JP2005259436A - Solar cell and its manufacturing method - Google Patents
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- JP2005259436A JP2005259436A JP2004067268A JP2004067268A JP2005259436A JP 2005259436 A JP2005259436 A JP 2005259436A JP 2004067268 A JP2004067268 A JP 2004067268A JP 2004067268 A JP2004067268 A JP 2004067268A JP 2005259436 A JP2005259436 A JP 2005259436A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
Description
本発明は、有機材料を用いた太陽電池及びその製法に関するものである。 The present invention relates to a solar cell using an organic material and a manufacturing method thereof.
化石燃料は、エネルギー源として現在主流を占めているが、有限であり、また、炭酸ガスによる地球温暖化の問題があり、代替エネルギーが求められている。
太陽電池は、このような問題がなく、注目を集めている。
現在、普及している太陽電池は、シリコン系である。
しかしながら、シリコン系太陽電池は、製造コストが高いという問題がある。
そこで、安価が有機材料を用いた太陽電池の開発が進められている。
有機太陽電池としては、電極間にポルフィリン誘導体を挟持したものが開示されている（特許文献１参照）。
しかし、ポルフィリン誘導体は、電荷輸送効果が十分でなかった。
Fossil fuels currently occupy the mainstream as an energy source, but are finite and have a problem of global warming due to carbon dioxide gas, and alternative energy is required.
Solar cells do not have such problems and are attracting attention.
Currently, solar cells that are widely used are silicon-based.
However, silicon-based solar cells have a problem of high manufacturing costs.
Therefore, development of inexpensive solar cells using organic materials has been promoted.
As an organic solar cell, a solar cell in which a porphyrin derivative is sandwiched between electrodes is disclosed (see Patent Document 1).
However, the porphyrin derivative has not been sufficient in charge transport effect.
そこで、光励起有機分子と電荷輸送高分子の混合溶液から電解重合による薄膜作成法による製造方法が開発された（非特許文献１参照）。 Then, the manufacturing method by the thin film preparation method by electropolymerization from the mixed solution of a photoexcited organic molecule and a charge transport polymer was developed (refer nonpatent literature 1).
しかし、この方法によると、光励起有機分子の電荷輸送高分子に対する量を少なくしないと成膜できないという問題があった。このため、光励起有機分子のドープ量は少なくせざるを得ず、光電変換性能が小さくなるという問題がある。また、光励起有機分子のドープ量が少ないため、アルミ等の金属界面とのショットキー障壁部位が少なくなり、電荷分離、移動が難しいため、乾式有機太陽電池に応用することは困難であった。 However, this method has a problem that the film cannot be formed unless the amount of the photoexcited organic molecule with respect to the charge transport polymer is reduced. For this reason, there is a problem that the doping amount of the photoexcited organic molecules must be reduced, and the photoelectric conversion performance is reduced. Further, since the amount of doped photoexcited organic molecules is small, the number of Schottky barrier portions with the metal interface such as aluminum is reduced, and charge separation and migration are difficult, so that it is difficult to apply to dry organic solar cells.
また、光励起有機分子と電荷輸送高分子の混合溶液をスピンコート法により成膜する方法は、光励起有機分子と電荷輸送高分子の結合が不十分であり、光励起有機分子で励起された電子の移動効率が低く、光電変換性能が低いという問題があった。 In addition, the method of forming a film of a mixed solution of photoexcited organic molecules and charge transporting polymer by spin coating method has insufficient bonding between photoexcited organic molecules and charge transporting polymer, and the movement of electrons excited by photoexcited organic molecules There was a problem that efficiency was low and photoelectric conversion performance was low.
更に、蒸着により成膜する方法もあるが（特許文献２参照）、これも光励起有機分子と電荷輸送高分子の結合が不十分であり、光励起有機分子で励起された電子の移動効率が低く、光電変換性能が低いという問題があった。
従って、本発明の目的は、このような問題点がなく、光電変換性能が高い太陽電池を提供することにある。 Accordingly, an object of the present invention is to provide a solar cell that does not have such problems and has high photoelectric conversion performance.
斯かる実情に鑑み、本発明者は、鋭意研究を行った結果、電荷輸送高分子を主成分とする電荷輸送高分子層と、光励起有機分子を主成分とする光励起有機分子層の２層に分け、これらの層を重合により形成し、かつ両層間も化学結合させれば、上記問題点がなく高性能の有機太陽電池が得られることを見出し本発明を完成した。 In view of such circumstances, as a result of intensive research, the inventor of the present invention has two layers: a charge transporting polymer layer mainly composed of a charge transporting polymer and a photoexcited organic molecule layer mainly composed of a photoexcited organic molecule. It was found that if these layers were formed by polymerization and both layers were chemically bonded, a high-performance organic solar cell could be obtained without the above-mentioned problems, and the present invention was completed.
即ち、本発明は次のものを提供するものである。 That is, the present invention provides the following.
＜１＞ ２つの電極間に電荷輸送高分子と光励起有機分子を有する太陽電池であって、電荷輸送高分子を主成分とする電荷輸送高分子層を重合により形成した後、該高分子層に化学結合して光励起有機分子を主成分とする光励起有機分子層を重合により形成したことを特徴とする有機太陽電池。 <1> A solar cell having a charge transport polymer and a photoexcited organic molecule between two electrodes, and after forming a charge transport polymer layer mainly composed of a charge transport polymer by polymerization, An organic solar cell characterized in that a photoexcited organic molecular layer mainly composed of photoexcited organic molecules by chemical bonding is formed by polymerization.
＜２＞ 重合が逐次重合である＜１＞記載の有機太陽電池。 <2> The organic solar cell according to <1>, wherein the polymerization is sequential polymerization.
＜３＞ 電荷輸送高分子層における電荷輸送高分子に対する光励起有機分子の含有比率が０．１〜８０ｍｏｌ％である＜１＞又は＜２＞記載の有機太陽電池。 <3> The organic solar cell according to <1> or <2>, wherein the content ratio of the photoexcited organic molecule to the charge transport polymer in the charge transport polymer layer is 0.1 to 80 mol%.
＜４＞ 電荷輸送高分子を主成分とする電荷輸送高分子層に接する電極から、光励起有機分子を主成分とする光励起有機分子層に接触する電極に近づくにつれて、両層の電荷輸送高分子の含有量比が段階的に減少すると共に、光励起有機分子の含有量比が段階的に増加し、かつ電荷輸送高分子と光励起有機分子は互いに共有結合していることを特徴とする＜１＞、＜２＞又は＜３＞記載の有機太陽電池。 <4> From the electrode in contact with the charge transport polymer layer mainly composed of the charge transport polymer to the electrode in contact with the photoexcited organic molecule layer mainly composed of the photoexcited organic molecule, <1> characterized in that the content ratio decreases stepwise, the content ratio of the photoexcited organic molecule increases stepwise, and the charge transport polymer and the photoexcited organic molecule are covalently bonded to each other. <2> or <3> The organic solar cell according to <3>.
＜５＞ 光励起有機分子を主成分とする光励起有機分子層中で、電荷輸送高分子に対する光励起有機分子の含有比率が０．１〜８０ｍｏｌ％である請求項１〜４の何れか１項記載の有機太陽電池。 <5> The content ratio of the photoexcited organic molecule to the charge transporting polymer in the photoexcited organic molecule layer mainly composed of the photoexcited organic molecule is 0.1 to 80 mol%. 5. Organic solar cell.
＜６＞ 電極上に電荷輸送高分子を主成分とする電荷輸送高分子層を重合により形成した後、該高分子層に化学結合して光励起有機分子を主成分とする光励起有機分子層を重合により形成し、次いで他方の電極を形成することを特徴とする有機太陽電池の製造方法。 <6> A charge transporting polymer layer mainly composed of a charge transporting polymer is formed on the electrode by polymerization, and then chemically bonded to the polymer layer to polymerize the photoexcited organic molecule layer mainly composed of photoexcited organic molecules. And then forming the other electrode. A method for producing an organic solar cell, comprising:
＜７＞ 電極上に、光励起有機分子を主成分とする光励起有機分子層を重合により形成した後、該有機分子層に化学結合して電荷輸送高分子を主成分とする電荷輸送高分子層を重合により形成し、次いで他方の電極を形成することを特徴とする有機太陽電池の製造方法。 <7> A photoexcited organic molecular layer mainly composed of photoexcited organic molecules is formed on the electrode by polymerization, and then a charge transporting polymer layer mainly composed of the charge transporting polymer is chemically bonded to the organic molecular layer. A method for producing an organic solar cell, characterized by forming by polymerization and then forming the other electrode.
＜８＞ 重合が電解重合である＜６＞又は＜７＞記載の製造方法。 <8> The production method according to <6> or <7>, wherein the polymerization is electrolytic polymerization.
＜９＞ 反応液を表面上に流動させて行うことを特徴とする＜６＞、＜７＞又は＜８＞記載の製造方法。 <9> The production method according to <6>, <7>, or <8>, wherein the reaction liquid is flowed on the surface.
本発明の有機太陽電池は、光電変換性能が高い乾式有機太陽電池である。 The organic solar cell of the present invention is a dry organic solar cell with high photoelectric conversion performance.
本発明の太陽電池は、２つの電極間に電荷輸送高分子と光励起有機分子を有する太陽電池であって、電荷輸送高分子を主成分とする電荷輸送高分子層を重合により形成した後、該高分子層に化学結合して光励起有機分子を主成分とする光励起有機分子層を重合により形成したことを特徴とする。 The solar cell of the present invention is a solar cell having a charge transport polymer and a photoexcited organic molecule between two electrodes, and after forming a charge transport polymer layer containing the charge transport polymer as a main component by polymerization, A photoexcited organic molecular layer mainly composed of photoexcited organic molecules bonded chemically to the polymer layer is formed by polymerization.
以下、本発明を図面を用いて詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to the drawings.
図１は、本発明の有機太陽電池の１例を示す断面図である。 FIG. 1 is a cross-sectional view showing an example of the organic solar battery of the present invention.
図１において、１は基板であり、材料としては、ガラスが一般的であるが、透明樹脂等も用いることができる。 In FIG. 1, reference numeral 1 denotes a substrate, and the material is generally glass, but a transparent resin or the like can also be used.
基板１上には、電極２が設けられている。この電極の材料としては、金、ＩＴＯ、ＦＴＯ等が挙げられる。電極を作成するには、このような金属を蒸着する方法が挙げられる。
電極２上には、電荷輸送高分子層３が設けられている。ここで用いられる電荷輸送高分子としては、ポリチオフェン、トリフェニルアミン、ポリアニリン、ポリピロール、フタロシアニン等が挙げられ、これらは、１種又は２種以上を選択して用いることができる。
An
On the
電荷輸送高分子層は、これら電荷輸送高分子を主成分とするが、後述する光励起有機分子を含むことが好ましい。電荷輸送高分子層中の電荷輸送高分子と光励起有機分子の量比は、同層中一定でもよいが、電極２から離れ、電極５に近づくにつれて、電荷輸送高分子の量が段階的に少なくなるような多層構造が好ましい。電荷輸送高分子層中の電荷輸送高分子に対する光励起有機分子の含有比率は、０．１〜８０ｍｏｌ％とすることが好ましい。
The charge transport polymer layer contains these charge transport polymers as the main component, but preferably contains photoexcited organic molecules described later. The amount ratio of the charge transport polymer and the photoexcited organic molecule in the charge transport polymer layer may be constant in the same layer, but the amount of the charge transport polymer gradually decreases as the distance from the
電荷輸送高分子層を形成する方法は、重合によるが、逐次重合で電解重合とすることが好ましい。逐次重合法によれば、共有結合による高効率電子移動が可能となり、好ましい。具体的には、例えば電荷輸送高分子としてポリチオフェン（ｐＴｈ）層を形成する場合、溶媒としてジクロロメタン、電解質としてテトラブチルアンモニウムヘキサフルオロホスフェート（ＴＢＡＰＦ６）、及びビチオフェン（ＢＩＴｈ）の混合溶液を用いて電解重合をおこなう。このとき、電位を０〜２Ｖで掃引（５０ｍＶ／ｓ）して電解重合反応によりｐＴｈ層を形成することが好ましい。 The method for forming the charge transporting polymer layer is based on polymerization, but it is preferable to perform sequential polymerization and electrolytic polymerization. The sequential polymerization method is preferable because it enables highly efficient electron transfer by covalent bond. Specifically, for example, when a polythiophene (pTh) layer is formed as a charge transport polymer, electrolytic polymerization is performed using a mixed solution of dichloromethane as a solvent, tetrabutylammonium hexafluorophosphate (TBAPF6), and bithiophene (BITh) as an electrolyte. To do. At this time, it is preferable to form a pTh layer by an electropolymerization reaction by sweeping the potential at 0 to 2 V (50 mV / s).
電荷輸送高分子層上３の上には、光励起有機分子層４が設けられている。これら両層は、化学接合させ、電荷の流れを良好にする。化学結合としては共有結合が好ましい。
A photoexcited organic
光励起有機分子層で用いられる光励起有機分子としては、ポルフィリン、フラーレン、フタロシアニン、ルテニウム錯体等が挙げられる。 Examples of the photoexcited organic molecule used in the photoexcited organic molecular layer include porphyrin, fullerene, phthalocyanine, and ruthenium complex.
光励起有機分子層は、これら光励起有機分子を主成分とするが前述の電荷輸送高分子を含むことが好ましい。光励起有機分子中の光励起有機分子と電荷輸送高分子との量比は、同層中一定でもよいが、電極２から離れ、電極５に近づくにつれて、電荷輸送高分子の量が段階的に少なくなるような多層構造が好ましい。このようにすることにより、電極５側の光励起有機分子量が増大し、電極界面とのショットキー障壁部位が増大し、電荷分離移動効率を向上させることができ、太陽電池の光電変換効率が向上する。電荷輸送高分子に対する光励起有機分子の量は、０．１〜８０ｍｏｌ％とすることが好ましい。
The photoexcited organic molecular layer is mainly composed of these photoexcited organic molecules, but preferably contains the above-described charge transporting polymer. The quantity ratio of the photoexcited organic molecule to the charge transporting polymer in the photoexcited organic molecule may be constant in the same layer, but the amount of the charge transporting polymer decreases stepwise as the distance from the
光励起有機分子層を形成する方法は、重合によるが、逐次重合で電解重合とすることが好ましい。具体的には、例えば光励起有機分子としてポルフィリン誘導体（ＴＴｈＰ）層を形成する場合、溶媒としてジクロロメタン、電解質としてテトラブチルアンモニウムヘキサフルオロホスフェート（ＴＢＡＰＦ６）、及びポルフィリン誘導体（ＴＴｈＰ）の混合溶液を用いて電解重合をおこなう。このとき、電位を０〜２Ｖで掃引（５０ｍＶ／ｓ）して電解重合反応によりＴＴｈＰ層を形成することが好ましい。このとき、ポリチオフェン（ｐＴｈ）に対するポルフィリン誘導体（ＴＴｈＰ）の相対量を増大させるために、電解重合回数を５〜４０サイクルで任意に調整することができる。 The method for forming the photoexcited organic molecular layer is based on polymerization, but it is preferable to perform electrolytic polymerization by sequential polymerization. Specifically, for example, when forming a porphyrin derivative (TThP) layer as a photoexcited organic molecule, electrolysis is performed using a mixed solution of dichloromethane as a solvent, tetrabutylammonium hexafluorophosphate (TBAPF6) as an electrolyte, and a porphyrin derivative (TThP). Polymerize. At this time, it is preferable to form a TThP layer by an electrolytic polymerization reaction by sweeping the potential at 0 to 2 V (50 mV / s). At this time, in order to increase the relative amount of the porphyrin derivative (TThP) to the polythiophene (pTh), the number of times of electrolytic polymerization can be arbitrarily adjusted in 5 to 40 cycles.
上記２つの電解重合反応時においては、反応液を表面上に流動させながら反応させることが好ましい。具体的には、反応液を攪拌させることが挙げられる。このようにすることにより、反応表面上に溶液の対流が生じ、膜の緻密化を促進させて再現性、均一性、膜強度を増加させることができ、電子又は正孔の伝導性を向上させることができる。さらに、短絡防止効果もある。反応液の流速は、０．０１〜３０００ｃｍ／秒が好ましく、更に、１〜３００ｃｍ／秒が好ましい。また、攪拌は、スターラーの回転速度が１〜５０００ｒｐｍが好ましく、特に１００〜５００ｒｐｍが好ましい。 At the time of the two electrolytic polymerization reactions, it is preferable that the reaction is carried out while flowing the reaction solution on the surface. Specifically, the reaction liquid can be stirred. By doing so, convection of the solution is generated on the reaction surface, and the densification of the film can be promoted, so that reproducibility, uniformity and film strength can be increased, and the conductivity of electrons or holes is improved. be able to. Furthermore, there is also a short circuit prevention effect. The flow rate of the reaction liquid is preferably 0.01 to 3000 cm / second, and more preferably 1 to 300 cm / second. The stirring is preferably performed at a stirrer rotational speed of 1 to 5000 rpm, particularly preferably 100 to 500 rpm.
光励起有機分子４上には、電極５が形成されている。この電極は、アルミニウム、等の蒸着により形成される。
電極５の上には、ガラス基板６がある。ガラス基板６は、電極５を蒸着した後、光励起有機分子層上に設置される。
本発明においては、上記層の他、他の層を設けてもよい。このような層としては、例えば、ポリ ３−ドデシルチオフェン（Ｐ３ＤＴ）を含有する短絡防止層等が挙げられる。
An
On the
In the present invention, in addition to the above layers, other layers may be provided. Examples of such a layer include a short-circuit prevention layer containing poly 3-dodecylthiophene (P3DT).
このような構造を有する本発明の太陽電池に、光を照射することにより、光励起有機分子の電子が励起され、発生した電子は、電極５の界面とのショットキー障壁を用いて電極５側に流れ、光励起有機分子で発生した正孔は、電荷輸送高分子を通り電極２に流れる。
By irradiating the solar cell of the present invention having such a structure with light, the electrons of the photoexcited organic molecules are excited, and the generated electrons are directed to the
以下、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example is given and the present invention is explained still in detail, the present invention is not limited to these.
１、２（逐次重合の系）
真空蒸着して作成したくし型金電極上にＰ３ＤＴクロロホルム溶液（２３ｍＭ）をスピンコート（６回）法により塗布し、Ｐ３ＤＴ（Ｓ）／Ａｕを得た。脱気条件下でＰ３ＤＴ（Ｓ）／Ａｕを作用極とし１ｍＭのＢｉＴｈおよび０．１ＭのｎＢｕ4ＮＰＦ6を含むＣＨ2Ｃｌ2溶液（１ｍＭ）中、５０ｍＶ／ｓｅｃで０〜２Ｖｖｓ．Ａｇ ｗｉｒｅの範囲で１０回電位挿引を行って、ＰｏｌｙＢｉＴｈ（１０）／Ｐ３ＤＴ（Ｓ）／Ａｕ（括弧内の数字は重合回数を示す。以下同じ）を得た。洗浄、乾燥の後、１ｍＭのＴＴｈＰおよび０．１ＭのｎＢｕ4ＮＰＦ6を含むＣＨ2Ｃｌ2溶液中、５０ｍＶ／ｓｅｃで０〜２Ｖｖｓ．Ａｇ ｗｉｒｅの範囲で１回もしくは１０回電位挿引を行い、ｐｏｌｙＴＴｈＰ（１）／ｐｏｌｙＢｉＴｈ（１０）／Ｐ３ＤＴ（Ｓ）／ＡｕまたはｐｏｌｙＴＴｈＰ（１０）／ｐｏｌｙＢｉＴｈ（１０）／Ｐ３ＤＴ（Ｓ）／Ａｕを得た。引き続きくし型マスクを施してＴＴｈＰ側にアルミニウムを真空蒸着し、Ａｌ／ＰｏｌｙＴＴｈＰ（１）／ｐｏｌｙＢｉＴｈ（１０）／Ｐ３ＤＴ（Ｓ）／Ａｕ または Ａｌ／ｐｏｌｙＴＴｈＰ（１０）／ｐｏｌｙＢｉＴｈ（１０）／Ｐ３ＤＴ（Ｓ）／Ａｕを得た。
1, 2 (Sequential polymerization system)
A P3DT chloroform solution (23 mM) was applied by spin coating (six times) on a comb-shaped gold electrode prepared by vacuum evaporation to obtain P3DT (S) / Au. In a CH 2 Cl 2 solution (1 mM) containing 1 mM BiTh and 0.1 M nBu 4 NPF 6 using P3DT (S) / Au as the working electrode under degassing conditions, 0 to 2 V vs. 0 at 50 mV / sec. Potential insertion was performed 10 times in the range of Ag wire to obtain PolyBiTh (10) / P3DT (S) / Au (the numbers in parentheses indicate the number of polymerizations; the same applies hereinafter). After washing and drying, 0 to 2 Vvs. At 50 mV / sec in a CH 2 Cl 2 solution containing 1 mM TThP and 0.1 M nBu 4 NPF 6 . In the range of Ag wire, potential insertion is performed once or 10 times, and polyTThP (1) / polyBiTh (10) / P3DT (S) / Au or polyTThP (10) / polyBiTh (10) / P3DT (S) / Au Obtained. Subsequently, a comb mask is applied, and aluminum is vacuum-deposited on the TThP side, and Al / PolyTThP (1) / polyBiTh (10) / P3DT (S) / Au or Al / polyTThP (10) / polyBiTh (10) / P3DT (S ) / Au was obtained.
３、４（比較例、混合の系）
真空蒸着して作成したくし型金電極上に Ｐ３ＤＴ クロロホルム溶液（２３ｍＭ）をスピンコート（６回）法により塗布し、Ｐ３ＤＴ（Ｓ）／Ａｕを得た。また同一の Ｐ３ＤＴ溶液を金電極上にデップコートしてＰ３ＤＴ（Ｄ）／Ａｕを得た。脱気条件下でこれらの電極を作用極とし０．２５ｍＭ ＴＴｈＰ、０．７５ｍＭ ＢｉＴｈ、０．１Ｍ ｎＢｕ4ＮＰＦ6を含むＣＨ2Ｃｌ2溶液中、５０ｍＶ／ｓｅｃで０〜２Ｖｖｓ．Ａｇ ｗｉｒｅの範囲で１０回電位挿引を行って、ｐｏｌｙ（ＢｉＴｈ＋ＴＴｈＰ）（１０）／Ｐ３ＤＴ（Ｓ）／Ａｕまたはｐｏｌｙ（ＢｉＴｈ＋ＴＴｈＰ）（１０）／Ｐ３ＤＴ（Ｄ）／Ａｕを得た。引き続きくし型マスクを施してＢｉＴｈ＋ＴＴｈＰ側にアルミニウムを真空蒸着し、Ａｌ／ｐｏｌｙ（ＢｉＴｈ＋ＴＴｈＰ）（１０）／Ｐ３ＤＴ（Ｓ）／ＡｕまたはＡｌ／ｐｏｌｙ（ＢｉＴｈ＋ＴＴｈＰ）（１０）／Ｐ３ＤＴ（Ｄ）／Ａｕを得た。
3, 4 (Comparative example, mixed system)
A P3DT chloroform solution (23 mM) was applied by spin coating (six times) on a comb-shaped gold electrode prepared by vacuum evaporation to obtain P3DT (S) / Au. The same P3DT solution was dip coated on the gold electrode to obtain P3DT (D) / Au. Under deaeration conditions, these electrodes were used as working electrodes. In a CH 2 Cl 2 solution containing 0.25 mM TThP, 0.75 mM BiTh, and 0.1 M nBu 4 NPF 6, 0 to 2 Vvs. The potential insertion was performed 10 times in the range of Ag wire to obtain poly (BiTh + TThP) (10) / P3DT (S) / Au or poly (BiTh + TThP) (10) / P3DT (D) / Au. Subsequently, a comb mask is applied, and aluminum is vacuum-deposited on the BiTh + TThP side, and Al / poly (BiTh + TThP) (10) / P3DT (S) / Au or Al / poly (BiTh + TThP) (10) / P3DT (D) / Au Obtained.
括弧内の数字は重合回数を示す。（S）はスピンコート、(D)はディッピングを示す。 The numbers in parentheses indicate the number of polymerizations. (S) shows spin coating, and (D) shows dipping.
１）、２）、３）を比較することで、逐次重合の効果により短絡光電流が増加していることが判る。 By comparing 1), 2) and 3), it can be seen that the short-circuit photocurrent is increased due to the effect of sequential polymerization.
［試験例１］ [Test Example 1]
塩化メチレンに対し、１．５０ｍｍｏｌ／ｌの濃度のビチオフェンと、０．２５ｍｍｏｌ／ｌの濃度のテトラチエニルポルフィリンとなるようにそれぞれを溶解し、さらに０．１ｍｍｏｌ／ｌの濃度になるようにテトラブチルアンモニウムヘキサフルオロリン酸を溶解させた。この溶液をナシ型フラスコに入れ、そこに電線によって外部から通電可能なＩＴＯガラスを浸漬させた。さらに対極用の白金電極と参照電極用の銀電極を液中に浸し、この溶液をフラスコ中で磁気撹拌した（攪拌は２５０ｒｐｍで行った）。サイクリックボルタンメトリーによってこのＩＴＯガラスの電位を自然電位から＋２Ｖまで毎分５０ｍＶの速さで昇圧し、その後直ちに同じ速度で０Ｖまで降圧した。ここまでの一連の操作の再現性を確認するため、同様の製膜をさらに２回（計３回）行った。 In methylene chloride, each of bithiophene at a concentration of 1.50 mmol / l and tetrathienylporphyrin at a concentration of 0.25 mmol / l are dissolved, and tetrabutyl is further added to a concentration of 0.1 mmol / l. Ammonium hexafluorophosphoric acid was dissolved. This solution was put into a pear-shaped flask, and ITO glass that can be energized from the outside by electric wires was immersed therein. Further, a platinum electrode for a counter electrode and a silver electrode for a reference electrode were immersed in the liquid, and this solution was magnetically stirred in a flask (stirring was performed at 250 rpm). The potential of the ITO glass was increased from the natural potential to +2 V by cyclic voltammetry at a rate of 50 mV per minute, and then immediately decreased to 0 V at the same rate. In order to confirm the reproducibility of the series of operations so far, the same film formation was further performed twice (total 3 times).
得られたサイクリックボルタモグラムを図３にまとめた。これらの曲線は非常に近接しており、再現性のある製膜ができていることが分かる。また、２Ｖ時での電流値が非常に高いことから、溶液との電子のやりとりが起こりやすい膜、すなわち緻密な構造で、かつ、電解液が染みこみやすい構造の膜になっていることが分かる。 The obtained cyclic voltammograms are summarized in FIG. These curves are very close and it can be seen that a reproducible film is formed. In addition, since the current value at 2 V is very high, it can be seen that the film is easy to exchange electrons with the solution, that is, a film having a dense structure and a structure in which the electrolyte solution can easily permeate. .
［試験例２］
水に対し、０．１ｍｍｏｌ／ｌの過塩素酸ナトリウムと５ｍｍｏｌ／ｌのメチルビオロゲンを溶解させたものを電解液とし、白金電極を対極に、銀電極を参照電極として、白色光を照射し、実施例１で作製した高分子複合膜電極（３枚中はじめの１枚）の光電流を測定して、外部量子効率を算出した結果を図４に示す。
[Test Example 2]
A solution in which 0.1 mmol / l sodium perchlorate and 5 mmol / l methyl viologen are dissolved in water is used as an electrolyte, a platinum electrode is used as a counter electrode, and a silver electrode is used as a reference electrode. FIG. 4 shows the result of calculating the external quantum efficiency by measuring the photocurrent of the polymer composite membrane electrode (first one of the three) prepared in Example 1.
この結果から、上述の方法によって作製された高分子複合膜電極は、非常に高い外部量子効率を示すことが分かる。 From this result, it can be seen that the polymer composite membrane electrode produced by the above-described method exhibits a very high external quantum efficiency.
［比較（試験）例１］
上記の試験例１における、撹拌しながら電解重合を行うことを止めて、溶液を静止状態にし、そのまま電解重合を行った結果のサイクリックボルタモグラムを図３にまとめた（計３回）。
[Comparative (Test) Example 1]
The cyclic voltammograms of the results of the above-described Test Example 1 obtained by stopping the electrolytic polymerization while stirring and making the solution stationary and performing the electrolytic polymerization as it is are summarized in FIG. 3 (total 3 times).
この結果から、攪拌下の場合と異なり、ピーク位置や形状、２Ｖ時の電流などに大きくばらつきがあることが分かる。また、２Ｖ時の電流値が低いため、溶液との電子のやりとりが起こりにくい膜、すなわち空隙は多いが電解液が染みこみにくい膜になっていることが分かる。 From this result, it can be seen that there is a large variation in the peak position, shape, current at 2 V, and the like, unlike the case of stirring. In addition, since the current value at 2 V is low, it can be seen that the film is less likely to exchange electrons with the solution, that is, the film has a large number of voids but does not easily soak in the electrolyte.
［比較（試験）例２］
また、試験例１での光電流測定と全く同様の方法で、比較（試験）例１で作製した高分子複合膜電極（３枚中はじめの１枚）の光電流測定を行って、外部量子効率を算出した結果を図４にまとめた。
撹拌なしの場合は外部量子効率も大幅に低下することが分かる。
[Comparison (Test) Example 2]
Further, the photocurrent measurement of the polymer composite membrane electrode (first one of the three) prepared in Comparative (Test) Example 1 was performed in the same manner as the photocurrent measurement in Test Example 1, and the external quantum was measured. The results of calculating the efficiency are summarized in FIG.
It can be seen that the external quantum efficiency is greatly reduced without stirring.
本発明の太陽電池は、重合、特に逐次重合により作成されるため、共有結合による高効率電子移動が可能となる。また、光励起有機分子と電荷輸送高分子との量比を変化させることにより、電極界面とのショットキー障壁部位が増大し、電荷分離移動効率を向上させることができ、太陽電池の光電変換効率が向上する。また、反応液を表面上に流動させながら反応させることにより、反応表面上に溶液の対流が生じ、膜の緻密化を促進させて再現性、均一性、膜強度を増加させることができ、電子又は正孔の伝導性を向上させることができ、更に短絡防止効果もある。 Since the solar cell of the present invention is produced by polymerization, particularly sequential polymerization, highly efficient electron transfer by a covalent bond is possible. In addition, by changing the quantity ratio between the photoexcited organic molecule and the charge transport polymer, the Schottky barrier site with the electrode interface can be increased, the charge separation transfer efficiency can be improved, and the photoelectric conversion efficiency of the solar cell can be improved. improves. In addition, by reacting while allowing the reaction solution to flow on the surface, convection of the solution occurs on the reaction surface, which can promote densification of the film and increase reproducibility, uniformity, and film strength. Alternatively, the hole conductivity can be improved, and further, there is an effect of preventing a short circuit.
１ 基板
２ 電極
３ 電荷輸送高分子層
４ 光励起有機分子層
５ 電極
６ 基板
1
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