JP2011204883A - Fullerene derivative, composite including the same, and organic photoelectric conversion element - Google Patents
Fullerene derivative, composite including the same, and organic photoelectric conversion element Download PDFInfo
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Abstract
Description
本発明は新規なフラーレン誘導体、それを含む組成物及び有機光電変換素子に関する。 The present invention relates to a novel fullerene derivative, a composition containing the same, and an organic photoelectric conversion device.
フラーレン誘導体は有機半導体材料として優れた半導体特性を示すので、有機光電変換素子等への応用が期待されている。中でも、電子受容性化合物として、前記フラーレン誘導体を用いた有機太陽電池は、シリコンなどに代表される太陽電池に比べて製造が容易で、かつ低コスト、さらには大面積が可能であるという利点があることから広く検討がなされている。有機太陽電池としては、相分離を利用したバルクへテロ構造体が第３世代の有機太陽電池として提案されている。このタイプの有機薄膜太陽電池の中で最も一般的に用いられているのはＰＣＢＭ（[６，６]−フェニルＣ６１−酪酸メチルエステル））とポリチオフェンの混合系である（非特許文献１参照）が、他の太陽電池と比較して効率が未だ低いという問題があるため、有機半導体材料を用いた有機光電変換素子の研究が全世界的に行われており、有機光電変換素子の光電変換効率向上においては、ナノスケールでの構造形成・制御技術が極めて重要であることが知られている。
ところで、フラーレン誘導体を含む有機太陽電池を製造する場合、フラーレン誘導体を有機溶媒に溶解させた溶液を塗布法により薄膜を作成する方法を用いることができるが、前記PCBMの有機溶剤への溶解性は必ずしも十分ではなく、高い溶解性フラーレン誘導体の研究が盛んに行われている。（特許文献１参照）
このような背景から、容易に合成することができ、塗布法により製造される有機光電変換素子として適用可能なフラーレン誘導体が望まれていた。
Since fullerene derivatives exhibit excellent semiconductor characteristics as organic semiconductor materials, application to organic photoelectric conversion elements and the like is expected. Among these, an organic solar battery using the fullerene derivative as an electron-accepting compound has an advantage that it is easy to manufacture and can be manufactured at a lower cost and a larger area than a solar battery typified by silicon. It has been widely studied because of it. As an organic solar cell, a bulk heterostructure using phase separation has been proposed as a third generation organic solar cell. The most commonly used organic thin-film solar cell of this type is a mixed system of PCBM ([6,6] -phenyl C61-butyric acid methyl ester)) and polythiophene (see Non-Patent Document 1). However, since there is a problem that the efficiency is still low compared with other solar cells, research on organic photoelectric conversion elements using organic semiconductor materials has been conducted worldwide, and the photoelectric conversion efficiency of organic photoelectric conversion elements For improvement, it is known that nanoscale structure formation and control technology is extremely important.
By the way, when manufacturing an organic solar cell containing a fullerene derivative, a method of forming a thin film by a coating method using a solution in which a fullerene derivative is dissolved in an organic solvent can be used, but the solubility of the PCBM in an organic solvent is However, this is not always sufficient, and researches on highly soluble fullerene derivatives have been actively conducted. (See Patent Document 1)
From such a background, a fullerene derivative that can be easily synthesized and can be applied as an organic photoelectric conversion element produced by a coating method has been desired.
本発明は、上記の課題に鑑みてなされたものである。即ち、本発明は有機光電変換素子及びそれに用いるフラーレン誘導体並びにそれを含む組成物を提供することを目的とする。 The present invention has been made in view of the above problems. That is, an object of the present invention is to provide an organic photoelectric conversion device, a fullerene derivative used therefor, and a composition containing the same.
本発明者等は、前記目的を達成するために鋭意研究を重ねた結果、下記式（１）で表されるフラーレン誘導体を用いることにより、前記の目的を達成することを見出し、本発明を完成するに至った。
すなわち、本発明は、
１．下記式（１）で表されるフラーレン誘導体、
As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using a fullerene derivative represented by the following formula (1), thereby completing the present invention. It came to do.
That is, the present invention
1. A fullerene derivative represented by the following formula (1):
[式（１）中、Ｒ1、Ｒ2は、水素原子もしくは炭素数１〜４のアルキル基、Ｒ3は式（２）、（３）又は(４)で表される基を示す。またｎは０〜３、ｍは１〜４の整数を表す。]
２．球状構造の炭素数が６０のＣ６０フラーレン誘導体である、前記１に記載のフラーレン誘導体、
３．前記１又は２に記載のフラーレン誘導体と電子供与性化合物とを含む組成物、
４．電子供与性化合物が高分子化合物である、前記３に記載の組成物、
５．前記１に記載のフラーレン誘導体を含む層を有する有機光電変換素子、
６．前記３又は４に記載の組成物を含む層を有する有機光電変換素子、
を提供するものである。
[In Formula (1), R < 1 >, R < 2 > shows a hydrogen atom or a C1-C4 alkyl group, R < 3 > shows group represented by Formula (2), (3) or (4). N represents an integer of 0 to 3, and m represents an integer of 1 to 4. ]
2. 2. The fullerene derivative according to 1 above, which is a C60 fullerene derivative having a spherical structure of 60 carbon atoms,
3. A composition comprising the fullerene derivative according to 1 or 2 and an electron donating compound,
4). 4. The composition according to 3 above, wherein the electron donating compound is a polymer compound,
5. The organic photoelectric conversion element which has a layer containing the fullerene derivative of said 1,
6). An organic photoelectric conversion element having a layer containing the composition according to 3 or 4 above,
Is to provide.
本発明のフラーレン誘導体は簡単な合成方法で得られ、そのフラーレン誘導体及びそれを含む組成物を有機光電変換素子の材料として用いることにより、容易に合成することができ、塗布法（ウェットプロセス）により製造される有機光電変換素子が得られる。 The fullerene derivative of the present invention can be obtained by a simple synthesis method, and can be easily synthesized by using the fullerene derivative and a composition containing the fullerene derivative as a material for an organic photoelectric conversion element, by a coating method (wet process). The manufactured organic photoelectric conversion element is obtained.
本発明のフラーレン誘導体は、下記式（１）で表される。
式（１）中、Ｒ1、Ｒ2は、水素原子もしくは炭素数１〜４のアルキル基を示し、アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、イソブチル基、ｔ−ブチル基が挙げられる。また、このアルキル基の水素原子は、フッソ原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子で置換されていても良い。
Ｒ1、Ｒ2としては、水素原子が好ましい。
Ｒ3は式（２）、（３）又は(４)で表される基を示す。式（２）において、ｎは０〜３の整数である。また、式（４）において、ｍは１〜４の整数である。
また、式（１）において、球状構造の炭素数が６０のＣ６０フラーレン誘導体であると好ましい。
Wherein (1), R 1, R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group , S-butyl group, isobutyl group, t-butyl group. Moreover, the hydrogen atom of this alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
R 1 and R 2 are preferably hydrogen atoms.
R 3 represents a group represented by the formula (2), (3) or (4). In Formula (2), n is an integer of 0-3. Moreover, in Formula (4), m is an integer of 1-4.
In the formula (1), a C60 fullerene derivative having a spherical structure with 60 carbon atoms is preferable.
本発明の式（１）で表されるフラーレン誘導体の製造方法としては、実施例のようにして製造できるがこれに限定されるものではなく、公知の方法を用いることができる。 As a manufacturing method of the fullerene derivative represented by Formula (1) of this invention, although it can manufacture like an Example, it is not limited to this, A well-known method can be used.
次に、本発明のフラーレン誘導体を含む組成物及び有機光電変換素子について説明する。
本発明のフラーレン誘導体を用いる有機光電変換素子は、少なくとも一方が透明又は半透明である一対の電極間に本発明のフラーレン誘導体を含む層を有する。本発明のフラーレン誘導体は、電子受容体として用いることが好ましい。本発明のフラーレン誘導体のみを用いて有機光電変換素子に含まれる層を形成してもよく、本発明のフラーレン誘導体と電子供与性化合物とを含む組成物を用いて有機光電変換素子に含まれる層を形成してもよい。
本発明のフラーレン誘導体又はそれを含む組成物が含有される有機光電変換素子の層としては、活性層が好ましい。
また、このような層の形成方法としては、特に限定されないが、例えば、スピンコーティング、ディップコーティング、スプレーコーティング、ドクターブレード、バーコート等の湿式法、真空蒸着法等が挙げられる。これらの中でも、本発明の有機光電変換素子がウェットプロセスにより製造されるという観点から、スピンコーティング、ディップコーティング、スプレーコーティング、ドクターブレード、バーコート等の湿式法が好ましい。
この溶液に含まれる溶媒としては、前記フラーレン誘導体および前記電子供与性化合物を溶解するものであれば特に限定されず、例えば、クロロベンゼン、オルトジクロロベンゼン、クロロホルム、ジクロロメタン、トルエン、テトラヒドロフラン等の公知のものを用いればよい。
Next, the composition containing the fullerene derivative of the present invention and the organic photoelectric conversion device will be described.
The organic photoelectric conversion element using the fullerene derivative of the present invention has a layer containing the fullerene derivative of the present invention between a pair of electrodes, at least one of which is transparent or translucent. The fullerene derivative of the present invention is preferably used as an electron acceptor. The layer included in the organic photoelectric conversion element may be formed using only the fullerene derivative of the present invention, and the layer included in the organic photoelectric conversion element using the composition containing the fullerene derivative of the present invention and the electron donating compound. May be formed.
As the layer of the organic photoelectric conversion element containing the fullerene derivative of the present invention or the composition containing the same, an active layer is preferable.
The method for forming such a layer is not particularly limited, and examples thereof include wet methods such as spin coating, dip coating, spray coating, doctor blade, and bar coating, and vacuum deposition methods. Among these, wet methods such as spin coating, dip coating, spray coating, doctor blade, and bar coating are preferable from the viewpoint that the organic photoelectric conversion element of the present invention is produced by a wet process.
The solvent contained in this solution is not particularly limited as long as it dissolves the fullerene derivative and the electron donating compound. For example, known solvents such as chlorobenzene, orthodichlorobenzene, chloroform, dichloromethane, toluene, and tetrahydrofuran May be used.
本発明のフラーレン誘導体と共に用いられる電子供与性化合物は、特に限定されず、有機光電変換素子において用いられる公知の材料を用いれば良いが、例えば、有機半導体材料又は無機半導体材料が挙げられ、フラーレン誘導体を含む層がウェットプロセスにより簡便な方法で得られることから有機半導体材料が好ましい。このような有機半導体材料としては、ポリアルキルチオフェン及びその誘導体、ポリフェニレン及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリシラン及びその誘導体、ポリアルキルチオフェン及びその誘導体、ポルフィリン誘導体、フタロシアニン、銅フタロシアニン、亜鉛フタロシアニン、チタニルフタロシアニン等のフタロシアニン誘導体、有機金属ポリマー等が挙げられるが、ポリアルキルチオフェン及びその誘導体が好ましい。また、これらの有機半導体材料の混合物であってもよい。
ポリフェニレンビニレンの誘導体としては、ポリ［２−メトキシ，５−（２’−エチル−ヘキシロキシ）−ｐ−フェニレン−ビニレン］（ＭＥＨ−ＰＰＶ）等を用いることができ、ポリチオフェン系高分子材料としては、ポリ−３−ヘキシルチオフェン（Ｐ３ＨＴ）等のポリ（３−アルキルチオフェン）、ジオクチルフルオレンエン−ビチオフェン共重合体（Ｆ８Ｔ２）を用いることができる。
本発明において、電子受容体と電子供与性材料の質量比は、有機光電変換層という理由から１：０．５〜１：４．０であると好ましい。
また、本発明のフラーレン誘導体を含む層及びフラーレン誘導体を含む組成物には、本発明より得られる効果を阻害しない範囲で、必要に応じ、界面活性剤、シリカ等の無機微粒子フィラー等の添加物を配合しても良い。
The electron donating compound used together with the fullerene derivative of the present invention is not particularly limited, and a known material used in an organic photoelectric conversion element may be used. Examples thereof include an organic semiconductor material or an inorganic semiconductor material, and a fullerene derivative. An organic semiconductor material is preferable because the layer containing can be obtained by a simple method by a wet process. Examples of such organic semiconductor materials include polyalkylthiophene and derivatives thereof, polyphenylene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polysilane and derivatives thereof, polyalkylthiophene and derivatives thereof, porphyrin derivatives, phthalocyanine, copper phthalocyanine, zinc phthalocyanine, Examples thereof include phthalocyanine derivatives such as titanyl phthalocyanine, organometallic polymers, and the like, and polyalkylthiophene and derivatives thereof are preferable. Moreover, the mixture of these organic-semiconductor materials may be sufficient.
As a derivative of polyphenylene vinylene, poly [2-methoxy, 5- (2′-ethyl-hexyloxy) -p-phenylene-vinylene] (MEH-PPV) or the like can be used. As a polythiophene polymer material, Poly (3-alkylthiophene) such as poly-3-hexylthiophene (P3HT) and dioctylfluorene-bithiophene copolymer (F8T2) can be used.
In the present invention, the mass ratio of the electron acceptor to the electron donating material is preferably 1: 0.5 to 1: 4.0 because of the organic photoelectric conversion layer.
In addition, the layer containing the fullerene derivative of the present invention and the composition containing the fullerene derivative may contain additives such as surfactants, inorganic fine particle fillers such as silica, and the like as long as the effects obtained from the present invention are not impaired. May be blended.
本発明の有機光電変換素子の電極材料としては、特に限定されないが、負極電極の場合電子受容体（ｎ型半導体）のＬＵＭＯレベルに対してエネルギー障壁が小さく、仕事関数が比較的小さなものから選ばれる。例としてＡｇ、Ａｌ、Ｐｔ，Ｉｒ、Ｃｒ、ＺｎＯ、ＣＮＴ及びそれらの合金・複合体などが挙げられる。負極電極の形成方法としては、例えば、真空蒸着、スパッタリング、イオンプレーティング、等のＰＶＤ（物理気相蒸着）、もしくは原子層蓄積法（ＡＬＤ）等のＣＶＤ（化学気相蒸着）等の方法で形成すればよい。
頂部電極としては電子供与性化合物（ｐ型半導体）のＨＯＭＯレベルとエネルギー障壁が小さく、比較的仕事関数が大きなものから選ばれ、透明でなければならない。例えばＩＴＯ，ＩｒＯ2、Ｉｎ2Ｏ3、ＳｎＯ2、ＩＺＯ、ＺｎＯ（Ｇａ、Ａｌドープ）、ＭｏＯ3等の材料から形成される。形成方法は負極電極と同様である。
また、有機光電変換素子において、（各層の接触界面に緩衝層（バッファ層）を設けることもできる。バッファ層としては、導電性の層であればよく、ポリ（３，４）−エチレンジオキシチオフェン／ポリスチレンスルフォネート（ＰＥＤＯＴ：ＰＳＳ）酸化モリブデン、フッ化リチウム、酸化チタン、金あるいはバソクプロイン等からなる導電性の層を好ましく使用することができる。なかでも、ＰＥＤＯＴ：ＰＳＳが好ましく用いることができる。
The electrode material of the organic photoelectric conversion element of the present invention is not particularly limited. In the case of the negative electrode, it is selected from those having a small energy barrier and a relatively small work function with respect to the LUMO level of the electron acceptor (n-type semiconductor). It is. Examples include Ag, Al, Pt, Ir, Cr, ZnO, CNT, and alloys and composites thereof. As a method for forming the negative electrode, for example, PVD (physical vapor deposition) such as vacuum deposition, sputtering, ion plating, or CVD (chemical vapor deposition) such as atomic layer deposition (ALD) is used. What is necessary is just to form.
The top electrode is selected from those having an electron donating compound (p-type semiconductor) having a low HOMO level and energy barrier, a relatively large work function, and must be transparent. For example, it is made of a material such as ITO, IrO 2 , In 2 O 3 , SnO 2 , IZO, ZnO (Ga, Al doped), MoO 3 or the like. The formation method is the same as that of the negative electrode.
In the organic photoelectric conversion element, a buffer layer (buffer layer) can be provided at the contact interface of each layer. The buffer layer may be a conductive layer, and poly (3,4) -ethylenedioxy A conductive layer made of thiophene / polystyrene sulfonate (PEDOT: PSS) molybdenum oxide, lithium fluoride, titanium oxide, gold, bathocuproine, etc. can be preferably used, among which PEDOT: PSS is preferably used. it can.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されない。
実施例１（フラーレン誘導体１の製造）
（１）前駆体の合成
文献（Angew. Chem. Int. Ed. 2004, 43, 1512-1516）に準じて合成した。すなわち撹拌機、冷却管を備えた５００ｍｌの丸底フラスコに、Ｃ６０；５１２ｍｇ、パラホルムアルデヒド；１１５ｍｇ、Ｎ−（ｐ−ヒドロキシフェニル）グリシン；２３４ｍｇ、トルエン；５００ｍｌを取って均一に溶解し、窒素雰囲気下５時間加熱還流した。その後、溶媒をエバポレーターで濃縮し、シリカゲルカラムクロマトグラフィー（展開溶媒トルエン）で精製して、前駆体として黒褐色の下式（Ｘ）に示す誘導体２３８ｍｇを得た。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
Example 1 (Production of fullerene derivative 1)
(1) Synthesis of precursor The compound was synthesized according to the literature (Angew. Chem. Int. Ed. 2004, 43, 1512-1516). That is, in a 500 ml round bottom flask equipped with a stirrer and a condenser tube, C60; 512 mg, paraformaldehyde; 115 mg, N- (p-hydroxyphenyl) glycine; 234 mg, toluene; The mixture was heated to reflux for 5 hours. Thereafter, the solvent was concentrated with an evaporator and purified by silica gel column chromatography (developing solvent toluene) to obtain 238 mg of a derivative represented by the following formula (X) of black brown as a precursor.
（２）フラーレン誘導体１の合成
得られた前駆体５６．３ｍｇをフラスコに測りとり、トルエン（脱水）を加え溶解させた。ここに１−エチルｌ−３−（３−ジメチルアミノプロピル）カルボキシジイミド（ＥＤＣＩ）３２ｍｇ、ＤＬ−チオクト酸３１ｍｇ、Ｎ，Ｎ−ジメチルアミノピリジン（ＤＭＡＰ）２ｍｇを加え、窒素雰囲気下室温で５時間撹拌した。その後、反応液に水を加え分液漏斗で分離し、有機層に硫酸ナトリウムを加えて乾燥させ、濾過により固形を除きエバポレーターで溶媒を除去した後、シリカゲルカラムクロマトグラフィー（展開溶媒：トルエン）で精製して下記フラーレン誘導体１（２８．５ｍｇ）を得た (収率４１％)。得られたフラーレン誘導体１のＮＭＲ及びＦＤ−ＭＳ測定結果を以下に示す。これにより、フラーレン誘導体１であることが確認できた。
Rf 0.57(トルエン); 1 HNMR (500 MHz, ppm, CDCl3 , J=Hz) δ;1.63 (m, 2H), 1.82 (m, 4H), 1.97 (m, 1H), 2.64 (t, 2H, J= 7.4 Hz), 2.52 (m, 1H), 3.16 (m, 1H), 3.22 (m, 1H), 3.64 (m, 1H), 5.10 (s, 3H), 5.30 (s, 1H), 7.21 (d, 2H, J=9.0), 7.33(d, 2H, J=9.0)；13 CNMR (125 MHz, ppm, CDCl3 ) δIR (neat, cm-1); FD-MS found 1043 (calcd for C76H21O2NS2 , exact mass: 1043.10)．
(2) Synthesis of fullerene derivative 1 56.3 mg of the obtained precursor was weighed into a flask, and toluene (dehydrated) was added and dissolved. To this, 32 mg of 1-ethyl l-3- (3-dimethylaminopropyl) carboxydiimide (EDCI), 31 mg of DL-thioctic acid and 2 mg of N, N-dimethylaminopyridine (DMAP) were added, and at room temperature for 5 hours under a nitrogen atmosphere. Stir. Then, water is added to the reaction solution and separated with a separatory funnel. Sodium sulfate is added to the organic layer and dried. The solid is removed by filtration, the solvent is removed with an evaporator, and silica gel column chromatography (developing solvent: toluene) is used. Purification gave the following fullerene derivative 1 (28.5 mg) (yield 41%). The NMR and FD-MS measurement results of the obtained fullerene derivative 1 are shown below. This confirmed that it was fullerene derivative 1.
Rf 0.57 (toluene); 1 HNMR (500 MHz, ppm, CDCl3, J = Hz) δ; 1.63 (m, 2H), 1.82 (m, 4H), 1.97 (m, 1H), 2.64 (t, 2H, J = 7.4 Hz), 2.52 (m, 1H), 3.16 (m, 1H), 3.22 (m, 1H), 3.64 (m, 1H), 5.10 (s, 3H), 5.30 (s, 1H), 7.21 (d , 2H, J = 9.0), 7.33 (d, 2H, J = 9.0); 13 CNMR (125 MHz, ppm, CDCl 3 ) δIR (neat, cm -1 ); FD-MS found 1043 (calcd for C 76 H 21 O 2 NS 2 , exact mass: 1043.10).
次に、得られたフラーレン誘導体１について、以下の評価を行った。
（ｉ）サイクリックボルタンメトリー（ＣＶ）によるフラーレン誘導体１の評価
製造したフラーレン誘導体１について、サイクリックボルタンメトリー（ＢＡＳ社製）を測定した。作用電極として金電極、対電極としてＰｔ線、参照電極としてＡｇ線を用いた。測定時の掃引速度は１００ｍＶ／ｓｅｃ、走査電位領域は−１．５Ｖ〜０Ｖであった。還元電位及び酸化電位の測定は、支持電解質としてのテトラブチルアンモニウムヘキサフルオロフォスフェート（ＴＢＡＰＦ６）をオルトジクロロベンゼン溶媒に溶解し飽和させた液に、フラーレン誘導体１を１×１０-3ｍｏｌ／Ｌの濃度に溶解させた溶液で測定した。測定の結果、フラーレン誘導体１は、−０．９１Ｖ及び１．２９Ｖにそれぞれ第一還元電位、第二還元電位を示した。これらはＰＣＢＭの値と近く、光電変換材料に適した材料と判断できる。
Next, the obtained fullerene derivative 1 was evaluated as follows.
(I) Evaluation of Fullerene Derivative 1 by Cyclic Voltammetry (CV) With respect to the produced fullerene derivative 1, cyclic voltammetry (manufactured by BAS) was measured. A gold electrode was used as the working electrode, a Pt line as the counter electrode, and an Ag line as the reference electrode. The sweep rate during measurement was 100 mV / sec, and the scanning potential region was −1.5 V to 0 V. The reduction potential and the oxidation potential were measured by dissolving fullerene derivative 1 in a solution of tetrabutylammonium hexafluorophosphate (TBAPF6) as a supporting electrolyte dissolved in orthodichlorobenzene solvent and saturated to 1 × 10 −3 mol / L. Measured with a solution dissolved in concentration. As a result of the measurement, the fullerene derivative 1 exhibited a first reduction potential and a second reduction potential at −0.91 V and 1.29 V, respectively. These are close to the value of PCBM and can be judged as materials suitable for the photoelectric conversion material.
（ii）紫外可視（ＵＶ−ＶＩＳ）吸収スペクトル測定によるフラーレン誘導体１の評価
紫外可視吸収スペクトルの測定は、(ＵＶ−３６００［商品名］、島津製作所)を用いて行った。フラーレン誘導体１をトルエンに９．６×１０-5ｍｏｌ／Ｌの濃度で完全に溶解し、３００〜１０００ｎｍの吸収スペクトルを測定したところ、７２５ｎｍに吸収端が認められた。この波長からバンドギャップを見積もったところ、１．７ｅＶであった。この値からもフラーレン誘導体１は光電変換材料に適した材料と判断できる。
(Ii) Evaluation of fullerene derivative 1 by ultraviolet-visible (UV-VIS) absorption spectrum measurement The ultraviolet-visible absorption spectrum was measured using (UV-3600 [trade name], Shimadzu Corporation). Fullerene derivative 1 was completely dissolved in toluene at a concentration of 9.6 × 10 −5 mol / L, and an absorption spectrum at 300 to 1000 nm was measured. As a result, an absorption edge was observed at 725 nm. The band gap was estimated from this wavelength and found to be 1.7 eV. Also from this value, it can be judged that the fullerene derivative 1 is a material suitable for a photoelectric conversion material.
(iii)有機薄膜太陽電池の作製、評価
窒素雰囲気下、電子供与性化合物としてレジオレギュラーポリ３−ヘキシルチオフェン（Ｐ３ＨＴ）（メルク社製 Ｌｉｓｉｃｏｎ ＳＰ００１［商品名］）３０ｍｇとフラーレン誘導体１（２４ｍｇ）をクロロベンゼン２ｍＬに溶解させ、５０度で２０時間撹拌した。ついで、孔径０．４５μｍのＰＴＦＥメンブレンフィルターで濾過し、塗布溶液を作製した。１００ｎｍの厚みでＩＴＯ 膜を付けたガラス基板（テクノプリント株式会社）を、中性洗剤、純水、アセトン、イソプロパノールで超音波洗浄した後、オゾンＵＶ処理して表面処理を行った。次に、ポリ（３，４）−エチレンジオキシチオフェン／ポリスチレンスルフォネート（ＰＥＤＯＴ：ＰＳＳ）水分散液（Ｈ．Ｃ．スタルク社製，Ｃｌｅｖｉｏｓ Ｐ ＡＬ４０８３）をスピンコートし、１４０℃で１０分間乾燥させ、膜厚４０ｎｍの膜を形成した。次に、グローブボックス中で前記塗布溶液をスピンコートにより塗布し、有機薄膜太陽電池の活性層（膜厚約１００ｎｍ）を得た。その後、真空蒸着によりＡｌを１００ｎｍの厚さで蒸着した。蒸着のときの真空度は１〜２×１０-3Ｐａであった。その後１５０度で１０分アニーリング処理を行った。
得られた有機薄膜太陽電池の光電変換効率は、ソーラシミュレーター(ワコム電創製、ＡＭ１．５Ｇフィルター［商品名］、放射照度１００ｍＷ／ｃｍ2)を用いて一定の光を照射し、発生する電流と電圧を測定して求めた。電流値は０．２８ｍＡ、電圧値は０．５３Ｖであった。この結果よりフラーレン誘導体１は光電変換素子の材料として好適である。
(iii) Production and Evaluation of Organic Thin Film Solar Cell Under a nitrogen atmosphere, 30 mg of regioregular poly-3-hexylthiophene (P3HT) (Lisicon SP001 [trade name] manufactured by Merck & Co., Inc.) and fullerene derivative 1 (24 mg) were used as electron donating compounds. It was dissolved in 2 mL of chlorobenzene and stirred at 50 degrees for 20 hours. Subsequently, it filtered with the PTFE membrane filter with the hole diameter of 0.45 micrometer, and produced the coating solution. A glass substrate (Technoprint Co., Ltd.) having an ITO film with a thickness of 100 nm was ultrasonically cleaned with a neutral detergent, pure water, acetone, and isopropanol, and then surface treated by ozone UV treatment. Next, a poly (3,4) -ethylenedioxythiophene / polystyrene sulfonate (PEDOT: PSS) aqueous dispersion (manufactured by HC Starck, Clevios P AL4083) was spin-coated, and 140 ° C. for 10 minutes. It dried and formed the film | membrane with a film thickness of 40 nm. Next, the coating solution was applied by spin coating in a glove box to obtain an active layer (film thickness of about 100 nm) of the organic thin film solar cell. Thereafter, Al was deposited to a thickness of 100 nm by vacuum deposition. The degree of vacuum at the time of vapor deposition was 1-2 × 10 −3 Pa. Thereafter, an annealing treatment was performed at 150 degrees for 10 minutes.
The photoelectric conversion efficiency of the obtained organic thin-film solar cell was determined by irradiating a certain amount of light using a solar simulator (manufactured by Wacom Denso, AM1.5G filter [trade name], irradiance of 100 mW / cm 2 ). It was determined by measuring the voltage. The current value was 0.28 mA, and the voltage value was 0.53V. From this result, the fullerene derivative 1 is suitable as a material for the photoelectric conversion element.
以上詳細に説明したように、本発明のフラーレン誘導体は容易な合成方法で得られ、そのフラーレン誘導体及びそれを含む組成物を有機光電変換素子の材料として用いることにより、塗布法により製造される有機光電変換素子が得られる。このため、実用性の高い、有機光電変換素子として極めて有用である。 As described above in detail, the fullerene derivative of the present invention can be obtained by an easy synthesis method, and the fullerene derivative and a composition containing the fullerene derivative can be used as a material for an organic photoelectric conversion element, thereby producing an organic compound produced by a coating method. A photoelectric conversion element is obtained. For this reason, it is extremely useful as an organic photoelectric conversion element having high practicality.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014218492A (en) * | 2012-07-17 | 2014-11-20 | 株式会社リコー | Fullerene derivative and method for producing the same |
| JP2015113301A (en) * | 2013-12-11 | 2015-06-22 | 株式会社リコー | Fullerene derivative and method of producing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005112816A (en) * | 2003-10-10 | 2005-04-28 | Mitsubishi Chemicals Corp | Sugar compound, method for use thereof, fullerene derivative and its production method |
| JP2007335760A (en) * | 2006-06-16 | 2007-12-27 | Fujifilm Corp | Photoelectric converting film, and solar battery photoelectric converting element, or imaging element including same |
| JP2009260324A (en) * | 2008-03-25 | 2009-11-05 | Sumitomo Chemical Co Ltd | Composition, and photoelectric converting element using it |
| JP2010278377A (en) * | 2009-06-01 | 2010-12-09 | Konica Minolta Holdings Inc | Organic photoelectric conversion element |
-
2010
- 2010-03-25 JP JP2010070315A patent/JP2011204883A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005112816A (en) * | 2003-10-10 | 2005-04-28 | Mitsubishi Chemicals Corp | Sugar compound, method for use thereof, fullerene derivative and its production method |
| JP2007335760A (en) * | 2006-06-16 | 2007-12-27 | Fujifilm Corp | Photoelectric converting film, and solar battery photoelectric converting element, or imaging element including same |
| JP2009260324A (en) * | 2008-03-25 | 2009-11-05 | Sumitomo Chemical Co Ltd | Composition, and photoelectric converting element using it |
| JP2010278377A (en) * | 2009-06-01 | 2010-12-09 | Konica Minolta Holdings Inc | Organic photoelectric conversion element |
Non-Patent Citations (1)
| Title |
|---|
| JPN6013051193; Ｍａｒｉａ Ｓｉｅｒｒａ， Ｍ． Ａｎｇｅｌｅｓ Ｈｅｒｒａｎｚ， Ｓｈｅｎｇ Ｚｈａｎｇ， Ｌｕｉｓ Ｓａｎｃｈｅｚ， Ｎａｚａｒｉｏ Ｍａｒｔｉｎ， ａｎｄ Ｌｕｉｓ Ｅｃｈｅｇｏｙｅｎ: 'Ｓｅｌｆ-Ａｓｓｅｍｂｌｙ ｏｆ Ｃ６０ ｄ-Ｅｘｔｅｎｄｅｄ Ｔｅｔｒａｔｈｉａｆｕｌｖａｌｅｎｅ （ｅｘＴＴＦ） Ｄｙａｄｓ ｏｎＧｏｌｄ Ｓｕｒｆａｃｅｓ' Ｌａｎｇｍｕｉｒ Ｖｏｌｕｍｅ ２２， Ｉｓｓｕｅ ２５, 20060902, Ｐａｇｅｓ １０６１９-１０６２４ * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014218492A (en) * | 2012-07-17 | 2014-11-20 | 株式会社リコー | Fullerene derivative and method for producing the same |
| JP2015113301A (en) * | 2013-12-11 | 2015-06-22 | 株式会社リコー | Fullerene derivative and method of producing the same |
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