerized by introducing.
電子輸送性化合物としては、例えば、BCP(2,9−ジメチル−4,7−ジフェニル−1,10−フェナントロリン)等のフェナントロリン誘導体;B4PyMPM(ビス−3,6−(3,5−ジ−4−ピリジルフェニル)−2−メチルピリミジン)等のオリゴピリジン誘導体;[60]フラーレン、及び[70]フラーレン等のナノカーボン誘導体等の低分子材料;並びに該低分子材料に重合性官能基を導入して高分子化したもの等が挙げられる。 Examples of the electron transporting compound include phenanthroline derivatives such as BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); B4PyMPM (bis-3,6- (3,5-di-4) Oligopyridine derivatives such as -pyridylphenyl) -2-methylpyrimidine); low molecular materials such as [60] fullerene and nanocarbon derivatives such as [70] fullerene; and a polymerizable functional group introduced into the low molecular material. And polymerized.
<正孔ブロック層>
正孔が活性層を通過するのを抑え、活性層内で電子と効率よく再結合させる目的で、活性層の陰極側に隣接して正孔ブロック層を設けてもよい。この正孔ブロック層には、活性化合物よりHOMO準位の深い化合物が用いられ、例えば、トリアゾール誘導体、オキサジアゾール誘導体、フェナントロリン誘導体、アルミニウム錯体等が用いられる。
<Hole blocking layer>
A hole blocking layer may be provided adjacent to the cathode side of the active layer for the purpose of suppressing the passage of holes through the active layer and efficiently recombining with electrons in the active layer. For the hole blocking layer, a compound having a deeper HOMO level than the active compound is used. For example, a triazole derivative, an oxadiazole derivative, a phenanthroline derivative, an aluminum complex, or the like is used.
さらに、励起子(エキシトン)が陰極金属で失活することを防ぐ目的で、活性層の陰極側に隣接してエキシトンブロック層を設けてもよい。このエキシトンブロック層には、活性化合物よりも、三重項励起エネルギーの大きな化合物が用いられ、該化合物としては、トリアゾール誘導体、フェナントロリン誘導体、アルミニウム錯体等が用いられる。 Furthermore, an exciton block layer may be provided adjacent to the cathode side of the active layer in order to prevent excitons (excitons) from being deactivated by the cathode metal. In this exciton block layer, a compound having a triplet excitation energy larger than that of the active compound is used. As the compound, a triazole derivative, a phenanthroline derivative, an aluminum complex, or the like is used.
<陰極>
陰極材料としては、仕事関数が低く(4eV以下)、かつ、化学的に安定なものが使用される。具体的には、Alや、MgAg、AlLi、又はAlCa等の合金の既知の陰極材料が挙げられる。これらの陰極材料の成膜方法としては、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、及びイオンプレーティング法等が用いられる。陰極の厚さは、通常10nm〜1μmであり、好ましくは50〜500nmである。
<Cathode>
As the cathode material, a material having a low work function (4 eV or less) and chemically stable is used. Specifically, a known cathode material of an alloy such as Al, MgAg, AlLi, or AlCa can be used. As a film forming method of these cathode materials, a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, an ion plating method, or the like is used. The thickness of the cathode is usually 10 nm to 1 μm, preferably 50 to 500 nm.
また、陰極から活性層への電子注入障壁を下げて電子の注入効率を上げる目的で、陰極より仕事関数の低い金属層を、陰極バッファ層として、陰極と該陰極に隣接する層の間に挿入してもよい。このような目的に使用できる低仕事関数の金属としては、アルカリ金属、アルカリ土類金属、希土類金属等が挙げられる。また、陰極より仕事関数の低いものであれば、合金又は金属化合物も使用することができる。これらの陰極バッファ層の成膜方法としては、蒸着法やスパッタ法等を用いることができる。陰極バッファ層の厚さは、通常0.05〜50nmであり、好ましくは0.1〜20nmである。 In addition, a metal layer having a lower work function than the cathode is inserted as a cathode buffer layer between the cathode and the layer adjacent to the cathode in order to lower the electron injection barrier from the cathode to the active layer and increase the efficiency of electron injection. May be. Examples of low work function metals that can be used for such purposes include alkali metals, alkaline earth metals, and rare earth metals. Moreover, an alloy or a metal compound can also be used if it has a work function lower than that of the cathode. As a method for forming these cathode buffer layers, vapor deposition, sputtering, or the like can be used. The thickness of the cathode buffer layer is usually 0.05 to 50 nm, preferably 0.1 to 20 nm.
さらに、陰極バッファ層は、上記の低仕事関数の金属等と電子輸送性化合物との混合物として形成させることもできる。この場合の成膜方法としては共蒸着法を用いることができる。また、溶液による塗布成膜が可能な場合は、スピンコート法、スプレーコート法、ディップコート法、及び印刷法(インクジェットプリント法、ディスペンサー塗布法)等の成膜方法を用いることができる。この場合の陰極バッファ層の厚さは、通常は0.1〜100nmであり、好ましくは0.5〜50nmである。陰極と有機物層との間に、導電性高分子からなる層、或いは、金属酸化物や金属フッ化物、有機絶縁材料等からなる平均膜厚2nm以下の層を設けてもよい。 Further, the cathode buffer layer can be formed as a mixture of the above-described low work function metal or the like and an electron transporting compound. In this case, a co-evaporation method can be used as a film forming method. In addition, in the case where coating film formation using a solution is possible, film formation methods such as a spin coating method, a spray coating method, a dip coating method, and a printing method (inkjet printing method, dispenser coating method) can be used. In this case, the thickness of the cathode buffer layer is usually 0.1 to 100 nm, preferably 0.5 to 50 nm. A layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like with an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer.
<基板>
前記素子を構成する基板には、太陽電池素子に要求される機械的強度を満たす材料が用いられる。
ボトムエミッション型の太陽電池素子には、可視光線に対して透明な基板が用いられ、例えば、ソーダガラス、及び無アルカリガラス等のガラス;アクリル樹脂、メタクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂、及びナイロン樹脂等の透明プラスチック;並びにシリコンからなる基板等が使用できる。
<Board>
A material that satisfies the mechanical strength required for the solar cell element is used for the substrate constituting the element.
For the bottom emission type solar cell element, a substrate transparent to visible light is used, for example, glass such as soda glass and non-alkali glass; acrylic resin, methacrylic resin, polycarbonate resin, polyester resin, and nylon resin. A transparent plastic such as silicon, and a substrate made of silicon can be used.
トップエミッション型の太陽電池素子には、ボトムエミッション型の太陽電池素子に用いられる基板に加えて、ステンレスや、銅、銀、金、白金、タングステン、チタン、タンタル若しくはニオブの単体又はこれらの合金からなる基板等が使用できる。
基板の厚さは、要求される機械的強度にもよるが、通常0.1〜10mm、好ましくは0.25〜2mmである。
なお、各層の膜厚は、概ね5nm〜5μmの範囲内である。
The top emission type solar cell element includes, in addition to the substrate used for the bottom emission type solar cell element, stainless steel, copper, silver, gold, platinum, tungsten, titanium, tantalum, niobium, or an alloy thereof. Can be used.
Although the thickness of a board | substrate is based also on the mechanical strength requested | required, it is 0.1-10 mm normally, Preferably it is 0.25-2 mm.
In addition, the film thickness of each layer is in the range of approximately 5 nm to 5 μm.
(太陽電池素子の形成方法)
上記の活性層は、例えば、蒸着法(抵抗加熱蒸着法、電子ビーム蒸着法等)、スパッタリング法等のドライプロセス、又は塗布法(スピンコート法、キャスティング法、ダイコート法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイアーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、インクジェットプリント法等)等のウェットプロセスにより形成することができる。これらの方法のうち、スピンコート法、ダイコート法、及びスプレーコート法が好ましく用いられる。
(Method for forming solar cell element)
The active layer is formed by, for example, a vapor deposition method (resistance heating vapor deposition method, electron beam vapor deposition method, etc.), a dry process such as a sputtering method, or a coating method (spin coating method, casting method, die coating method, micro gravure coating method, gravure method). It can be formed by wet processes such as coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, etc. it can. Of these methods, spin coating, die coating, and spray coating are preferably used.
なお、太陽電池素子を長期間、安定的に用いるために、その周囲に保護層及び/又は保護カバーを装着することが好ましい。前記保護層には、高分子化合物、金属酸化物、金属フッ化物、及び金属ホウ化物等が用いられる。前記保護カバーには、ガラス板、表面に低透水化処理を施したプラスチック板、及び金属等が用いられ、該カバーを熱硬化性樹脂や光硬化性樹脂で素子基板と貼り合わせて密閉する方法が好適に用いられる。さらに、前記空間に窒素やアルゴンのような不活性ガスを封入すれば、陰極の酸化を防止することができ、酸化バリウム等の乾燥剤を空間内に入れれば、製造工程で吸着した水分が太陽電池素子にタメージを与えるのを抑制できる。 In addition, in order to use a solar cell element stably for a long period of time, it is preferable to attach a protective layer and / or a protective cover around it. For the protective layer, a polymer compound, a metal oxide, a metal fluoride, a metal boride, or the like is used. The protective cover is made of a glass plate, a plastic plate having a low water permeability treatment on the surface, a metal, or the like, and the cover is bonded to the element substrate with a thermosetting resin or a photocurable resin and sealed. Are preferably used. Furthermore, if an inert gas such as nitrogen or argon is sealed in the space, oxidation of the cathode can be prevented, and if a desiccant such as barium oxide is placed in the space, moisture adsorbed in the manufacturing process is absorbed by the sun. The battery element can be prevented from being damaged.
[用途]
本発明の有機薄膜太陽電池は、マトリックス方式またはセグメント方式による画素として画像表示装置に好適に用いられる。また、上記有機薄膜太陽電池は、画素を形成せずに、面発光光源としても好適に用いられる。
[Usage]
The organic thin film solar cell of the present invention is suitably used for an image display device as a pixel by a matrix method or a segment method. Moreover, the said organic thin film solar cell is used suitably also as a surface emitting light source, without forming a pixel.
本発明の有機薄膜太陽電池は、具体的には、コンピュータ、テレビ、携帯端末、携帯電話、カーナビゲーション、標識、看板、ビデオカメラのビューファインダー等における表示装置、バックライト、電子写真、照明、レジスト露光、読み取り装置、インテリア照明、光通信システム等における光照射装置に好適に用いられる。 Specifically, the organic thin film solar cell of the present invention includes a display device, backlight, electrophotography, illumination, resist, etc. for computers, televisions, portable terminals, cellular phones, car navigation systems, signs, signboards, video camera viewfinders, etc. It is suitably used for a light irradiation device in exposure, reading device, interior lighting, optical communication system and the like.
以下、本発明を実施例に基づいてさらに具体的に説明するが、本発明は下記実施例により制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not restrict | limited by the following Example.
[BDT−ASQ及びD−BDT−ASQの合成]
BDT−ASQ及びD−BDT−ASQを下記のスキームに従って合成した。
[Synthesis of BDT-ASQ and D-BDT-ASQ]
BDT-ASQ and D-BDT-ASQ were synthesized according to the following scheme.
[合成例1]化合物1a及び1bの合成
3−((5−ブロモ−1−ブチル−3,3−ジメチルインドリン−2−イリデン)メチル)4−エトキシシクロブタ−3−エン−1,2−ジオン(2.40g、5.75mmol)及び4,8−ビス[5−(2−エチルヘキシル)チオフェン−2−イル]−2,6−ビス(トリメチルスタニル)ベンゾ[1,2−b:4,5−b’]ジチオフェン(2.00g、2.21mmol)を200mLのトルエンに溶解させ、30分間窒素で脱気した。次いで、Pd(PPh3)4 660mgを窒素下に添加し、混合物を36時間加熱還流した。溶媒を除去した後、粗生成物をシリカゲルカラムクロマトグラフィーで精製し(溶離液;ジクロロメタン/酢酸エチル=30:1)、黄色固体の化合物1aを0.80g(収率29%)、化合物1bを1.02g(収率36%)得た。
Synthesis Example 1 Synthesis of Compounds 1a and 1b 3-((5-Bromo-1-butyl-3,3-dimethylindoline-2-ylidene) methyl) 4-ethoxycyclobut-3-ene-1,2- Dione (2.40 g, 5.75 mmol) and 4,8-bis [5- (2-ethylhexyl) thiophen-2-yl] -2,6-bis (trimethylstannyl) benzo [1,2-b: 4 , 5-b ′] dithiophene (2.00 g, 2.21 mmol) was dissolved in 200 mL of toluene and degassed with nitrogen for 30 minutes. Then 660 mg of Pd (PPh 3 ) 4 was added under nitrogen and the mixture was heated to reflux for 36 hours. After removing the solvent, the crude product was purified by silica gel column chromatography (eluent; dichloromethane / ethyl acetate = 30: 1), 0.80 g (yield 29%) of Compound 1a as a yellow solid, and Compound 1b 1.02 g (yield 36%) was obtained.
化合物1a及び1bの1H NMRの測定結果を以下に示す。
化合物1a;3−((5−(4,8−ビス(5−(2−エチルヘキシル)チオフェン−2−イル)ベンゾ[1,2−b:4,5−b’]ジチオフェン−2−イル)−1−ブチル−3,3−ジメチルインドリン−2−イリデン)メチル)−4−エトキシシクトブタ−3−エン−1,2−ジオン
1H NMR(400 MHz, THF-d8, ppm) δ: 7.86 (s, 1H, ArH), 7.81 (s, 1H, ArH), 7.73 (d, 3H, J=8.0 HZ, ArH), 7.65 (d, 1H, J=8.4 HZ, ArH), 7.40-7.29 (m, 5H, ArH), 7.04 (d, 1H, J=8.4 HZ, ArH), 7.00 (d, 2H, J=3.2 HZ, ArH), 5.46 (s, 1H, =CH-), 4.86 (q, 2H, J=7.2 HZ, -OCH2-), 3.93 (t, 2H, J=7.2 HZ, -NCH2-), 2.94 (d, 4H, J=6.8 HZ, -CH2-),1.78-1.72 (m, 2H, -CH2-), 1.66 (s, 6H, -CH3), 1.52-1.35 (m, 23H, -CH2-, -CH3), 1.00-0.92 (m, 15H, -CH3)
化合物1b;4,4’−(5,5’−(4,8−ビス(5−(2−エチルヘキシル)チオフェン−2−イル)ベンゾ[1,2−b:4,5−b’]ジチオフェン−2,6−ジイル)ビス(1−ブチル−3,3−ジメチルインドリン−5−イル−2−イリデン))ビス(メタニルイリデン))ビス(3−エトキシシクロブタ−3−エン−1,2−ジオン)
1H NMR(400 MHz, THF-d8, ppm) δ: 7.79 (s, 2H, ArH), 7.70 (s, 2H, ArH), 7.64 (d, 2H, J=8.4 HZ, ArH), 7.38 (d, 2H, J=3.2 HZ, ArH), 7.04 (d, 2H, J=8.4 HZ, ArH), 7.00 (d,2H, J=3.2 HZ, ArH), 5.46 (s, 2H, =CH-), 4.87 (q, 4H, J=7.2 HZ, -OCH2-), 3.93 (t, 4H, J=7.6 HZ, -NCH2-), 2.94 (d, 4H, J=6.4 HZ, -CH2-), 1.76-1.67(m, 4H, -CH2-), 1.66 (s, 12H, -CH3), 1.50-1.39 (m, 28H, -CH2-, -CH3), 1.01-0.93 (m, 18H, -CH3).
The measurement results of 1 H NMR of compounds 1a and 1b are shown below.
Compound 1a; 3-((5- (4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b ′] dithiophen-2-yl) -1-butyl-3,3-dimethylindoline-2-ylidene) methyl) -4-ethoxyoctbut-3-ene-1,2-dione
1 H NMR (400 MHz, THF-d8, ppm) δ: 7.86 (s, 1H, ArH), 7.81 (s, 1H, ArH), 7.73 (d, 3H, J = 8.0 HZ, ArH), 7.65 (d , 1H, J = 8.4 HZ, ArH), 7.40-7.29 (m, 5H, ArH), 7.04 (d, 1H, J = 8.4 HZ, ArH), 7.00 (d, 2H, J = 3.2 HZ, ArH), 5.46 (s, 1H, = CH-), 4.86 (q, 2H, J = 7.2 HZ, -OCH 2- ), 3.93 (t, 2H, J = 7.2 HZ, -NCH 2- ), 2.94 (d, 4H , J = 6.8 HZ, -CH 2- ), 1.78-1.72 (m, 2H, -CH 2- ), 1.66 (s, 6H, -CH 3 ), 1.52-1.35 (m, 23H, -CH 2- , -CH 3 ), 1.00-0.92 (m, 15H, -CH 3 )
Compound 1b; 4,4 ′-(5,5 ′-(4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b ′] dithiophene -2,6-diyl) bis (1-butyl-3,3-dimethylindoline-5-yl-2-ylidene)) bis (methanylylidene)) bis (3-ethoxycyclobut-3-ene-1,2- Zeon)
1 H NMR (400 MHz, THF-d8, ppm) δ: 7.79 (s, 2H, ArH), 7.70 (s, 2H, ArH), 7.64 (d, 2H, J = 8.4 HZ, ArH), 7.38 (d , 2H, J = 3.2 HZ, ArH), 7.04 (d, 2H, J = 8.4 HZ, ArH), 7.00 (d, 2H, J = 3.2 HZ, ArH), 5.46 (s, 2H, = CH-), 4.87 (q, 4H, J = 7.2 HZ, -OCH 2- ), 3.93 (t, 4H, J = 7.6 HZ, -NCH 2- ), 2.94 (d, 4H, J = 6.4 HZ, -CH 2- ) , 1.76-1.67 (m, 4H, -CH 2- ), 1.66 (s, 12H, -CH 3 ), 1.50-1.39 (m, 28H, -CH 2- , -CH 3 ), 1.01-0.93 (m, 18H, -CH 3 ).
[合成例2]化合物2aの合成
化合物1a(0.80g、0.81mmol)を80mLのアセトンに溶解させ、30分間加熱還流した。この溶液中に、6M塩酸を8mL滴下し、さらに5時間加熱還流した。次いで、200mLの脱イオン水を滴下すると、反応混合物中に黄色固体が沈殿した。この混合物をろ過し、生成物を脱イオン水で精製し、化合物2aを0.64g(収率82%)を得た。
[Synthesis Example 2] Synthesis of Compound 2a Compound 1a (0.80 g, 0.81 mmol) was dissolved in 80 mL of acetone and heated to reflux for 30 minutes. To this solution, 8 mL of 6M hydrochloric acid was added dropwise, and the mixture was further heated to reflux for 5 hours. Then 200 mL of deionized water was added dropwise and a yellow solid precipitated in the reaction mixture. This mixture was filtered, and the product was purified with deionized water to obtain 0.64 g (yield 82%) of compound 2a.
化合物2aの1H NMRの測定結果を以下に示す。
化合物2a;3−((5−(4,8−ビス(5−(2−エチルヘキシル)チオフェン−2−イル)ベンゾ[1,2−b:4,5−b’]ジチオフェン−2−イル)−1−ブチル−3,3−ジメチルインドリン−2−イリデン)メチル)−4−ヒドロキシシクロブタ−3−エン−1,2−ジオン
1H NMR(400 MHz, THF-d8, ppm) δ: 7.86 (s, 1H, ArH), 7.80 (s, 1H, ArH), 7.73 (d, 3H, J=8.0 HZ, ArH), 7.64 (d, 1H, J=8.4 HZ, ArH), 7.40-7.28 (m, 5H, ArH), 7.01-6.99 (m, 3H, ArH), 5.55 (s, 1H, =CH-), 3.91 (t, 2H, J=7.2 HZ, -NCH2-), 2.94(d, 4H, J=6.8 HZ, -CH2-),1.77-1.72 (m, 2H, -CH2-), 1.67(s, 6H, -CH3), 1.53-1.35 (m, 20H, -CH2-), 1.00-0.92 (m, 15H, -CH3).
The measurement result of 1 H NMR of compound 2a is shown below.
Compound 2a; 3-((5- (4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b ′] dithiophen-2-yl) -1-butyl-3,3-dimethylindoline-2-ylidene) methyl) -4-hydroxycyclobut-3-ene-1,2-dione
1 H NMR (400 MHz, THF-d8, ppm) δ: 7.86 (s, 1H, ArH), 7.80 (s, 1H, ArH), 7.73 (d, 3H, J = 8.0 HZ, ArH), 7.64 (d , 1H, J = 8.4 HZ, ArH), 7.40-7.28 (m, 5H, ArH), 7.01-6.99 (m, 3H, ArH), 5.55 (s, 1H, = CH-), 3.91 (t, 2H, J = 7.2 HZ, -NCH 2- ), 2.94 (d, 4H, J = 6.8 HZ, -CH 2- ), 1.77-1.72 (m, 2H, -CH 2- ), 1.67 (s, 6H, -CH 3 ), 1.53-1.35 (m, 20H, -CH 2- ), 1.00-0.92 (m, 15H, -CH 3 ).
[合成例3]化合物2bの合成
化合物1b(0.90g、0.72mmol)を、アセトン60mL及びTHF110mLの混合溶媒に溶解させ、30分間加熱還流した。この溶液中に、6M 塩酸アセトン溶液を20mL滴下し、3時間加熱還流した。次いで、600mLの脱イオン水を滴下すると、反応混合物中に橙色固体が沈殿した。この混合物をろ過し、生成物を脱イオン水で精製し、化合物2bを0.78g(収率91%)を得た。
[Synthesis Example 3] Synthesis of Compound 2b Compound 1b (0.90 g, 0.72 mmol) was dissolved in a mixed solvent of 60 mL of acetone and 110 mL of THF and heated to reflux for 30 minutes. Into this solution, 20 mL of 6M hydrochloric acid acetone solution was dropped and heated to reflux for 3 hours. Then 600 mL of deionized water was added dropwise and an orange solid precipitated in the reaction mixture. The mixture was filtered, and the product was purified with deionized water to obtain 0.78 g (yield 91%) of compound 2b.
化合物2bの1H NMRの測定結果を以下に示す。
化合物2b;4,4’−((5,5’−(4,8−ビス(5−(2−エチルヘキシル)チオフェン−2−イル)ベンゾ[1,2−b:4,5−b’]ジチオフェン−2,6−ジイル)ビス(1−ブチル−3,3−ジメチルインドリン−5−イル−2−イリデン))ビス(メタニルイリデン))ビス(3−ヒドロキシシクロブタ−3−エン−1,2−ジオン)
1H NMR(400 MHz, THF-d8, ppm) δ: 7.78 (s, 2H, ArH), 7.69 (s, 2H, ArH), 7.63 (d, 2H, J=8.4 HZ, ArH), 7.38 (d, 2H, J=3.6 HZ, ArH), 7.02-7.00 (m, 4H, ArH), 5.55 (s, 2H, =CH-), 3.92 (t, 4H, J=6.8 HZ, -NCH2-), 2.94 (d, 4H, J=6.4 HZ, -CH2-), 1.77-1.70(m, 4H, -CH2-), 1.67 (s, 12H, -CH3), 1.55-1.35 (m, 22H,-CH2-), 1.01-0.93 (m, 18H, -CH3).
The measurement result of 1 H NMR of compound 2b is shown below.
Compound 2b; 4,4 ′-((5,5 ′-(4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b ′] Dithiophene-2,6-diyl) bis (1-butyl-3,3-dimethylindoline-5-yl-2-ylidene)) bis (methanylylidene)) bis (3-hydroxycyclobut-3-ene-1,2 -Dione)
1 H NMR (400 MHz, THF-d8, ppm) δ: 7.78 (s, 2H, ArH), 7.69 (s, 2H, ArH), 7.63 (d, 2H, J = 8.4 HZ, ArH), 7.38 (d , 2H, J = 3.6 HZ, ArH), 7.02-7.00 (m, 4H, ArH), 5.55 (s, 2H, = CH-), 3.92 (t, 4H, J = 6.8 HZ, -NCH 2- ), 2.94 (d, 4H, J = 6.4 HZ, -CH 2- ), 1.77-1.70 (m, 4H, -CH 2- ), 1.67 (s, 12H, -CH 3 ), 1.55-1.35 (m, 22H, -CH 2- ), 1.01-0.93 (m, 18H, -CH 3 ).
[実施例1]BDT−ASQの合成
化合物2a(0.50g、0.52mmol)及び5−(1,3,3a,8b−テトラヒドロシクロペンタ[b]インドール−4(2H)−イル)ベンゼン−1,3−ジオール(0.20g、0.73 mmol)を、トルエン50mL及びn−ブタノール50mLの混合溶媒に溶解させ、窒素で30分間脱気した。次いで、溶液を140℃で36時間加熱した。粗生成物をシリカゲルカラムクロマトグラフィーで精製し(溶離液;ジクロロメタン/酢酸エチル=10:1)、暗赤色固体を得た。ジクロロメタン及びメタノール4:1(体積比)の溶媒で再結晶して、暗赤色固体0.44gを得た(収率70%)。
Example 1 Synthesis of BDT-ASQ Compound 2a (0.50 g, 0.52 mmol) and 5- (1,3,3a, 8b-tetrahydrocyclopenta [b] indole-4 (2H) -yl)
BDT−ASQの融点(mp)、1H NMR(図2(a))、13C NMR(図2(b))、純度(purity)及びHR−MS(高分解能質量スペクトル)の測定結果を示す。
BDT−ASQ;4−((5−(4,8−ビス(5−(2−エチルヘキシル)チオフェン−2−イル)ベンゾ[1,2−b:4,5−b’]ジチオフェン−2−イル)−1−ブチル−3,3−ジメチル−3H−インドール−1−イウム−2−イル)メチレン)−2−(2,6−ジヒドロキシ−4−(1,3,3a,8b−テトラヒドロシクロペンタ[b]インドール−4(2H)−イル)フェニル)−3−オキソシクロブタ−1−エノレート
mp:206-207℃;
1H NMR (400 MHz, CDCl3, ppm):δ:12.40 (s, 2H, -OH), 7.84(d, 2H, J=1.6 HZ, ArH), 7.72-7.66 (m, 4H, ArH), 7.43-7.33 (m, 6H, ArH), 7.19-7.15 (m, 2H, ArH), 7.06 (d, 1H, J=8.0 HZ, ArH), 6.97-6.93 (m, 3H, ArH), 6.35 (s, 2H, ArH), 5.90 (s, 1H, =CH-), 4.70 (t, 1H, J=8.0, 2.8 HZ, -NCH-), 4.04(t, 2H, J=7.2 HZ, -NCH2-), 3.92 (t, 1H, J=8.0 HZ, -CH-), 2.93 (d, 4H, J=6.4 HZ, -CH2-), 2.09-1.91 (m, 4H, -CH2-), 1.84-1.64(m, 11H, -CH2-, -CH3), 1.51-1.36 (m, 19H, -CH2-), 1.02-0.93 (m, 15H, -CH3);
13C NMR (100 MHz, CDCl3, ppm):δ: 172.6, 170.9, 169.5, 163.1, 152.9, 146.1, 145.0, 143.9, 143.5, 143.3, 141.7, 139.0, 138.7, 137.7, 137.4, 137.0, 136.9, 134.1, 131.7, 128.9, 128.5, 127.9, 127.8, 127.4, 126.6, 126.4, 125.6, 125.5, 124.9, 123.7, 123.6, 122.5, 120.3, 119.1, 118.9, 113.8, 110.7, 105.0, 96.7, 88.0, 68.7, 50.1, 45.5, 44.2, 41.5, 34.6, 34.3, 33.7, 32.5, 29.4, 28.9, 26.8, 25.8, 24.3, 23.1, 20.3, 14.2, 13.8, 11.0;
purity:100% (HPLC, 溶離液: THF/H2O=83:17);
HR-MS(ESI): m/z [M+H]+ calcd. for C76H81N2O4S4,1213.5079; found,1213.5074;
元素分析:calcd. for C76H80N2O4S4: C75.21, H 6.64, N 2.31, S 10.57; found, C 75.28, H 6.93, N 2.26, S 10.75.
図4にBDT−ASQの熱重量測定(TGA)の結果を示す。BDT−ASQは、高い熱安定性を有することがわかる。
The measurement results of melting point (mp), 1 H NMR (FIG. 2 (a)), 13 C NMR (FIG. 2 (b)), purity (purity) and HR-MS (high resolution mass spectrum) of BDT-ASQ are shown. .
BDT-ASQ; 4-((5- (4,8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5-b ′] dithiophen-2-yl ) -1-Butyl-3,3-dimethyl-3H-indol-1-ium-2-yl) methylene) -2- (2,6-dihydroxy-4- (1,3,3a, 8b-tetrahydrocyclopenta) [B] Indol-4 (2H) -yl) phenyl) -3-oxocyclobut-1-enolate
mp: 206-207 ° C;
1 H NMR (400 MHz, CDCl 3 , ppm): δ: 12.40 (s, 2H, -OH), 7.84 (d, 2H, J = 1.6 HZ, ArH), 7.72-7.66 (m, 4H, ArH), 7.43-7.33 (m, 6H, ArH), 7.19-7.15 (m, 2H, ArH), 7.06 (d, 1H, J = 8.0 HZ, ArH), 6.97-6.93 (m, 3H, ArH), 6.35 (s , 2H, ArH), 5.90 (s, 1H, = CH-), 4.70 (t, 1H, J = 8.0, 2.8 HZ, -NCH-), 4.04 (t, 2H, J = 7.2 HZ, -NCH 2- ), 3.92 (t, 1H, J = 8.0 HZ, -CH-), 2.93 (d, 4H, J = 6.4 HZ, -CH 2- ), 2.09-1.91 (m, 4H, -CH 2- ), 1.84 -1.64 (m, 11H, -CH 2- , -CH 3 ), 1.51-1.36 (m, 19H, -CH 2- ), 1.02-0.93 (m, 15H, -CH 3 );
13 C NMR (100 MHz, CDCl 3 , ppm): δ: 172.6, 170.9, 169.5, 163.1, 152.9, 146.1, 145.0, 143.9, 143.5, 143.3, 141.7, 139.0, 138.7, 137.7, 137.4, 137.0, 136.9, 134.1 , 131.7, 128.9, 128.5, 127.9, 127.8, 127.4, 126.6, 126.4, 125.6, 125.5, 124.9, 123.7, 123.6, 122.5, 120.3, 119.1, 118.9, 113.8, 110.7, 105.0, 96.7, 88.0, 68.7, 50.1, 45.5 , 44.2, 41.5, 34.6, 34.3, 33.7, 32.5, 29.4, 28.9, 26.8, 25.8, 24.3, 23.1, 20.3, 14.2, 13.8, 11.0;
purity: 100% (HPLC, eluent: THF / H 2 O = 83: 17);
HR-MS (ESI): m / z [M + H] + calcd. For C 76 H 81 N 2 O 4 S 4 , 1213.5079; found, 1213.5074;
Elemental analysis: calcd. For C 76 H 80 N 2 O 4 S 4 : C75.21, H 6.64, N 2.31, S 10.57; found, C 75.28, H 6.93, N 2.26, S 10.75.
FIG. 4 shows the results of thermogravimetry (TGA) of BDT-ASQ. It can be seen that BDT-ASQ has high thermal stability.
[実施例2]D−BDT−ASQの合成
化合物2b(0.51g、0.43mmol)及び5−(1,3,3a,8b−テトラヒドロシクロペンタ[b]インドール−4(2H)−イル)ベンゼン−1,3−ジオール(0.30g、1.12mmol)をトルエン60mL及びn−ブタノール60mLに溶解させ、窒素で30分間脱気した後、140℃で36時間加熱した。反応を終了して冷却した後、メタノール120mLを滴下して、暗赤色固体を得た。この暗赤色固体をろ別し、シリカゲルカラムクロマトグラフィーで精製した(溶離液、ジクロロメタン/酢酸エチル=100:1)。得られた暗赤色固体をジクロロメタン及びヘキサンの混合溶媒(ジクロロメタン:ヘキサン=10:1)で再結晶を行い、黒色固体を得た(0.54g、収率75%)。
Example 2 Synthesis of D-BDT-ASQ Compound 2b (0.51 g, 0.43 mmol) and 5- (1,3,3a, 8b-tetrahydrocyclopenta [b] indol-4 (2H) -yl) Benzene-1,3-diol (0.30 g, 1.12 mmol) was dissolved in 60 mL of toluene and 60 mL of n-butanol, degassed with nitrogen for 30 minutes, and then heated at 140 ° C. for 36 hours. After finishing the reaction and cooling, 120 mL of methanol was added dropwise to obtain a dark red solid. The dark red solid was filtered off and purified by silica gel column chromatography (eluent, dichloromethane / ethyl acetate = 100: 1). The obtained dark red solid was recrystallized with a mixed solvent of dichloromethane and hexane (dichloromethane: hexane = 10: 1) to obtain a black solid (0.54 g, yield 75%).
D−BDT−ASQの融点(mp)、1H NMR(図3(a))、13C NMR(図3(b))、純度(purity)及びHR−MS(高分解能質量スペクトル)の測定結果を示す。
D−BDT−ASQ;4,4’−((5,5’−(4,8’−ビス(5−(2−エチルヘキシル)チオフェン−2−イル)ベンゾ[1,2−b:4,5−b’]ジチオフェン−2,6−ジイル)ビス(1−ブチル−3,3−ジメチル−3H−インドール−1−イウム−5,2−ジイル))ビス(メタニルイリデン))ビス(2−(2,6−ジヒドロキシ−4−(1,3,3a,8b−テトラヒドロシクロペンタ[b]インドール−4(2H)−イル)フェニル)−3−オキソシクロブタ−1−エノレート)
mp303-304 ℃;
1H NMR (400 MHz, CDCl3, ppm) δ:12.41 (s, 4H, -OH), 7.84(s, 2H, ArH), 7.71 (d, 2H, J=8.4 HZ, ArH), 7.66 (d, 2H, J=1.6 HZ, ArH), 7.39(t, 4H, J=4.0 HZ, ArH), 7.18 (t, 4H, J=6.0 HZ, ArH), 7.09 (d, 2H, J=8.4 HZ, ArH), 6.99 (d, 2H, J=3.2 HZ, ArH), 6.97 (t, 2H, J=7.6 HZ, ArH), 6.34 (s, 4H, ArH), 5.91 (s, 2H, =CH-), 4.70 (t, 2H, J=8.0, 2.8 HZ, -NCH-), 4.08 (t, 4H, J=7.2 HZ, -NCH2-), 3.92 (t, 2H, J=7.6 HZ, -CH-), 2.94 (d, 4H, J=6.8 HZ,-CH2-), 2.11-1.90 (m, 10H, -CH2-), 1.85-1.64 (m, 20H, -CH2-,-CH3), 1.53-1.36 (m, 20H, -CH2-), 1.03-0.93 (m, 18H, -CH3);
13C NMR (100 MHz, CDCl3, ppm) δ: 172.5, 171.1, 169.4, 163.1, 153.0, 146.2, 143.9, 143.8, 143.3, 141.8, 138.9, 137.6, 137.0, 136.8, 131.6, 127.9, 127.4, 126.7, 125.6, 124.9, 123.7, 122.6, 120.3, 119.1, 113.8, 110.7, 105.0, 96.7, 88.0, 68.7, 50.1, 45.5, 44.2, 41.5, 34.6, 34.3, 33.7, 32.5, 29.4, 28.9, 26.8, 25.8, 24.3, 23.1, 20.3, 14.2, 13.8, 11.0;
purity:100% (HPLC, eluent: THF/H2O=83:17);
HR-MS(ESI): m/z [M+2H]+ calcd. for C106H112N4O8S4, 1697.7397; found,1697.7400;
elemental anal. Calcd. for C106H110N4O8S4: C 75.05, H 6.54, N 3.30, S 7.56; found, C 75.08, H 6.84, N 3.25, S 7.50.
図4にD−BDT−ASQの熱重量測定(TGA)の結果を示す。D−BDT−ASQは、高い熱安定性を有することがわかる。
Measurement results of melting point (mp), 1 H NMR (FIG. 3 (a)), 13 C NMR (FIG. 3 (b)), purity (purity) and HR-MS (high resolution mass spectrum) of D-BDT-ASQ Indicates.
D-BDT-ASQ; 4,4 ′-((5,5 ′-(4,8′-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo [1,2-b: 4,5 -B '] dithiophene-2,6-diyl) bis (1-butyl-3,3-dimethyl-3H-indole-1-ium-5,2-diyl)) bis (methanylylidene)) bis (2- (2 , 6-Dihydroxy-4- (1,3,3a, 8b-tetrahydrocyclopenta [b] indole-4 (2H) -yl) phenyl) -3-oxocyclobut-1-enolate)
mp303-304 ℃;
1 H NMR (400 MHz, CDCl 3 , ppm) δ: 12.41 (s, 4H, -OH), 7.84 (s, 2H, ArH), 7.71 (d, 2H, J = 8.4 HZ, ArH), 7.66 (d , 2H, J = 1.6 HZ, ArH), 7.39 (t, 4H, J = 4.0 HZ, ArH), 7.18 (t, 4H, J = 6.0 HZ, ArH), 7.09 (d, 2H, J = 8.4 HZ, ArH), 6.99 (d, 2H, J = 3.2 HZ, ArH), 6.97 (t, 2H, J = 7.6 HZ, ArH), 6.34 (s, 4H, ArH), 5.91 (s, 2H, = CH-) , 4.70 (t, 2H, J = 8.0, 2.8 HZ, -NCH-), 4.08 (t, 4H, J = 7.2 HZ, -NCH 2- ), 3.92 (t, 2H, J = 7.6 HZ, -CH- ), 2.94 (d, 4H, J = 6.8 HZ, -CH 2- ), 2.11-1.90 (m, 10H, -CH 2- ), 1.85-1.64 (m, 20H, -CH 2- , -CH 3 ) , 1.53-1.36 (m, 20H, -CH 2- ), 1.03-0.93 (m, 18H, -CH 3 );
13 C NMR (100 MHz, CDCl 3 , ppm) δ: 172.5, 171.1, 169.4, 163.1, 153.0, 146.2, 143.9, 143.8, 143.3, 141.8, 138.9, 137.6, 137.0, 136.8, 131.6, 127.9, 127.4, 126.7, 125.6, 124.9, 123.7, 122.6, 120.3, 119.1, 113.8, 110.7, 105.0, 96.7, 88.0, 68.7, 50.1, 45.5, 44.2, 41.5, 34.6, 34.3, 33.7, 32.5, 29.4, 28.9, 26.8, 25.8, 24.3, 23.1, 20.3, 14.2, 13.8, 11.0;
purity: 100% (HPLC, eluent: THF / H 2 O = 83: 17);
HR-MS (ESI): m / z [M + 2H] + calcd.for C 106 H 112 N 4 O 8 S 4 , 1697.7397; found, 1697.7400;
elemental anal.Calcd.for C 106 H 110 N 4 O 8 S 4 : C 75.05, H 6.54, N 3.30, S 7.56; found, C 75.08, H 6.84, N 3.25, S 7.50.
FIG. 4 shows the results of thermogravimetry (TGA) of D-BDT-ASQ. It can be seen that D-BDT-ASQ has high thermal stability.
[比較例1]
比較例として、下記構造式を有するS−ASQを用いた。
As a comparative example, S-ASQ having the following structural formula was used.
[試験例1]光学的及び電気化学的評価
比較例1のS−ASQ、及び、実施例1〜2で得られたBDT−ASQ及びD−BDT−ASQをクロロホルムに溶解させ、3.00×10-6mol/L溶液を調製した。
S−ASQ、BDT−ASQ、及びD−BDT−ASQのそれぞれについて調製したクロロホルム溶液を、石英ガラスに入れて測定した場合(図5(a))、及びキャストフィルムにして測定した場合(図5(b))の紫外・可視・近赤外分光分析(UV−Vis−NIR)を行った。
Test Example 1 Optical and Electrochemical Evaluation S-ASQ of Comparative Example 1 and BDT-ASQ and D-BDT-ASQ obtained in Examples 1 and 2 were dissolved in chloroform, and 3.00 × A 10 −6 mol / L solution was prepared.
When the chloroform solutions prepared for each of S-ASQ, BDT-ASQ, and D-BDT-ASQ are measured by placing them in quartz glass (FIG. 5 (a)), and when measured as a cast film (FIG. 5). (B)) was subjected to ultraviolet-visible-near-infrared spectroscopic analysis (UV-Vis-NIR).
UV−Vis−NIR吸収スペクトルでは、キャストフィルムの場合(図5(b))、BDT−ASQ及びD−BDT−ASQはS−ASQに比べてそれぞれ34nm及び47nm長波長シフトしていた。具体的には、S−ASQ<BDT−ASQ<D−BDT−ASQの順に長波長化していた。ただし、そのエネルギー差はわずか0.03eV程度であった。
S−ASQ及びBDT−ASQは、表1に示すとおり、同等程度の高いモル吸光係数(〜2.0M-1cm-1)を示したが、D−BDT−ASQでは4.0M-1cm-1と、高い値を示した。
BDT−ASQ及びD−BDT−ASQのいずれも、溶液で測定した場合よりも、キャストフィルムで測定した場合のほうが、長波長シフトしており、かつ、ブロードな波形を示した。300〜450nmに観測される吸収帯は、BDTセグメントのπ−π*遷移によるものと考えられる。吸収スペクトルの開始位置(onset position)から、BDT−ASQ及びD−BDT−ASQの光学バンドギャップ(Eg opt)はそれぞれ、1.39eV及び1.36eVと見積もり、S−ASQよりも0.02eV及び0.05eV低いことがわかった。なお、D−BDT−ASQの光学バンドギャップ(Eg opt)1.36eVは、これまでに知られるASQ系の光起電材料のなかで最も低い値である。
In the UV-Vis-NIR absorption spectrum, in the case of a cast film (FIG. 5B), BDT-ASQ and D-BDT-ASQ were shifted by 34 nm and 47 nm longer than S-ASQ, respectively. Specifically, the wavelength was increased in the order of S-ASQ <BDT-ASQ <D-BDT-ASQ. However, the energy difference was only about 0.03 eV.
S-ASQ and BDT-ASQ, as shown in Table 1, showed high molar extinction coefficient of almost equal to (~2.0M -1 cm -1), D -BDT-ASQ in 4.0 M -1 cm It showed a high value of -1 .
Both BDT-ASQ and D-BDT-ASQ had a longer wavelength shift and a broader waveform when measured with a cast film than when measured with a solution. The absorption band observed at 300 to 450 nm is considered to be due to the π-π * transition of the BDT segment. From the onset position of the absorption spectrum, the optical band gaps (E g opt ) of BDT-ASQ and D-BDT-ASQ are estimated to be 1.39 eV and 1.36 eV, respectively, and 0.02 eV from S-ASQ. And 0.05 eV lower. The optical band gap (E g opt ) of 1.36 eV of D-BDT-ASQ is the lowest value among ASQ-based photovoltaic materials known so far.
また、サイクリックボルタンメトリー(CV)では、表1に示すとおり、BDT−ASQのHOMO及びLUMOのエネルギーはそれぞれ−5.16eV及び−3.54eVであり、D−BDT−ASQのHOMO及びLUMOのエネルギーはそれぞれ−5.15eV及び−3.55eVであった。これは、S−ASQのHOMO及びLUMOのエネルギー(HOMO:−5.10eV及びLUMO:−3.43eV)に比べて、BDT−ASQでは、HOMOが0.06eV低下し、LUMOでは0.11eV低下しており、D−BDT−ASQでは、HOMOが0.05eV低下し、LUMOでは0.12eV低下しており、BDT構造が導入されたことにより、低バンドギャップ化したことが示唆される。 Moreover, in cyclic voltammetry (CV), as shown in Table 1, the HOMO and LUMO energies of BDT-ASQ are −5.16 eV and −3.54 eV, respectively, and the HOMO and LUMO energies of D-BDT-ASQ, respectively. Were −5.15 eV and −3.55 eV, respectively. Compared to the HOMO and LUMO energies of S-ASQ (HOMO: -5.10 eV and LUMO: -3.43 eV), BDT-ASQ reduces HOMO by 0.06 eV and LUMO decreases by 0.11 eV. In D-BDT-ASQ, HOMO decreased by 0.05 eV and LUMO decreased by 0.12 eV, suggesting that the band gap was reduced by introducing the BDT structure.
[試験例2]有機太陽電池の光起電力評価
陽極として、ガラス基板の全面に酸化インジウムスズ(ITO)膜が塗布されたITO基板を準備し、ITO電極の上に、正孔輸送層として、6nm厚の酸化モリブデン(VI)(MoO3)層を積層させ、その上に活性層として、ドナー(Donor)材料にBDT−ASQ、D−BDT−ASQ又はS−ASQと、アクセプター(Acceptor)材料に[6,6]−フェニルC71酪酸メチル(PC71BM)とを1:7の質量比で混合したものを70〜100nm厚となるように塗布し、その上に電子輸送層として、10nm厚の2,9−ジメチル−4,7−ジフェニル−1,10−フェナントロリン(BCP)を積層し、陰極として100nm厚のアルミニウム板を積層させて、BHJ型太陽電池の素子(ITO/MoO3/ASQ:PC71BM/BCP/Al構造)を作製し、特性評価を行った。なお、前記素子構造中に記載の「ASQ」は、BDT−ASQ、D−BDT−ASQ、又はS−ASQを表す。
[Test Example 2] Photovoltaic evaluation of organic solar cell As an anode, an ITO substrate in which an indium tin oxide (ITO) film was coated on the entire surface of a glass substrate was prepared, and a hole transport layer was formed on the ITO electrode. A molybdenum (VI) (MoO 3 ) layer having a thickness of 6 nm is stacked, and as an active layer thereon, BDT-ASQ, D-BDT-ASQ, or S-ASQ is used as a donor material, and an acceptor material is used. [6,6] -Phenyl C71 methyl butyrate (PC 71 BM) mixed at a mass ratio of 1: 7 was applied to a thickness of 70 to 100 nm, and an electron transport layer was formed thereon with a thickness of 10 nm. Of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and a 100 nm thick aluminum plate as a cathode, Solar cell element: to produce a (ITO / MoO 3 / ASQ PC 71 BM / BCP / Al structure) was subjected to characteristic evaluation. Note that “ASQ” described in the element structure represents BDT-ASQ, D-BDT-ASQ, or S-ASQ.
表2より、S−ASQを用いた素子のPCEは3.82%、Vocは0.87V、Jscは10.71mAcm-2、FFは0.41であり、BDT−ASQを用いた素子では、PCEは4.11%、Vocは0.93V、Jscは10.79mAcm-2、FFは0.41であり、D−BDT−ASQを用いた素子では、PCEは5.75%、Vocは0.92V、Jscは12.50mAcm-2、FFは0.50であった。BDT−ASQ及びD−BDT−ASQは、S−ASQと比べて、Vocが0.05〜0.06V高いことがわかった。これは、BDT−ASQ及びD−BDT−ASQのHOMOのエネルギーレベルが、S−ASQよりも0.05〜0.06eV低いというCVの結果と一致する。
S−ASQのPCEは4.31%であったが、BDT−ASQ及びD−BDT−ASQのPCEはそれぞれ4.77%及び6.33%であった。
太陽電池は外で常温よりも高い温度下に使用されることが想定されるため、80℃の条件下に実験を行った。S−ASQ、BDT−ASQ及びD−BDT−ASQのすべての素子でVocはわずかに低下し、JscとFFはわずかに増大した。また、D−BDT−ASQを用いた素子で、PCEは7.41%と、最も高い値を示した。
From Table 2, the element using S-ASQ had a PCE of 3.82%, V oc of 0.87 V, J sc of 10.71 mAcm −2 , and FF of 0.41, and an element using BDT-ASQ. Then, PCE is 4.11%, V oc is 0.93 V, J sc is 10.79 mAcm −2 , and FF is 0.41. In the element using D-BDT-ASQ, PCE is 5.75%. , V oc was 0.92 V, J sc was 12.50 mAcm −2 , and FF was 0.50. BDT-ASQ and D-BDT-ASQ were found to have a V oc higher by 0.05 to 0.06 V than S-ASQ. This is consistent with the CV result that the HOMO energy levels of BDT-ASQ and D-BDT-ASQ are 0.05-0.06 eV lower than S-ASQ.
The PCE of S-ASQ was 4.31%, while the PCE of BDT-ASQ and D-BDT-ASQ were 4.77% and 6.33%, respectively.
Since the solar cell is assumed to be used outside and at a temperature higher than normal temperature, the experiment was performed under the condition of 80 ° C. In all elements of S-ASQ, BDT-ASQ and D-BDT-ASQ, V oc decreased slightly and J sc and FF increased slightly. Further, in the element using D-BDT-ASQ, PCE showed the highest value of 7.41%.
次いで、ドナー材料であるD−BDT−ASQと、アクセプター材料である[6,6]−フェニルC71酪酸メチル(PC71BM)とを種々の質量比で用いて、BHJ型太陽電池の素子を作製した場合の特性評価結果を図7(a)及び(b)並びに表3に示す。 Next, BHJ-type solar cell devices are manufactured using D-BDT-ASQ, which is a donor material, and [6,6] -phenyl C71 methyl butyrate (PC 71 BM), which is an acceptor material, in various mass ratios. FIG. 7A and FIG. 7B and Table 3 show the result of characteristic evaluation in this case.
ドナーとアクセプターとの質量比(D/A)が1:3〜1:9であるとき、素子のPCEは5%を超えていた。D/Aが1:7付近であるとき、PCEが最も高い値となることがわかった。
D−BDT−ASQでは、平面で非対称な二量体構造を有するため、かさ高い縮合環構造を有するBDTがドナーの役割を果たす。S−ASQに比べて、D−BDT−ASQでは0.05eV低いHOMOエネルギーレベルを有するのみならず、長波長シフトすることがわかった。さらに重要なことに、D−BDT−ASQの正孔移動度は単膜、及び、アクセプター材料との混合膜のいずれにおいても、S−ASQに比べて高い。結果的に、D−BDT−ASQを用いたBHJ型太陽電池の素子は、S−ASQを用いた場合よりも、Voc、Jsc、FFのいずれも高く、D/A比が1:7付近のとき、PCEが最高値で7.41%という優れた結果を示した。この数値は、これまで知られたスクワレン系の単接合型有機太陽電池のなかで最高値であり、このような平面で非対称な二量体構造を改良することが、今後、高性能な光起電材料を得るのに重要な方法であるといえる。
When the mass ratio (D / A) between the donor and the acceptor was 1: 3 to 1: 9, the PCE of the device exceeded 5%. It was found that when D / A was around 1: 7, PCE was the highest value.
In D-BDT-ASQ, since it has a planar asymmetric dimer structure, BDT having a bulky condensed ring structure plays the role of a donor. Compared to S-ASQ, D-BDT-ASQ not only has a HOMO energy level lower by 0.05 eV, but also has a longer wavelength shift. More importantly, the hole mobility of D-BDT-ASQ is higher than that of S-ASQ in both single films and mixed films with acceptor materials. As a result, the element of the BHJ type solar cell using D-BDT-ASQ has a higher V oc , J sc , and FF and a D / A ratio of 1: 7 than when S-ASQ is used. In the vicinity, the PCE showed the excellent result of the highest value of 7.41%. This figure is the highest among the squalene-based single-junction organic solar cells known so far, and improvement of such a planar asymmetric dimer structure will lead to high-performance photovoltaics in the future. It can be said that this is an important method for obtaining electric materials.
1 基板
2 陰極
3 正孔輸送層
4 活性層
5 電子輸送層
6 陰極
DESCRIPTION OF
Claims (4)
R2及びR3が脂肪族基の場合、R2及びR3は連結して環を形成してもよく、
R5及びR6が脂肪族基の場合、R5及びR6は連結して環を形成してもよく、
Xは、フェニル基、又は、下記構造式で表される1価の置換基を示し、
Arは2価の芳香族基を示す。)
When R 2 and R 3 are aliphatic groups, R 2 and R 3 may be linked to form a ring,
When R 5 and R 6 are aliphatic groups, R 5 and R 6 may be linked to form a ring,
X represents a phenyl group or a monovalent substituent represented by the following structural formula;
Ar represents a divalent aromatic group. )
Arがチオフェニレン基を示し、かつ、
R1〜R6はそれぞれ独立に炭素原子数1〜20の1価の脂肪族基を示すことを特徴とする、請求項1又は2に記載のスクアリリウム誘導体。 In the general formula (1),
Ar represents a thiophenylene group, and
The squarylium derivative according to claim 1 or 2, wherein R 1 to R 6 each independently represents a monovalent aliphatic group having 1 to 20 carbon atoms.
Priority Applications (1)
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JP2011165963A (en) * | 2010-02-10 | 2011-08-25 | Osaka Prefecture Univ | Organic dye and organic thin-film solar cell |
JP2013199541A (en) * | 2012-03-23 | 2013-10-03 | Osaka Prefecture Univ | Squarylium compound, thin film including the same, and organic thin-film solar cell |
CN104163785A (en) * | 2014-06-16 | 2014-11-26 | 四川大学 | A series of asymmetric squarine micromolecules containing indoline derivative structure, and application thereof |
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JP2011165963A (en) * | 2010-02-10 | 2011-08-25 | Osaka Prefecture Univ | Organic dye and organic thin-film solar cell |
JP2013199541A (en) * | 2012-03-23 | 2013-10-03 | Osaka Prefecture Univ | Squarylium compound, thin film including the same, and organic thin-film solar cell |
CN104163785A (en) * | 2014-06-16 | 2014-11-26 | 四川大学 | A series of asymmetric squarine micromolecules containing indoline derivative structure, and application thereof |
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J. MATER. CHEM. A, vol. 2, JPN6020024267, 2014, pages 18313 - 18321, ISSN: 0004301038 * |
ORGANIC ELECTRONICS, vol. 32, JPN6020024266, 2 March 2016 (2016-03-02), pages 179 - 186, ISSN: 0004301037 * |
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