JP2016111036A - Photovoltaic element - Google Patents
Photovoltaic element Download PDFInfo
- Publication number
- JP2016111036A JP2016111036A JP2014243748A JP2014243748A JP2016111036A JP 2016111036 A JP2016111036 A JP 2016111036A JP 2014243748 A JP2014243748 A JP 2014243748A JP 2014243748 A JP2014243748 A JP 2014243748A JP 2016111036 A JP2016111036 A JP 2016111036A
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- Prior art keywords
- layer
- photoelectric conversion
- electron
- solution
- compound
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Photovoltaic Devices (AREA)
Abstract
Description
本発明は光起電力素子に関する。 The present invention relates to a photovoltaic device.
太陽電池は、現在深刻さを増すエネルギー問題に対して有力な環境に優しいエネルギー源として注目されている。現在、太陽電池の光起電力素子の半導体材料としては、単結晶シリコン、多結晶シリコン、アモルファスシリコン、化合物半導体などの無機物が使用されている。しかし、無機半導体を用いて製造される太陽電池は、火力発電などの発電方式と比べてコストが高いために、一般家庭に広く普及するには至っていない。コスト高の要因は主として、真空かつ高温下で半導体薄膜を形成するプロセスにある。そこで、製造プロセスの簡略化が期待される半導体材料として、共役系重合体や有機結晶などの有機半導体や有機色素を用いた有機太陽電池が検討されている。このような有機太陽電池においては、半導体材料を塗布法で作製することが可能なため、製造プロセスを大幅に簡略化することができる。 Solar cells are currently attracting attention as a potential environmentally friendly energy source for increasing energy problems. At present, inorganic materials such as single crystal silicon, polycrystalline silicon, amorphous silicon, and compound semiconductors are used as semiconductor materials for photovoltaic elements of solar cells. However, solar cells manufactured using inorganic semiconductors have not been widely used in ordinary households because they are more expensive than power generation methods such as thermal power generation. The high cost factor is mainly in the process of forming the semiconductor thin film under vacuum and high temperature. Therefore, organic semiconductor cells using organic semiconductors such as conjugated polymers and organic crystals and organic dyes are being studied as semiconductor materials that are expected to simplify the manufacturing process. In such an organic solar cell, since a semiconductor material can be produced by a coating method, the manufacturing process can be greatly simplified.
しかし、共役系重合体などを用いた有機太陽電池は、従来の無機半導体を用いた太陽電池と比べて光電変換効率および熱安定性が低いために、まだ実用化には至っていない。有機太陽電池の実用化のためには、高い光電変換効率とともに、それを長時間持続できる熱安定性、すなわち高耐久性の実現が必須である。 However, organic solar cells using a conjugated polymer or the like have not yet been put into practical use because they have lower photoelectric conversion efficiency and thermal stability than conventional solar cells using inorganic semiconductors. In order to put organic solar cells into practical use, it is essential to realize high photoelectric conversion efficiency and thermal stability that can sustain them for a long time, that is, high durability.
有機太陽電池の光電変換効率および耐久性を向上させる方法の一つとして、正孔取出し層を発電層と陽極の間に設置する方法が挙げられる。正孔取出し層の材料としては酸化タングステンや酸化モリブデンのような無機酸化物が知られている(例えば特許文献1)。 One method for improving the photoelectric conversion efficiency and durability of the organic solar cell is to install a hole extraction layer between the power generation layer and the anode. As materials for the hole extraction layer, inorganic oxides such as tungsten oxide and molybdenum oxide are known (for example, Patent Document 1).
しかし、本発明者らが検討を行ったところ、特許文献1に開示されている無機酸化物を単独で正孔取出し層として用いた素子の場合においては、初期の光電変換効率は優れていたものの、十分な熱安定性は得られず、耐久性は十分ではなかった。
However, when the present inventors examined, in the case of the element which used the inorganic oxide currently disclosed by
本発明は、熱安定性に優れた光起電力素子を提供することを目的とするものである。 An object of this invention is to provide the photovoltaic device excellent in thermal stability.
本発明者らが鋭意検討を重ねた結果、低い熱安定性は、正孔取出し層である無機酸化物と光電変換層の界面の熱安定性(例えば、エネルギー準位の整合性など)が悪いことが原因であると推察された。このことから本発明者らは、正孔取出し層と光電変換層との界面を安定化させることが重要であると考えた。そして、正孔取出し層と光電変換層との界面を安定化させるために、種々の材料を正孔取出し層と光電変換層の界面に挿入したところ、多価アルコールを界面に配置することで安定化させることが可能であることを見出した。 As a result of intensive studies by the present inventors, low thermal stability is poor in thermal stability (for example, energy level consistency) at the interface between the inorganic oxide as the hole extraction layer and the photoelectric conversion layer. It was inferred that this was the cause. Based on this, the present inventors considered that it is important to stabilize the interface between the hole extraction layer and the photoelectric conversion layer. In order to stabilize the interface between the hole extraction layer and the photoelectric conversion layer, various materials are inserted into the interface between the hole extraction layer and the photoelectric conversion layer. It was found that it is possible to make it.
すなわち、本発明は、少なくとも陰極、光電変換層、多価アルコールを含む正孔取出し層、および陽極をこの順に有する光起電力素子である。 That is, the present invention is a photovoltaic device having at least a cathode, a photoelectric conversion layer, a hole extraction layer containing a polyhydric alcohol, and an anode in this order.
本発明によれば、熱安定性に優れた光起電力素子を提供することができる。 According to the present invention, a photovoltaic device excellent in thermal stability can be provided.
本発明の光起電力素子について説明する。図1は本発明の光起電力素子の一態様を示す断面図である。図1の光起電力素子は、基板1の上に、陰極2、光電変換層3、正孔取出し層4および陽極5をこの順に有している。
The photovoltaic device of the present invention will be described. FIG. 1 is a cross-sectional view showing one embodiment of the photovoltaic element of the present invention. The photovoltaic element of FIG. 1 has a
基板1は、光電変換材料の種類や用途に応じて、電極材料や有機半導体層が積層できる基板であり、例えば、無アルカリガラス、石英ガラス、アルミニウム、鉄、銅、およびステンレスなどの合金、等の無機材料、ポリエステル、ポリカーボネート、ポリオレフィン、ポリアミド、ポリイミド、ポリフェニレンスルフィド、ポリパラキシレンポリメチルメタクリレート、エポキシ樹脂やフッ素系樹脂等の有機材料から任意の方法によって作製されたフィルムや板が使用可能である。また基板側から光を入射して用いる場合は、上記に示した各基板に80%程度の光透過性を持たせておくことが好ましい。
The
電極(陰極2および陽極5)の素材としては、金、白金、銀、銅、鉄、亜鉛、錫、アルミニウム、インジウム、クロム、ニッケル、コバルト、スカンジウム、バナジウム、イットリウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウム、モリブデン、タングステン、チタンなどの金属のほか、金属酸化物、複合金属酸化物(インジウム錫酸化物(ITO)、インジウム亜鉛酸化物(IZO)、アルミニウム亜鉛酸化物(AZO)、ガリウム亜鉛酸化物(GZO)など)、アルカリ金属やアルカリ土類金属(リチウム、マグネシウム、ナトリウム、カリウム、カルシウム、ストロンチウム、バリウム)なども好ましく用いられる。さらに、上記の金属からなる合金や上記の金属の積層体からなる電極も好ましく用いられる。また、グラファイト、グラファイト層間化合物、カーボンナノチューブ、グラフェン、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体を含む電極も好ましく用いられる。また、上記の電極材料は2種以上の材料から成る混合層、及び、積層構造であってもよい。
Materials for electrodes (
陰極2に用いられる導電性素材は、光電変換層3とオーミック接合するものであることが好ましい。さらに、後述する電子取出し層を用いた場合においては、陰極2に用いられる導電性素材は電子取出し層とオーミック接合するものであることが好ましい。また、陽極5に用いられる導電性素材は、正孔取出し層4とオーミック接合するものであることが好ましい。
The conductive material used for the
光起電力素子の陰極2または陽極5は光透過性を有する。少なくともいずれか一方が光透過性を有すればよいが、両方が光透過性を有してもよい。ここで光透過性を有するとは、光電変換層に入射光が到達して起電力が発生する程度に光を透過することを意味する。すなわち、光透過率として0%を超える値を有する場合、光透過性を有するという。この光透過性を有する電極は、400nm以上900nm以下の全ての波長領域において60−100%の光透過率を有することが好ましい。また、光透過性を有する電極の厚さは十分な導電性が得られればよく、材料によって異なるが、20nm〜300nmが好ましい。なお、光透過性を有しない電極は、導電性があれば十分であり、厚さも特に限定されない。
The
本発明の光起電力素子には、光電変換層3と陰極2の間に電子取出し層が設けられていてもよい。電子取出し層により、キャリアを取り出すのに適した界面状態を形成できるとともに、電極間の短絡を防止する効果がある。電子取出し層を形成する材料としては、例えば、1,4,5,8−ナフタレンテトラカルボキシリックジアンハイドライド、3,4,9,10−ペリレンテトラカルボキシリックジアンハイドライド、N,N'−ジオクチル−3,4,9,10−ナフチルテトラカルボキシジイミド、オキサゾール誘導体(2−(4−ビフェニリル)−5−(4−t−ブチルフェニル)−1,3,4−オキサジアゾール、2,5−ジ(1−ナフチル)−1,3,4−オキサジアゾール等)、トリアゾール誘導体(3−(4−ビフェニリル)−4−フェニル−5−(4−t−ブチルフェニル)−1,2,4−トリアゾール等)、フェナントロリン誘導体、フラーレン誘導体、カーボンナノチューブ、ポリ−p−フェニレンビニレン系重合体にシアノ基を導入した誘導体(CN−PPV)などの電子輸送性を有する有機半導体が挙げられる。また、TiO2などの酸化チタン(TiOx)、ZnOなどの酸化亜鉛(ZnOx)、SiO2などの酸化ケイ素(SiOx)、SnO2などの酸化錫(SnOx)、In2O3などの酸化インジウム(InOx)、MoO3などの酸化モリブデン(MoOx)、WO3などの酸化タングステン(WOx)、Ta2O3などの酸化タンタル(TaOx)、BaTiO3などのチタン酸バリウム(BaTixOy)、BaZrO3などのジルコン酸バリウム(BaZrxOy)、ZrO2などの酸化ジルコニウム(ZrOx)、HfO2などの酸化ハフニウム(HfOx)、Al2O3などの酸化アルミニウム(AlOx)、Y2O3などの酸化イットリウム(YOx)、ZrSiO4などのケイ酸ジルコニウム(ZrSixOy)のような金属酸化物、Si3N4などの窒化ケイ素(SiNx)のような窒化物、CdSなどの硫化カドミウム(CdSx)、ZnSeなどのセレン化亜鉛(ZnSex)、ZnSなどの硫化亜鉛(ZnSx)、CdTeなどのテルル化カドミウム(CdTex)のような半導体などの無機材料も電子取出し層材料として好ましく用いることができる。これらの中でも無機酸化物であることが好ましく、電子取出し効率や電子移動の観点からn型半導体であることがより好ましい。さらに、n型半導体性の観点からは、前記無機酸化物が少なくとも亜鉛、チタン、すず、インジウムのいずれかを含むことが好ましく、少なくとも亜鉛、チタンを含むことがさらに好ましい。また、前記電子取出し層は、電子取出しや電子移動を阻害しない範囲において、上記無機化合物以外のものを含んでいてもよい。したがって、無機化合物層を形成する際に、金属塩や金属アルコキシドなどの前駆体溶液を塗布・加熱して形成する方法や、ナノ粒子分散液を基板に塗布して層を形成する方法を用いた場合において、加熱温度や時間、及びナノ粒子の合成条件により、完全には反応が進行しておらず、部分的に加水分解したり、部分的に縮合したりすることで、中間生成物となったり、前駆体と中間性生物、最終生成物などの混合物となったりしても良い。電子取出し層は、電子取出しに十分な厚さがあればよいが、厚くし過ぎると電子取出し効率が低下することがある。所望する光起電力素子の光電変換効率に応じて適宜最適な膜厚に設定すればよいため一概に言えるものではないが、一般的には0.1nm〜1000nmの厚さが好ましく、より好ましくは0.5nm〜100nm、さらに好ましくは5nm〜50nmである。
In the photovoltaic device of the present invention, an electron extraction layer may be provided between the
次に、光電変換層3について説明する。光電変換層3は、陰極2と、正孔取出し層4との間に存在し、少なくとも後述する電子供与性有機半導体および電子受容性有機半導体を含む。光電変換層の例としては、電子供与性有機半導体と電子受容性有機半導体の混合物からなる層、電子供与性有機半導体からなる層と電子受容性有機半導体からなる層を積層した構造、電子供与性有機半導体からなる層と電子受容性有機半導体からなる層の間に、これらの混合物からなる層を積層した構造などが挙げられる。光電変換層は、電子供与性有機半導体または電子受容性有機半導体を2種以上含有していてもよい。また、電子供与性有機半導体と電子受容性有機半導体は、混合層を形成していることが好ましい。
Next, the
光電変換層における電子供与性有機半導体と電子受容性有機半導体の含有比率は特に限定されないが、電子供与性有機半導体:電子受容性有機半導体の重量分率が、1〜99:99〜1の範囲であることが好ましく、より好ましくは10〜90:90〜10の範囲であり、さらに好ましくは20〜60:80〜40の範囲である。 The content ratio of the electron-donating organic semiconductor and the electron-accepting organic semiconductor in the photoelectric conversion layer is not particularly limited, but the weight fraction of the electron-donating organic semiconductor: electron-accepting organic semiconductor is in the range of 1 to 99: 99-1. More preferably, it is the range of 10-90: 90-10, More preferably, it is the range of 20-60: 80-40.
光電変換層の厚さは、電子供与性有機半導体および電子受容性有機半導体が光吸収によって光起電力を生じるのに十分であればよい。好ましい厚さは材料によって異なるが、一般的には10nm〜1000nmが好ましく、より好ましくは50nm〜500nmである。また、光電変換層は界面活性剤やバインダー樹脂、フィラー等の他の成分を含むものであってもよい。 The thickness of the photoelectric conversion layer may be sufficient for the electron donating organic semiconductor and the electron accepting organic semiconductor to generate a photovoltaic force by light absorption. The preferred thickness varies depending on the material, but generally it is preferably 10 nm to 1000 nm, more preferably 50 nm to 500 nm. The photoelectric conversion layer may contain other components such as a surfactant, a binder resin, and a filler.
電子供与性有機半導体は、p型半導体特性を示す有機物であれば特に限定されない。例えば、ポリチオフェン系重合体、2,1,3−ベンゾチアジアゾール−チオフェン系共重合体、キノキサリン−チオフェン系共重合体、チオフェンーベンゾジチオフェン系共重合体、ポリ−p−フェニレンビニレン系重合体、ポリ−p−フェニレン系重合体、ポリフルオレン系重合体、ポリピロール系重合体、ポリアニリン系重合体、ポリアセチレン系重合体、ポリチエニレンビニレン系重合体などの共役系重合体、H2フタロシアニン(H2Pc)、銅フタロシアニン(CuPc)、亜鉛フタロシアニン(ZnPc)等のフタロシアニン誘導体、ポルフィリン誘導体、N,N’−ジフェニル−N,N’−ジ(3−メチルフェニル)−4,4’−ジフェニル−1,1’−ジアミン(TPD)、N,N’−ジナフチル−N,N’−ジフェニル−4,4’−ジフェニル−1,1’−ジアミン(NPD)等のトリアリールアミン誘導体、4,4’−ジ(カルバゾール−9−イル)ビフェニル(CBP)等のカルバゾール誘導体、オリゴチオフェン誘導体(ターチオフェン、クウォーターチオフェン、セキシチオフェン、オクチチオフェンなど)等の低分子有機化合物などが挙げられる。これらを2種以上用いてもよい。 An electron donating organic semiconductor will not be specifically limited if it is an organic substance which shows p-type semiconductor characteristics. For example, polythiophene polymer, 2,1,3-benzothiadiazole-thiophene copolymer, quinoxaline-thiophene copolymer, thiophene-benzodithiophene copolymer, poly-p-phenylene vinylene polymer, Conjugated polymers such as poly-p-phenylene polymer, polyfluorene polymer, polypyrrole polymer, polyaniline polymer, polyacetylene polymer, polythienylene vinylene polymer, H 2 phthalocyanine (H 2 Pc), phthalocyanine derivatives such as copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), porphyrin derivatives, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1 , 1′-diamine (TPD), N, N′-dinaphthyl-N, N′-diphenyl-4, Triarylamine derivatives such as'-diphenyl-1,1'-diamine (NPD), carbazole derivatives such as 4,4'-di (carbazol-9-yl) biphenyl (CBP), oligothiophene derivatives (terthiophene, quarter Low molecular organic compounds such as thiophene, sexithiophene, and octithiophene). Two or more of these may be used.
ポリチオフェン系重合体とは、チオフェン骨格を主鎖に有する共役系重合体を指し、側鎖を有するものも含む。具体的には、ポリ−3−メチルチオフェン、ポリ−3−ブチルチオフェン、ポリ−3−ヘキシルチオフェン、ポリ−3−オクチルチオフェン、ポリ−3−デシルチオフェンなどのポリ−3−アルキルチオフェン、ポリ−3−メトキシチオフェン、ポリ−3−エトキシチオフェン、ポリ−3−ドデシルオキシチオフェンなどのポリ−3−アルコキシチオフェン、ポリ−3−メトキシ−4−メチルチオフェン、ポリ−3−ドデシルオキシ−4−メチルチオフェンなどのポリ−3−アルコキシ−4−アルキルチオフェンなどが挙げられる。 The polythiophene polymer refers to a conjugated polymer having a thiophene skeleton in the main chain, and includes those having side chains. Specifically, poly-3-alkylthiophene such as poly-3-methylthiophene, poly-3-butylthiophene, poly-3-hexylthiophene, poly-3-octylthiophene, poly-3-decylthiophene, poly- Poly-3-alkoxythiophene such as 3-methoxythiophene, poly-3-ethoxythiophene, poly-3-dodecyloxythiophene, poly-3-methoxy-4-methylthiophene, poly-3-dodecyloxy-4-methylthiophene And poly-3-alkoxy-4-alkylthiophene.
2,1,3−ベンゾチアジアゾール−チオフェン系共重合体とは、チオフェン骨格と2,1,3−ベンゾチアジアゾール骨格を主鎖に有する共役系共重合体を指す。2,1,3−ベンゾチアジアゾール−チオフェン系共重合体として、具体的には下記のような構造が挙げられる。下記式において、nは1〜1000の整数を示す。 The 2,1,3-benzothiadiazole-thiophene copolymer refers to a conjugated copolymer having a thiophene skeleton and a 2,1,3-benzothiadiazole skeleton in the main chain. Specific examples of the 2,1,3-benzothiadiazole-thiophene copolymer include the following structures. In the following formula, n represents an integer of 1 to 1000.
キノキサリン−チオフェン系共重合体とは、チオフェン骨格とキノキサリン骨格を主鎖に有する共役系共重合体を指す。キノキサリン−チオフェン系共重合体として、具体的には下記のような構造が挙げられる。下記式において、nは1〜1000の整数を示す。 The quinoxaline-thiophene copolymer refers to a conjugated copolymer having a thiophene skeleton and a quinoxaline skeleton in the main chain. Specific examples of the quinoxaline-thiophene copolymer include the following structures. In the following formula, n represents an integer of 1 to 1000.
チオフェン−ベンゾジチオフェン系重合体とは、チオフェン骨格とベンゾジチオフェン骨格を主鎖に有する共役系共重合体を指す。チオフェン−ベンゾジチオフェン系共重合体として、具体的には下記のような構造が挙げられる。下記式において、nは1〜1000の整数を示す。 The thiophene-benzodithiophene polymer refers to a conjugated copolymer having a thiophene skeleton and a benzodithiophene skeleton in the main chain. Specific examples of the thiophene-benzodithiophene copolymer include the following structures. In the following formula, n represents an integer of 1 to 1000.
ポリ−p−フェニレンビニレン系重合体とは、p−フェニレンビニレン骨格を主鎖に有する共役系重合体を指し、側鎖を有するものも含む。具体的には、ポリ[2−メトキシ−5−(2−エチルヘキシルオキシ)−1,4−フェニレンビニレン]、ポリ[2−メトキシ−5−(3’,7’−ジメチルオクチルオキシ)−1,4−フェニレンビニレン]などが挙げられる。 The poly-p-phenylene vinylene polymer refers to a conjugated polymer having a p-phenylene vinylene skeleton in the main chain, and includes those having side chains. Specifically, poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], poly [2-methoxy-5- (3 ′, 7′-dimethyloctyloxy) -1, 4-phenylene vinylene] and the like.
電子受容性有機半導体は、n型半導体特性を示す有機物であれば特に限定されない。例えば、1,4,5,8−ナフタレンテトラカルボキシリックジアンハイドライド、3,4,9,10−ペリレンテトラカルボキシリックジアンハイドライド、N,N'−ジオクチル−3,4,9,10−ナフチルテトラカルボキシジイミド、オキサゾール誘導体(2−(4−ビフェニリル)−5−(4−t−ブチルフェニル)−1,3,4−オキサジアゾール、2,5−ジ(1−ナフチル)−1,3,4−オキサジアゾール等)、トリアゾール誘導体(3−(4−ビフェニリル)−4−フェニル−5−(4−t−ブチルフェニル)−1,2,4−トリアゾール等)、フェナントロリン誘導体、フラーレン誘導体、カーボンナノチューブ、ポリ−p−フェニレンビニレン系重合体にシアノ基を導入した誘導体(CN−PPV)などが挙げられる。これらを2種以上用いてもよい。安定でキャリア移動度の高いn型半導体であることから、フラーレン誘導体が好ましく用いられる。 The electron-accepting organic semiconductor is not particularly limited as long as it is an organic substance exhibiting n-type semiconductor characteristics. For example, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, N, N′-dioctyl-3,4,9,10-naphthyltetracarboxyl Diimide, oxazole derivative (2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-di (1-naphthyl) -1,3,4 -Oxadiazole, etc.), triazole derivatives (3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole, etc.), phenanthroline derivatives, fullerene derivatives, carbon Nanotubes, derivatives in which a cyano group is introduced into a poly-p-phenylene vinylene polymer (CN-PPV), and the like can be mentioned. . Two or more of these may be used. A fullerene derivative is preferably used because it is an n-type semiconductor that is stable and has high carrier mobility.
フラーレン誘導体の具体例として、C60、C70、C76、C78、C82、C84、C90、C94を始めとする無置換のものと、[6,6]−フェニルC61 ブチリックアシッドメチルエステル([6,6]−C61−PCBM、または[60]PCBM)、[5,6]−フェニルC61 ブチリックアシッドメチルエステル、[6,6]−フェニルC61 ブチリックアシッドヘキシルエステル、[6,6]−フェニルC61 ブチリックアシッドドデシルエステル、フェニルC71 ブチリックアシッドメチルエステル([70]PCBM)を始めとする置換誘導体などが挙げられる。なかでも[70]PCBMがより好ましい。 Specific examples of the fullerene derivative include unsubstituted ones such as C 60 , C 70 , C 76 , C 78 , C 82 , C 84 , C 90 , C 94 and [6,6] -phenyl C61 butyric. Acid methyl ester ([6,6] -C61-PCBM, or [60] PCBM), [5,6] -phenyl C61 butyric acid methyl ester, [6,6] -phenyl C61 butyric acid hexyl ester, [ Examples include substituted derivatives such as 6,6] -phenyl C61 butyric acid dodecyl ester and phenyl C71 butyric acid methyl ester ([70] PCBM). Among these, [70] PCBM is more preferable.
次に、正孔取出し層4について説明する。本発明における正孔取出し層4は、多価アルコールと、正孔輸送性材料を含む。本発明における正孔取出し層4は、多価アルコールと正孔輸送性材料が混合した構造であっても、多価アルコールの層が正孔輸送性材料の層の光電変換層側に積層した構造であってもよい。混合層の場合、正孔取出し層における正孔輸送性材料と多価アルコールの含有比率は多価アルコールが正孔取出し層/発電層界面に存在すれば十分であり、正孔輸送性材料:多価アルコールが重量比率で1:99〜99:1の範囲であることが好ましく、より好ましくは10:90〜90:10の範囲である。正孔取出し層の厚さは5nmから600nmが好ましく、より好ましくは10nmから200nmである。多価アルコール層と正孔輸送材料を積層した構造の場合、多価アルコール層の厚さは正孔輸送性材料の表面エネルギー準位を相対的に下降させるだけ効果が得られれば特に限定されないが、絶縁物であるため、10nm以下が好ましく、5nm以下がより好ましい。
Next, the
本発明における多価アルコールとは、1分子中のヒドロキシル基の数が2以上のアルコール化合物のことを指す。多価アルコールは、正孔輸送性材料の表面エネルギー準位を相対的に下降させるだけの影響を及ぼすことができる材料であれば特に限定されない。すなわち、「アドヴァンスト マテリアルズ(Advanced Materials)」、2014年、26巻、494−500頁にあるように、X線光電子分光 (XPS)や、紫外光電子分光 (UPS)で測定した正孔取出し層のフェルミ準位が大きくなる効果があればよい。表面エネルギーのシフト効果は、多価アルコールを無機酸化物(ITOなど)にスピンコートなどで10nm以下程度の厚みで塗布した後、光電子分光装置(AC−2)などで無機酸化物の表面エネルギーを測定することで確認できる。多価アルコールとして、例えば、グリセリン、ソルビトール、マルチトール、キシリトール、スクロースなどの糖アルコールが挙げられる。多価アルコールとしては、1分子中のヒドロキシル基の数が6以上のものが正孔輸送性材料との相互作用が強まり、界面を安定化する効果が高まるため好ましく、特にソルビトールが好ましい。また、側鎖に複数のヒドロキシル基を有するポリマーも好ましく、ポリビニルアルコール(PVA)は特に好ましい。 The polyhydric alcohol in the present invention refers to an alcohol compound having 2 or more hydroxyl groups in one molecule. The polyhydric alcohol is not particularly limited as long as it can affect the surface energy level of the hole transporting material relatively lower. That is, as shown in “Advanced Materials”, 2014, Vol. 26, pp. 494-500, a hole extraction layer measured by X-ray photoelectron spectroscopy (XPS) or ultraviolet photoelectron spectroscopy (UPS). It is sufficient if there is an effect of increasing the Fermi level of. The surface energy shift effect is achieved by applying polyhydric alcohol to an inorganic oxide (ITO, etc.) with a thickness of about 10 nm or less by spin coating, etc., and then applying the surface energy of the inorganic oxide with a photoelectron spectrometer (AC-2) or the like. It can be confirmed by measuring. Examples of the polyhydric alcohol include sugar alcohols such as glycerin, sorbitol, maltitol, xylitol, and sucrose. As the polyhydric alcohol, those having 6 or more hydroxyl groups in one molecule are preferable because the interaction with the hole transporting material is strengthened and the effect of stabilizing the interface is enhanced, and sorbitol is particularly preferable. A polymer having a plurality of hydroxyl groups in the side chain is also preferred, and polyvinyl alcohol (PVA) is particularly preferred.
正孔輸送性材料としては、ポリチオフェン系重合体、ポリ−p−フェニレンビニレン系重合体、ポリフルオレン系重合体、ポリピロール重合体、ポリアニリン重合体、ポリフラン重合体、ポリピリジン重合体、ポリカルバゾール重合体などの導電性高分子や、フタロシアニン誘導体(H2Pc、CuPc、ZnPcなど)、ポルフィリン誘導体、アセン系化合物(テトラセン、ペンタセンなど)などのp型半導体特性を示す低分子有機化合物、カーボンナノチューブやグラフェン、酸化グラフェンなどの炭素化合物、MoO3などの酸化モリブデン(MoOx)、WO3などの酸化タングステン(WOx)、NiOなどの酸化ニッケル(NiOx)、V2O5などの酸化バナジウム(VOx)、ZrO2などの酸化ジルコニウム(ZrOx)、Cu2Oなどの酸化銅(CuOx)、ヨウ化銅、RuO4などの酸化ルテニウム(RuOx)、Re2O7などの酸化ルテニウム(ReOx)などの無機化合物が好ましく用いられる。特に酸化モリブデン、酸化バナジウム、酸化タングステンは好ましく用いられる。正孔輸送性材料は単独の化合物を用いてもよいし、2種以上の化合物を混合してもよい。また積層構造であってもよい。 Examples of hole transporting materials include polythiophene polymers, poly-p-phenylene vinylene polymers, polyfluorene polymers, polypyrrole polymers, polyaniline polymers, polyfuran polymers, polypyridine polymers, polycarbazole polymers, etc. Conductive polymers, phthalocyanine derivatives (H 2 Pc, CuPc, ZnPc, etc.), porphyrin derivatives, low molecular organic compounds exhibiting p-type semiconductor properties such as acene compounds (tetracene, pentacene, etc.), carbon nanotubes and graphene, Carbon compounds such as graphene oxide, molybdenum oxides such as MoO 3 (MoO x ), tungsten oxides such as WO 3 (WO x ), nickel oxides such as NiO (NiO x ), vanadium oxides such as V 2 O 5 (VO x) ), Zirconium oxides such as ZrO 2 ( ZrO x ), copper oxides such as Cu 2 O (CuO x ), copper iodide, ruthenium oxide (RuO x ) such as RuO 4, and inorganic compounds such as ruthenium oxide (ReO x ) such as Re 2 O 7 are preferably used. It is done. In particular, molybdenum oxide, vanadium oxide, and tungsten oxide are preferably used. As the hole transporting material, a single compound may be used, or two or more compounds may be mixed. Moreover, a laminated structure may be sufficient.
本発明の光起電力素子は、1つ以上の電荷再結合層を介して2層以上の光電変換層を積層(タンデム化)して直列接合を形成してもよい。例えば、基板/陰極/第1の光電変換層/第1の正孔取出し層/電荷再結合層/第2の光電変換層/第2の正孔取出し層/陽極という積層構成を挙げることができる。この場合、電荷再結合層は隣接する光電変換層の陰極および陽極を兼ねていると考えることができる。このように積層することにより、開放電圧を向上させることができる。なお、陰極と第1の光電変換層の間、および電荷再結合層と第2の光電変換層の間に上述の電子取出し層を設けてもよい。 In the photovoltaic device of the present invention, two or more photoelectric conversion layers may be stacked (tandemized) via one or more charge recombination layers to form a series junction. For example, a laminated structure of substrate / cathode / first photoelectric conversion layer / first hole extraction layer / charge recombination layer / second photoelectric conversion layer / second hole extraction layer / anode can be exemplified. . In this case, it can be considered that the charge recombination layer also serves as the cathode and anode of the adjacent photoelectric conversion layer. By laminating in this way, the open circuit voltage can be improved. Note that the above-described electron extraction layer may be provided between the cathode and the first photoelectric conversion layer and between the charge recombination layer and the second photoelectric conversion layer.
ここで用いられる電荷再結合層は、複数の光電変換層が光吸収できるようにするため、光透過性を有する必要がある。また、電荷再結合層は、十分に正孔と電子が再結合するように設計されていればよいので、必ずしも膜である必要は無く、例えば光電変換層上に一様に形成された金属クラスターであってもかまわない。従って、電荷再結合層には、上述の金、白金、クロム、ニッケル、リチウム、マグネシウム、カルシウム、錫、銀、アルミニウムなどから成る数オングストロームから数十オングストローム程度の光透過性を有する非常に薄い金属膜や金属クラスター(合金を含む)、ITO、IZO、AZO、GZO、FTO、酸化チタンや酸化モリブデンなどの光透過性の高い金属酸化物膜およびクラスター、PSSが添加されたPEDOTなどの導電性有機材料膜、またはこれらの複合体等が用いられる。例えば、銀を、真空蒸着法を用いて水晶振動子膜厚モニター上で数オングストローム〜1nmとなるように蒸着すれば、一様な銀クラスターが形成できる。その他にも、酸化チタン膜を形成するならば、アドヴァンスト マテリアルズ(Advanced Materials)、2006年、18巻、572−576頁に記載のゾルゲル法を用いればよい。ITO、IZOなどの複合金属酸化物であるならば、スパッタリング法を用いて製膜すればよい。これら電荷再結合層形成法や種類は、電荷再結合層形成時の光電変換層への非破壊性や、次に積層される光電変換層の形成法等を考慮して適当に選択すればよい。 The charge recombination layer used here needs to have optical transparency so that a plurality of photoelectric conversion layers can absorb light. In addition, the charge recombination layer need only be designed so that holes and electrons are sufficiently recombined. Therefore, the charge recombination layer does not necessarily have to be a film, for example, a metal cluster uniformly formed on the photoelectric conversion layer. It doesn't matter. Therefore, the charge recombination layer is a very thin metal having a light transmittance of about several angstroms to several tens of angstroms made of the above-mentioned gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, aluminum, etc. Films, metal clusters (including alloys), ITO, IZO, AZO, GZO, FTO, highly transparent metal oxide films and clusters such as titanium oxide and molybdenum oxide, and conductive organic materials such as PEDOT with PSS added A material film or a composite of these is used. For example, uniform silver clusters can be formed by depositing silver so as to be several angstroms to 1 nm on a crystal oscillator film thickness monitor using a vacuum deposition method. In addition, if a titanium oxide film is formed, the sol-gel method described in Advanced Materials, 2006, Vol. 18, 572-576 may be used. If it is a composite metal oxide such as ITO or IZO, the film may be formed by sputtering. These charge recombination layer formation methods and types may be appropriately selected in consideration of the non-destructive property to the photoelectric conversion layer at the time of charge recombination layer formation, the formation method of the next photoelectric conversion layer, and the like. .
次に本発明の光起電力素子の製造方法について説明する。基板上に電極(陰極)をスパッタリング法などにより形成する。陰極と光電変換層の間に電子輸送層を設ける場合には、金属塩や金属アルコキシドなどの前駆体溶液を塗布・加熱して形成する方法や、ナノ粒子分散液を基板に塗布して層を形成する方法、電子輸送性有機半導体溶液を塗布・乾燥して形成する方法を用いて所望の電子取出し層を形成すればよい。塗布法には、スピンコート塗布、ブレードコート塗布、スリットダイコート塗布、スクリーン印刷塗布、バーコーター塗布、鋳型塗布、印刷転写法、浸漬引き上げ法、インクジェット法、スプレー法など何れの方法を用いることができ、塗膜厚さ制御や配向制御など、得ようとする塗膜特性に応じて塗布方法を選択すればよい。 Next, the manufacturing method of the photovoltaic element of this invention is demonstrated. An electrode (cathode) is formed on the substrate by sputtering or the like. When an electron transport layer is provided between the cathode and the photoelectric conversion layer, a method in which a precursor solution such as a metal salt or a metal alkoxide is applied and heated, or a layer is formed by applying a nanoparticle dispersion on a substrate. What is necessary is just to form a desired electron extraction layer using the method of forming, and the method of apply | coating and drying an electron transport organic-semiconductor solution. As the coating method, any method such as spin coating, blade coating, slit die coating, screen printing coating, bar coater coating, mold coating, print transfer method, dip-up method, ink jet method, spray method, etc. can be used. The coating method may be selected according to the properties of the coating film to be obtained, such as coating thickness control and orientation control.
次に、電子供与性有機半導体材料、および電子受容性有機材料を含む光起電力素子用材料を溶媒に溶解させて溶液を作り、陰極、もしくは電子輸送層上に塗布し光電変換層を形成する。このとき用いられる溶媒は、有機半導体が溶媒中に適当に溶解または分散できるものであれば特に限定されないが、有機溶媒が好ましく、例えば、ヘキサン、ヘプタン、オクタン、イソオクタン、ノナン、デカン、シクロヘキサン、デカリン、ビシクロヘキシルなどの脂肪族炭化水素類、メタノール、エタノール、ブタノール、プロパノール、エチレングリコール、グリセリンなどのアルコール類、アセトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、イソホロンなどのケトン類、酢酸エチル、酢酸ブチル、乳酸メチル、γ−ブチロラクトン、ジエチレングリコールモノブチルエーテルアセテート、ジメチルカーボネートなどのエステル類、エチルエーテル、メチルターシャリーブチルエーテル、テトラヒドロフラン、1,4−ジオキサン、テトラヒドロピラン、3,4−ジヒドロ−2H−ピラン、イソクロマン、エチレングリコールモノメチルエーテル、ジグリムなどのエーテル類、アンモニア、エタノールアミンなどのアミン類、N,N−ジメチルホルムアミド、ジメチルアセトアミド、N−メチル−2−ピロリドンなどのアミド類、スルホランなどのスルホン類、ジメチルスルホキシドなどのスルホキシド類、二硫化炭素、1,8−オクタンジチオールなどのチオール類、アセトニトリル、アクリロニトリルなどのニトリル類、酢酸、乳酸などの脂肪酸類、フラン、チオフェン、ピロール、ピリジンなどの複素環式化合物類、ベンゼン、トルエン、キシレン、エチルベンゼン、クメン、n−ブチルベンゼン、sec−ブチルベンゼン、tert−ブチルベンゼン、スチレン、メシチレン、1,2,4−トリメチルベンゼン、p−シメン、シクロヘキシルベンゼン、ジエチルベンゼン、ペンチルベンゼン、ジペンチルベンゼン、ドデシルベンゼン、エチニルベンゼン、テトラリン、アニソール、フェネトール、ブチルフェニルエーテル、ペンチルフェニルエーテル、ベラトロール、1,3−ジメトキシベンゼン、1,2,4−トリメトキシベンゼン、2−メトキシトルエン、2,5−ジメチルアニソール、o−クロロフェノール、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、1−クロロナフタレン、1−ブロモナフタレン、1−メチルナフタレン、o−ジヨードベンゼン、アセトフェノン、2,3−ベンゾフラン、2,3−ジヒドロベンゾフラン、1,4−ベンゾジオキサン、酢酸フェニル、安息香酸メチル、クレゾール、アニリン、ニトロベンゼンなどの芳香族炭化水素類、ジクロロメタン、1,2−ジクロロエチレン、トリクロロエチレン、テトラクロロエチレン、クロロホルム、四塩化炭素、ジクロロエタン、トリクロロエタン、1,3−ジクロロプロパン、1,1,1,2―テトラクロロエタン、1,1,1,3−テトラクロロプロパン、1,2,2,3−テトラクロロプロパン、1,1,2,3−テトラクロロプロパン、ペンタクロロプロパン、ヘキサクロロプロパン、ヘプタクロロプロパン、1−ブロモプロパン、1,2−ジブロモプロパン、2,2−ジブロモプロパン、1,3−ジブロモプロパン、1,2,3−トリブロモプロパン、1,4−ジブロモブタン、1,5−ジブロモペンタン、1,6−ジブロモヘキサン、1,7−ジブロモヘプタン、1,8−ジブロモオクタン、1−ヨードプロパン、1,3−ジヨードプロパン、1,4−ジヨードブタン、1,5−ジヨードペンタン、1,6−ジヨードヘキサン、1,7−ジヨードヘプタン、1,8−ジヨードオクタンなどのハロゲン炭化水素類などが挙げられる。中でも好ましくは、トルエン、キシレン、メシチレン、1,2,4−トリメチルベンゼン、テトラリン、アニソール、フェネトールベラトロール、1,3−ジメトキシベンゼン、1,2,4−トリメトキシベンゼン、2−メトキシトルエン、2,5−ジメチルアニソール、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、1−クロロナフタレンなどの芳香族炭化水素類や、クロロホルム、ジクロロメタン、1,2−ジブロモプロパン、1,3−ジブロモプロパン、1,2,3−トリブロモプロパン、1,4−ジブロモブタン、1,6−ジブロモヘキサン、1,8−ジブロモオクタン、1,3−ジヨードプロパン、1,4−ジヨードブタン、1,5−ジヨードペンタン、1,6−ジヨードヘキサン、1,7−ジヨードヘプタン、1,8−ジヨードオクタンなどのハロゲン炭化水素類などが挙げられる。なお、これらを2種以上混合して用いてもよい。 Next, a photovoltaic element material containing an electron-donating organic semiconductor material and an electron-accepting organic material is dissolved in a solvent to form a solution, which is applied on the cathode or the electron transport layer to form a photoelectric conversion layer. . The solvent used at this time is not particularly limited as long as the organic semiconductor can be appropriately dissolved or dispersed in the solvent, but an organic solvent is preferable, for example, hexane, heptane, octane, isooctane, nonane, decane, cyclohexane, decalin. , Aliphatic hydrocarbons such as bicyclohexyl, alcohols such as methanol, ethanol, butanol, propanol, ethylene glycol, glycerin, ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, isophorone, ethyl acetate, butyl acetate, Esters such as methyl lactate, γ-butyrolactone, diethylene glycol monobutyl ether acetate, dimethyl carbonate, ethyl ether, methyl tertiary butyl ether, tetrahydrofuran, 1 4-dioxane, tetrahydropyran, 3,4-dihydro-2H-pyran, isochroman, ethers such as ethylene glycol monomethyl ether, diglyme, amines such as ammonia and ethanolamine, N, N-dimethylformamide, dimethylacetamide, N -Amides such as methyl-2-pyrrolidone, sulfones such as sulfolane, sulfoxides such as dimethyl sulfoxide, thiols such as carbon disulfide and 1,8-octanedithiol, nitriles such as acetonitrile and acrylonitrile, acetic acid, lactic acid Fatty acids such as, heterocyclic compounds such as furan, thiophene, pyrrole, pyridine, benzene, toluene, xylene, ethylbenzene, cumene, n-butylbenzene, sec-butylbenzene, tert-butylben Zen, styrene, mesitylene, 1,2,4-trimethylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene, ethynylbenzene, tetralin, anisole, phenetole, butylphenyl ether, pentylphenyl ether, Veratrol, 1,3-dimethoxybenzene, 1,2,4-trimethoxybenzene, 2-methoxytoluene, 2,5-dimethylanisole, o-chlorophenol, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1 -Bromonaphthalene, 1-methylnaphthalene, o-diiodobenzene, acetophenone, 2,3-benzofuran, 2,3-dihydrobenzofuran, 1,4-benzodioxane, acetate Nyl, aromatic hydrocarbons such as methyl benzoate, cresol, aniline, nitrobenzene, dichloromethane, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, 1,3-dichloropropane, 1, 1,1,2-tetrachloroethane, 1,1,1,3-tetrachloropropane, 1,2,2,3-tetrachloropropane, 1,1,2,3-tetrachloropropane, pentachloropropane, hexachloropropane, heptachloropropane 1-bromopropane, 1,2-dibromopropane, 2,2-dibromopropane, 1,3-dibromopropane, 1,2,3-tribromopropane, 1,4-dibromobutane, 1,5-dibromopentane 1,6-dibromo Xane, 1,7-dibromoheptane, 1,8-dibromooctane, 1-iodopropane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexane , Halogen hydrocarbons such as 1,7-diiodoheptane and 1,8-diiodooctane. Of these, toluene, xylene, mesitylene, 1,2,4-trimethylbenzene, tetralin, anisole, phenetol veratrol, 1,3-dimethoxybenzene, 1,2,4-trimethoxybenzene, 2-methoxytoluene, Aromatic hydrocarbons such as 2,5-dimethylanisole, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, chloroform, dichloromethane, 1,2-dibromopropane, 1,3-dibromopropane, 1,2, 3-tribromopropane, 1,4-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1 , 6-diiodohexane, 1,7-diiodoheptane, 1, - and halogen hydrocarbons such as di-iodo octane. Two or more of these may be mixed and used.
電子供与性有機材料および電子受容性有機材料を混合して光電変換層を形成する場合は、本発明の電子供与性有機材料と電子受容性有機材料を所望の比率で溶媒に添加し、加熱、攪拌、超音波照射などの方法を用いて溶解させ溶液を作り、陰極、もしくは電子取出し層上に塗布する。また、本発明の電子供与性有機材料および電子受容性有機材料を積層して光電変換層を形成する場合は、例えば本発明電子供与性有機材料の溶液を塗布して電子供与性有機材料を有する層を形成した後に、電子受容性有機材料の溶液を塗布して層を形成する。電子供与性有機材料および電子受容性有機材料が、分子量が1000以下程度の低分子量体である場合には、蒸着法を用いて層を形成することも可能である。 When a photoelectric conversion layer is formed by mixing an electron-donating organic material and an electron-accepting organic material, the electron-donating organic material and the electron-accepting organic material of the present invention are added to a solvent at a desired ratio, and heated. The solution is dissolved by using a method such as stirring or ultrasonic irradiation, and applied to the cathode or the electron extraction layer. When the photoelectric conversion layer is formed by laminating the electron donating organic material and the electron accepting organic material of the present invention, for example, a solution of the electron donating organic material of the present invention is applied to have the electron donating organic material. After forming the layer, a solution of the electron-accepting organic material is applied to form the layer. When the electron-donating organic material and the electron-accepting organic material are low molecular weight substances having a molecular weight of about 1000 or less, it is possible to form a layer using a vapor deposition method.
光電変換層の形成には前述の電子取出し層と同様の塗布法を用いることができ、膜厚制御や配向制御など、得ようとする光電変換層特性に応じて形成方法を選択すればよい。例えばスピンコート塗布を行う場合には、本発明の電子供与性有機材料、および電子受容性有機材料が1〜20g/lの濃度(本発明の電子供与性有機材料と電子受容性有機材料と溶媒を含む溶液の体積に対する、本発明の電子供与性有機材料と電子受容性有機材料の重量)であることが好ましく、この濃度にすることで厚さ5〜200nmの均質な光電変換層を得ることができる。形成した光電変換層に対して、溶媒を除去するために、減圧下または不活性雰囲気下(窒素やアルゴン雰囲気下)などでアニーリング処理を行ってもよい。アニーリング処理の好ましい温度は40℃〜300℃、より好ましくは50℃〜200℃である。このアニーリング処理は、正孔取出し層陽極の形成後に行ってもよい。 For the formation of the photoelectric conversion layer, the same coating method as that for the above-described electron extraction layer can be used, and the formation method may be selected according to the characteristics of the photoelectric conversion layer to be obtained, such as film thickness control and orientation control. For example, when spin coating is performed, the electron donating organic material of the present invention and the electron accepting organic material have a concentration of 1 to 20 g / l (the electron donating organic material, the electron accepting organic material and the solvent of the present invention). The weight of the electron-donating organic material and the electron-accepting organic material of the present invention with respect to the volume of the solution containing the organic compound is preferable, and by obtaining this concentration, a homogeneous photoelectric conversion layer having a thickness of 5 to 200 nm can be obtained. Can do. In order to remove the solvent, the formed photoelectric conversion layer may be subjected to an annealing treatment under reduced pressure or under an inert atmosphere (nitrogen or argon atmosphere). A preferable temperature for the annealing treatment is 40 ° C to 300 ° C, more preferably 50 ° C to 200 ° C. This annealing treatment may be performed after the formation of the hole extraction layer anode.
次に、塗布法や蒸着法によって光電変換層上に正孔取出し層を形成する。正孔取出し層が、多価アルコールと正孔輸送性材料から成る混合層の場合、所望の正孔輸送性材料(PEDOT:PSSなど)と多価アルコールの混合溶液を調製し、光電変換層上に塗布した後、真空恒温槽やホットプレートなどを用いて溶媒を除去することで形成できる。また、金属酸化物などの前駆体と多価アルコールの混合溶液を光電変換層上に塗布した後、真空恒温槽やホットプレートなどを用いて反応を進行させることでも形成できる。正孔取出し層が、多価アルコールと正孔輸送性材料との積層構造の場合、多価アルコールと正孔輸送性材料それぞれの溶液を順に光電変換層上に塗布、乾燥することで形成できる。また、多価アルコールを光電変換層上に塗布した後、酸化モリブデンなどの無機材料に真空蒸着法やスパッタ法を用いて製膜することでも形成できる。塗布法には、前述の電子取出し層の形成の場合と同様の塗布法を用いることができる。 Next, a hole extraction layer is formed on the photoelectric conversion layer by a coating method or a vapor deposition method. When the hole extraction layer is a mixed layer composed of a polyhydric alcohol and a hole transporting material, prepare a mixed solution of the desired hole transporting material (such as PEDOT: PSS) and the polyhydric alcohol, on the photoelectric conversion layer After the coating, it can be formed by removing the solvent using a vacuum thermostat or a hot plate. Alternatively, it can be formed by applying a mixed solution of a precursor such as a metal oxide and a polyhydric alcohol on the photoelectric conversion layer and then allowing the reaction to proceed using a vacuum thermostat or a hot plate. When the hole extraction layer has a laminated structure of a polyhydric alcohol and a hole transporting material, the hole extraction layer can be formed by applying and drying a solution of each of the polyhydric alcohol and the hole transporting material on the photoelectric conversion layer in order. Alternatively, it can be formed by applying a polyhydric alcohol on the photoelectric conversion layer and then depositing the film on an inorganic material such as molybdenum oxide using a vacuum deposition method or a sputtering method. As the coating method, the same coating method as in the case of forming the electron extraction layer described above can be used.
陽極は、正孔取出し層の上にAgなどの金属電極を真空蒸着法やスパッタ法により形成する。正孔取出し層を真空蒸着した場合は、引き続き、真空を保持したまま金属電極を続けて形成することが好ましい。 For the anode, a metal electrode such as Ag is formed on the hole extraction layer by vacuum deposition or sputtering. When the hole extraction layer is vacuum-deposited, it is preferable to continue to form the metal electrode while maintaining the vacuum.
なお、以上は最初に基板上に陰極を形成し、陰極側から順に層を形成して光起電力素子を作成する方法について説明したが、基板上に電極(陽極)をスパッタリング法などにより形成し、当該電極の上に、多価アルコールを含む正孔取出し層、光電変換層、電子取出し層、および電極(陰極)をこの順に形成する光起電力素子製造方法も挙げられる。この場合、光起電力素子の積層構造が逆になり、正孔取出し層は光電変換層の下に形成されることになるが、その他は前記同様である。 In the above, the method for forming a photovoltaic element by first forming a cathode on a substrate and forming layers sequentially from the cathode side has been described. However, an electrode (anode) is formed on the substrate by a sputtering method or the like. Moreover, the photovoltaic device manufacturing method which forms the hole extraction layer containing a polyhydric alcohol, a photoelectric converting layer, an electron extraction layer, and an electrode (cathode) in this order on the said electrode is also mentioned. In this case, the laminated structure of the photovoltaic elements is reversed, and the hole extraction layer is formed under the photoelectric conversion layer, but the other is the same as described above.
本発明の光起電力素子は、光電変換機能、光整流機能などを利用した種々の光電変換デバイスへの応用が可能である。例えば光電池(太陽電池など)、電子素子(光センサ、光スイッチ、フォトトランジスタなど)、光記録材(光メモリなど)、撮像素子などに有用である。 The photovoltaic element of the present invention can be applied to various photoelectric conversion devices using a photoelectric conversion function, an optical rectification function, and the like. For example, it is useful for photovoltaic cells (such as solar cells), electronic devices (such as optical sensors, optical switches, and phototransistors), optical recording materials (such as optical memories), and imaging devices.
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。なお、本発明は下記実施例に限定されるものではない。また実施例等で用いた化合物のうち、略語を使用しているものについて、以下に示す。
Isc:短絡電流密度
Voc:開放電圧
η:光電変換効率
ITO:インジウム錫酸化物
PVA:ポリビニルアルコール
A−1:下記式で表される化合物
Hereinafter, the present invention will be described more specifically based on examples. In addition, this invention is not limited to the following Example. Of the compounds used in the examples and the like, those using abbreviations are shown below.
Isc: short circuit current density Voc: open circuit voltage η: photoelectric conversion efficiency ITO: indium tin oxide PVA: polyvinyl alcohol A-1: compound represented by the following formula
[70]PCBM:フェニル C71 ブチリックアシッドメチルエステル
CF:クロロホルム
各実施例・比較例における光電変換効率は、次式により求めた。
η(%)=Isc(mA/cm2)×Voc(V)×FF/照射光強度(mW/cm2)×100
FF=JVmax/(Isc(mA/cm2)×Voc(V))
JVmax(mW/cm2)は、印加電圧が0Vから開放電圧までの間で電流密度と印加電圧の積が最大となる点における電流密度と印加電圧の積の値である。
[70] PCBM: Phenyl C71 Butyric acid methyl ester CF: Chloroform The photoelectric conversion efficiency in each example and comparative example was determined by the following formula.
η (%) = Isc (mA / cm 2 ) × Voc (V) × FF / irradiation light intensity (mW / cm 2 ) × 100
FF = JVmax / (Isc (mA / cm 2 ) × Voc (V))
JVmax (mW / cm 2 ) is a value of the product of the current density and the applied voltage at the point where the product of the current density and the applied voltage is maximum between the applied voltage of 0 V and the open circuit voltage.
各実施例・比較例における光電変換効率の保持率は、次式により求めた。
保持率(%)=100℃2時間の加熱試験後の光電変換効率(%)/作製直後の光電変換効率(%)×100
合成例1
化合物A−1を式1に示す方法で合成した。なお、合成例1記載の化合物(1−i)はジャーナルオブザアメリカンケミカルソサエティ(Journal of the American Chemical Society)、2009年、131巻、7792−7799頁に記載されている方法を参考に、化合物(1−p)はアンゲバンテケミ インターナショナルエディション(Angewandte Chem Internatioal Edition)、2011年、50巻、9697−9702頁に記載されている方法を参考にして合成した。
The retention rate of photoelectric conversion efficiency in each example and comparative example was determined by the following equation.
Retention rate (%) = photoelectric conversion efficiency after heating test at 100 ° C. for 2 hours (%) / photoelectric conversion efficiency immediately after production (%) × 100
Synthesis example 1
Compound A-1 was synthesized by the method shown in
メチル−2−チオフェンカルボキシレート(東京化成工業(株)製)38g(0.27mol)およびクロロメチルメチルエーテル(東京化成工業(株)製)108g(1.34mol)を0℃で撹拌しているところに、四塩化スズ(和光純薬工業(株)製)125g(0.48mol)を1時間かけて加え、その後室温で8時間撹拌した。撹拌終了後、水100mlを0℃でゆっくり加え、クロロホルムで3回抽出した。有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで溶媒を乾燥後、溶媒を減圧除去した。得られた茶褐色固体をメタノールから再結晶することにより化合物(1−b)を薄黄色固体(24.8g、収率39%)として得た。化合物(1−b)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):7.71(s,1H),4.79(s,1H),4.59(s,1H),3.88(s,3H)ppm。
38 g (0.27 mol) of methyl-2-thiophenecarboxylate (Tokyo Chemical Industry Co., Ltd.) and 108 g (1.34 mol) of chloromethyl methyl ether (Tokyo Chemical Industry Co., Ltd.) are stirred at 0 ° C. Then, 125 g (0.48 mol) of tin tetrachloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added over 1 hour, and then stirred at room temperature for 8 hours. After completion of stirring, 100 ml of water was slowly added at 0 ° C., and extracted with chloroform three times. The organic layer was washed with saturated brine, the solvent was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The obtained brown solid was recrystallized from methanol to obtain compound (1-b) as a pale yellow solid (24.8 g, yield 39%). The measurement result of 1 H-NMR of the compound (1-b) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 7.71 (s, 1H), 4.79 (s, 1H), 4.59 (s, 1H), 3.88 (s, 3H) ppm.
上記化合物(1−b)24.8g(0.10mmol)をメタノール(佐々木化学工業(株)製)1.2Lに溶解させ、60℃で撹拌しているところに硫化ナトリウム(アルドリッチ社製)8.9g(0.11mol)のメタノール溶液100mlを1時間かけて滴下し、さらに60℃で4時間撹拌した。反応終了後、溶媒を減圧除去し、クロロホルム200mlと水200mlを加え、不溶物をろ別した。有機層を水で2回、飽和食塩水で1回洗浄し、無水硫酸マグネシウムで乾燥後、溶媒を減圧除去した。粗精製物をシリカゲルカラムクロマトグラフィー(溶離液、クロロホルム)で精製することにより化合物(1−c)を白色固体(9.8g、収率48%)として得た。化合物(1−c)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):7.48(s,1H),4.19(t,J=3.0Hz,2H),4.05(t,J=3.0Hz,2H),3.87(s,3H)ppm。
24.8 g (0.10 mmol) of the above compound (1-b) was dissolved in 1.2 L of methanol (manufactured by Sasaki Chemical Co., Ltd.) and stirred at 60 ° C., and sodium sulfide (manufactured by Aldrich) 8 .9 g (0.11 mol) of methanol solution (100 ml) was added dropwise over 1 hour, and the mixture was further stirred at 60 ° C. for 4 hours. After completion of the reaction, the solvent was removed under reduced pressure, 200 ml of chloroform and 200 ml of water were added, and insoluble matters were filtered off. The organic layer was washed twice with water and once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (eluent, chloroform) to give compound (1-c) as a white solid (9.8 g, yield 48%). The measurement result of 1 H-NMR of the compound (1-c) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 7.48 (s, 1H), 4.19 (t, J = 3.0 Hz, 2H), 4.05 (t, J = 3.0 Hz, 2H), 3.87 (s, 3H) ppm.
上記化合物(1−c)9.8g(49mmol)に水100mlついで3M水酸化ナトリウム水溶液30mlを加え、80℃で4時間加熱撹拌した。反応終了後、濃塩酸15mlを0℃で加え、析出した固体をろ取し、水で数回洗浄した。得られた固体を乾燥し、化合物(1−d)を白色固体(8.9g、収率98%)として得た。
1H−NMR(270MHz,DMSO−d6):7.46(s,1H),4.18(t,J=3.2Hz,2H),4.01(t,J=3.2Hz,2H)ppm。
To 9.8 g (49 mmol) of the above compound (1-c), 100 ml of water and 30 ml of 3M aqueous sodium hydroxide solution were added, followed by heating and stirring at 80 ° C. for 4 hours. After completion of the reaction, 15 ml of concentrated hydrochloric acid was added at 0 ° C., and the precipitated solid was collected by filtration and washed several times with water. The obtained solid was dried to obtain compound (1-d) as a white solid (8.9 g, yield 98%).
1 H-NMR (270 MHz, DMSO-d 6 ): 7.46 (s, 1H), 4.18 (t, J = 3.2 Hz, 2H), 4.01 (t, J = 3.2 Hz, 2H) ) Ppm.
上記化合物(1−d)1.46g(7.8mmol)を脱水テトラヒドロフラン(和光純薬工業(株)製)60mlに溶解し、−78℃で撹拌しているところに、ノルマルブチルリチウムヘキサン溶液(1.6M、和光純薬工業(株)製)10.7ml(17.2mmol)を滴下し、−78℃で1時間攪拌した。次いでN−フルオロベンゼンスルホンイミド(東京化成工業(株)製)4.91g(15.6mmol)の乾燥テトラヒドロフラン溶液20mlを−78℃で10分間かけて滴下し、室温で12時間攪拌した。反応終了後、水50mlをゆっくり加えた。3M塩酸を加えて水層を酸性にした後、クロロホルムで3回抽出した。有機層を無水硫酸マグネシウムで乾燥後、溶媒を減圧留去した。シリカゲルカラムクロマトグラフィー(溶離液、酢酸エチル)で副生成物を除去した後に酢酸エチルから再結晶することで化合物(1−e)を薄黄色粉末(980mg、収率61%)として得た。化合物(1−e)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,DMSO−d6):13.31(brs,1H),4.20(t,J=3.0Hz,2H),4.03(t,J=3.0Hz,2H)ppm。
1.46 g (7.8 mmol) of the above compound (1-d) was dissolved in 60 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred at −78 ° C. to obtain a normal butyl lithium hexane solution ( 1.6 M, 10.7 ml (17.2 mmol) manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise, and the mixture was stirred at -78 ° C for 1 hour. Next, 20 ml of a dry tetrahydrofuran solution of 4.91 g (15.6 mmol) of N-fluorobenzenesulfonimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at −78 ° C. over 10 minutes, followed by stirring at room temperature for 12 hours. After completion of the reaction, 50 ml of water was slowly added. 3M Hydrochloric acid was added to acidify the aqueous layer, and the mixture was extracted 3 times with chloroform. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. By-product was removed by silica gel column chromatography (eluent, ethyl acetate) and then recrystallized from ethyl acetate to obtain compound (1-e) as a pale yellow powder (980 mg, 61% yield). The measurement result of 1 H-NMR of the compound (1-e) is shown below.
1 H-NMR (270 MHz, DMSO-d 6 ): 13.31 (brs, 1H), 4.20 (t, J = 3.0 Hz, 2H), 4.03 (t, J = 3.0 Hz, 2H) ) Ppm.
上記化合物(1−e)800mg(3.9mmol)の脱水ジクロロメタン(和光純薬工業(株)製)溶液10mlに、オキサリルクロリド(東京化成工業(株)製)1ml、次いでジメチルホルムアミド(和光純薬工業(株)製)1滴を加え、室温で3時間攪拌した。溶媒と過剰の塩化オキサリルを減圧除去することで、化合物(1−f)を黄色オイルとして得た。化合物(1−f)はそのまま次の反応に用いた。 To 10 ml of a dehydrated dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 800 mg (3.9 mmol) of the above compound (1-e), 1 ml of oxalyl chloride (Tokyo Chemical Industry Co., Ltd.), and then dimethylformamide (Wako Pure Chemical Industries, Ltd.) 1 drop of Kogyo Co., Ltd. was added and stirred at room temperature for 3 hours. The solvent and excess oxalyl chloride were removed under reduced pressure to obtain compound (1-f) as a yellow oil. Compound (1-f) was used in the next reaction as it was.
上記化合物(1−f、粗精製物)のジクロロメタン溶液10mlを1−オクタノール(和光純薬工業(株)製)1.3g(10mmol)およびトリエチルアミン(和光純薬工業(株)製)800mg(8mmol)のジクロロメタン溶液15mlに室温で加え、6時間室温で撹拌した。反応溶液を1M塩酸で2回、水で1回、飽和食塩水で1回洗浄し、無水硫酸マグネシウムで乾燥後、溶媒を減圧留去した。シリカゲルカラムクロマトグラフィー(溶離液、クロロホルム)で精製することにより化合物(1−g)を薄黄色固体(1.12g、収率90%)として得た。化合物(1−g)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):4.27(t,J=6.7Hz,2H),4.16(t,J=3.0Hz,2H),4.01(t,J=3.0Hz,2H),1.72(m,2H),1.5−1.3(m,12H),0.88(t,J=7.0Hz,3H)ppm。
10 ml of a dichloromethane solution of the above compound (1-f, roughly purified product) 1.3 g (10 mmol) of 1-octanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 800 mg (8 mmol) of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) ) In dichloromethane (15 ml) at room temperature and stirred for 6 hours at room temperature. The reaction solution was washed twice with 1M hydrochloric acid, once with water and once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (eluent, chloroform) gave compound (1-g) as a pale yellow solid (1.12 g, yield 90%). The measurement result of 1 H-NMR of the compound (1-g) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 4.27 (t, J = 6.7 Hz, 2H), 4.16 (t, J = 3.0 Hz, 2H), 4.01 (t, J = 3) 0.0 Hz, 2H), 1.72 (m, 2H), 1.5-1.3 (m, 12H), 0.88 (t, J = 7.0 Hz, 3H) ppm.
上記化合物(1−g)1.1g(3.5mmol)の酢酸エチル溶液40mlに、メタクロロ安息香酸(ナカライテスク(株)製)630mg(3.6mmol)の酢酸エチル溶液10mlを0℃で滴下し、室温で5時間攪拌した。溶媒を減圧除去した後に無水酢酸30mlを加え、3時間加熱還流した。溶媒を再び減圧除去した後にシリカゲルカラムクロマトグラフィー(溶離液、ジクロロメタン:ヘキサン=1:1)で精製することにより化合物(1−h)を薄黄色オイル(1.03g、収率94%)として得た。化合物(1−h)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):7.65(d,J=2.7Hz,1H),7.28(dd,J=2.7Hz and 5.4Hz,1H),4.31(t,J=6.8Hz,2H),1.75(m,2H),1.42−1.29(m,12H),0.89(t,J=6.8Hz,3H)ppm。
To 40 ml of an ethyl acetate solution of 1.1 g (3.5 mmol) of the above compound (1-g), 10 ml of an ethyl acetate solution of 630 mg (3.6 mmol) of metachlorobenzoic acid (manufactured by Nacalai Tesque) was added dropwise at 0 ° C. And stirred at room temperature for 5 hours. After removing the solvent under reduced pressure, 30 ml of acetic anhydride was added, and the mixture was heated to reflux for 3 hours. The solvent was removed again under reduced pressure, and the residue was purified by silica gel column chromatography (eluent, dichloromethane: hexane = 1: 1) to obtain compound (1-h) as a pale yellow oil (1.03 g, yield 94%). It was. The measurement result of 1 H-NMR of the compound (1-h) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 7.65 (d, J = 2.7 Hz, 1H), 7.28 (dd, J = 2.7 Hz and 5.4 Hz, 1H), 4.31 (t , J = 6.8 Hz, 2H), 1.75 (m, 2H), 1.42-1.29 (m, 12H), 0.89 (t, J = 6.8 Hz, 3H) ppm.
上記化合物(1−h)1.0g(3.2mmol)のジメチルホルムアミド溶液20mlに、N−ブロモスクシンイミド(和光純薬工業(株)製)1.25g(7.0mmol)を室温で加え、3時間室温で撹拌した。反応終了後、5%チオ硫酸ナトリウム水溶液10mlを加え、5分間攪拌した。酢酸エチル80mlを加え、有機層を水で5回、飽和食塩水で1回洗浄し、無水硫酸マグネシウムで乾燥後、溶媒を減圧留去した。シリカゲルカラムクロマトグラフィー(溶離液、クロロホルム:ヘキサン=1:3)で精製することにより化合物(1−i)を薄黄色固体(1.2g、収率79%)として得た。化合物(1−i)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):4.32(t,J=6.5Hz,2H),1.75(m,2H),1.42−1.29(m,12H),0.89(t,J=6.8Hz,3H)ppm。
To 20 ml of a dimethylformamide solution of 1.0 g (3.2 mmol) of the above compound (1-h), 1.25 g (7.0 mmol) of N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.) is added at room temperature. Stir for hours at room temperature. After completion of the reaction, 10 ml of 5% aqueous sodium thiosulfate solution was added and stirred for 5 minutes. 80 ml of ethyl acetate was added, the organic layer was washed 5 times with water and once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (eluent, chloroform: hexane = 1: 3) gave compound (1-i) as a pale yellow solid (1.2 g, yield 79%). The measurement result of 1 H-NMR of compound (1-i) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 4.32 (t, J = 6.5 Hz, 2H), 1.75 (m, 2H), 1.42-1.29 (m, 12H), 0. 89 (t, J = 6.8 Hz, 3H) ppm.
ジエチルアミン(和光純薬工業(株)製)110g(1.5mol)のジクロロメタン溶液300mlに、3−チオフェンカルボニルクロリド(和光純薬工業(株)製)100g(0.68mol)を0℃で1時間かけて加え、室温で3時間攪拌した。撹拌終了後、水200mlを加え、有機層を水で3回、飽和食塩水で1回洗浄した。無水硫酸マグネシウムで乾燥後、溶媒を減圧留去した。残渣を減圧蒸留することにより、化合物(1−k)を淡橙色液体(102g、収率82%)として得た。化合物(1−k)の1H−NMRの測定結果を以下に示す。 To 300 ml of dichloromethane solution of 110 g (1.5 mol) of diethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), 100 g (0.68 mol) of 3-thiophenecarbonyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) at 0 ° C. for 1 hour. And stirred at room temperature for 3 hours. After completion of the stirring, 200 ml of water was added, and the organic layer was washed three times with water and once with a saturated saline solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain compound (1-k) as a pale orange liquid (102 g, yield 82%). The measurement result of 1 H-NMR of the compound (1-k) is shown below.
1H−NMR(270MHz,CDCl3):7.47(dd,J=3.2Hz and 1.0Hz,1H),7.32(dd,J=5.0Hz and 3.2Hz,1H),7.19(dd,J=5.0Hz and 1.0Hz,1H),3.43(brs,4H),1.20(t,J=6.5Hz,6H)ppm。 1 H-NMR (270 MHz, CDCl 3 ): 7.47 (dd, J = 3.2 Hz and 1.0 Hz, 1H), 7.32 (dd, J = 5.0 Hz and 3.2 Hz, 1H), 7 .19 (dd, J = 5.0 Hz and 1.0 Hz, 1H), 3.43 (brs, 4H), 1.20 (t, J = 6.5 Hz, 6H) ppm.
上記化合物(1−k)73.3g(0.40mol)の脱水テトラヒドロフラン(和光純薬工業(株)製)溶液400mlに、ノルマルブチルリチウムヘキサン溶液(1.6M、和光純薬工業(株)製)250ml(0.40mol)を0℃で30分間かけて滴下した。滴下終了後、室温で4時間攪拌した。撹拌終了後、水100mlをゆっくり加えしばらく撹拌した後、反応混合物を水800mlに注いだ。析出した固体をろ取し、水、メタノール、ついでヘキサンの順で洗浄することにより化合物(1−l)を黄色固体(23.8g、収率27%)として得た。化合物(1−l)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):7.69(d,J=4.9Hz,2H),7.64(d,J=4.9Hz,2H)ppm。
In 400 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 73.3 g (0.40 mol) of the above compound (1-k), normal butyl lithium hexane solution (1.6M, manufactured by Wako Pure Chemical Industries, Ltd.) ) 250 ml (0.40 mol) was added dropwise at 0 ° C. over 30 minutes. After completion of dropping, the mixture was stirred at room temperature for 4 hours. After stirring, 100 ml of water was slowly added and stirred for a while, and then the reaction mixture was poured into 800 ml of water. The precipitated solid was collected by filtration and washed with water, methanol, and hexane in this order to obtain compound (1-l) as a yellow solid (23.8 g, yield 27%). The measurement result of 1 H-NMR of the compound (1-l) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 7.69 (d, J = 4.9 Hz, 2H), 7.64 (d, J = 4.9 Hz, 2H) ppm.
チオフェン42g(0.50mol)の脱水テトラヒドロフラン(和光純薬工業(株)製)溶液400mlに、ノルマルブチルリチウムヘキサン溶液(1.6M、和光純薬工業(株)製)250ml(0.40mol)を−78℃で30分間かけて滴下した。反応混合物を−78℃で1時間攪拌した後、2−エチルヘキシルブロミド(和光純薬工業(株)製)76.4g(0.40mol)を−78℃で15分間かけて滴下した。反応溶液を室温で30分間撹拌した後、60℃で6時間加熱撹拌した。撹拌終了後、反応溶液を室温まで冷却し、水200mlおよびジエチルエーテル200mlを加えた。有機層を水で2回、飽和食塩水で洗浄後、無水硫酸マグネシウムで乾燥し、溶媒を減圧留去した。残渣を減圧蒸留することで化合物(1−n)を無色液体(28.3g、36%)として得た。化合物(1−n)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):7.11(d,4.9Hz,1H),6.92(dd,4.9Hz and 3.2Hz,1H),6.76(d,J=3.2Hz,1H),2.76(d,J=6.8Hz,2H),1.62(m,1H),1.4−1.3(m,8H),0.88(m,6H)ppm。
To 400 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 42 g (0.50 mol) of thiophene, 250 ml (0.40 mol) of normal butyl lithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.) was added. The solution was added dropwise at −78 ° C. over 30 minutes. The reaction mixture was stirred at -78 ° C for 1 hour, and then 76.4 g (0.40 mol) of 2-ethylhexyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at -78 ° C over 15 minutes. The reaction solution was stirred at room temperature for 30 minutes and then heated and stirred at 60 ° C. for 6 hours. After completion of the stirring, the reaction solution was cooled to room temperature, and 200 ml of water and 200 ml of diethyl ether were added. The organic layer was washed twice with water and saturated brine, and then dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was distilled under reduced pressure to obtain compound (1-n) as a colorless liquid (28.3 g, 36%). The measurement result of 1 H-NMR of the compound (1-n) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 7.11 (d, 4.9 Hz, 1 H), 6.92 (dd, 4.9 Hz and 3.2 Hz, 1 H), 6.76 (d, J = 3 .2 Hz, 1H), 2.76 (d, J = 6.8 Hz, 2H), 1.62 (m, 1H), 1.4-1.3 (m, 8H), 0.88 (m, 6H) ) Ppm.
上記化合物(1−n)17.5g(89mmol)の脱水テトラヒドロフラン(和光純薬工業(株)製)溶液400mlに、ノルマルブチルリチウムヘキサン溶液(1.6M、和光純薬工業(株)製)57ml(89mmol)を0℃で30分間かけて滴下した。反応溶液を50℃で1時間撹拌した後、上記化合物(1−l)4.9g(22mmol)を50℃で加え、そのまま1時間撹拌した。撹拌終了後、反応溶液を0℃に冷却し、塩化すず二水和物(和光純薬工業(株)製)39.2g(175mmol)を10%塩酸80mlに溶かした溶液を加え、室温で1時間撹拌した。撹拌終了後、水200ml、ジエチルエーテル200mlを加え、有機層を水で2回、次いで飽和食塩水で洗浄した。無水硫酸マグネシウムで乾燥後、溶媒を減圧留去した。シリカゲルカラムクロマトグラフィー(溶離液、ヘキサン)で精製することにより化合物(1−o)を黄色オイル(7.7g、収率59%)として得た。化合物(1−o)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):7.63(d,J=5.7Hz,1H),7.45(d,J=5.7Hz,1H),7.29(d,J=3.6Hz,1H),6.88(d,J=3.6Hz,1H),2.86(d,J=7.0Hz,2H),1.70−1.61(m,1H),1.56−1.41(m,8H),0.97−0.89(m,6H)ppm。
To 400 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 17.5 g (89 mmol) of the above compound (1-n), 57 ml of normal butyl lithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.) (89 mmol) was added dropwise at 0 ° C. over 30 minutes. The reaction solution was stirred at 50 ° C. for 1 hour, and then 4.9 g (22 mmol) of the above compound (1-1) was added at 50 ° C. and stirred as it was for 1 hour. After completion of the stirring, the reaction solution was cooled to 0 ° C., and a solution of 39.2 g (175 mmol) of tin chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 80 ml of 10% hydrochloric acid was added. Stir for hours. After completion of the stirring, 200 ml of water and 200 ml of diethyl ether were added, and the organic layer was washed twice with water and then with a saturated saline solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (eluent, hexane) gave compound (1-o) as a yellow oil (7.7 g, yield 59%). The measurement result of 1 H-NMR of the compound (1-o) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 7.63 (d, J = 5.7 Hz, 1H), 7.45 (d, J = 5.7 Hz, 1H), 7.29 (d, J = 3 .6 Hz, 1H), 6.88 (d, J = 3.6 Hz, 1H), 2.86 (d, J = 7.0 Hz, 2H), 1.70-1.61 (m, 1H), 1 .56-1.41 (m, 8H), 0.97-0.89 (m, 6H) ppm.
上記化合物(1−o)870mg(1.5mmol)の脱水テトラヒドロフラン(和光純薬工業(株)製)溶液25mlに、ノルマルブチルリチウムヘキサン溶液(1.6M、和光純薬工業(株)製)2.0ml(3.3mmol)を−78℃でシリンジを用いて加え、−78℃で30分間、室温で30分間攪拌した。反応混合物を−78℃まで冷却した後、トリメチルスズクロリド(和光純薬工業(株)製)800mg(4.0mmol)を−78℃で一度に加え、室温で4時間撹拌した。撹拌終了後、ジエチルエーテル50mlおよび水50mlを加え5分間室温で撹拌した後、有機層を水で2回、次いで飽和食塩水で洗浄した。無水硫酸ナトリウムで溶媒を乾燥後、溶媒を減圧留去した。得られた橙色オイルをエタノールより再結晶することで、化合物(1−p)を薄黄色固体(710mg、収率52%)として得た。化合物(1−p)の1H−NMRの測定結果を以下に示す。
1H−NMR(270MHz,CDCl3):7.68(s,2H),7.31(d,J=3.2Hz,2H),6.90(d,J=3.2Hz,2H),2.87(d,J=6.2Hz,4H),1.69(m,2H),1.40−1.30(m,16H),1.0−0.9(m,12H),0.39(s,18H)ppm。
To 25 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) solution of 870 mg (1.5 mmol) of the above compound (1-o), normal butyl lithium hexane solution (1.6M, manufactured by Wako Pure Chemical Industries, Ltd.) 2 0.0 ml (3.3 mmol) was added at −78 ° C. using a syringe, and the mixture was stirred at −78 ° C. for 30 minutes and at room temperature for 30 minutes. After cooling the reaction mixture to −78 ° C., 800 mg (4.0 mmol) of trimethyltin chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at once at −78 ° C., and the mixture was stirred at room temperature for 4 hours. After completion of the stirring, 50 ml of diethyl ether and 50 ml of water were added and stirred at room temperature for 5 minutes, and then the organic layer was washed twice with water and then with a saturated saline solution. After drying the solvent with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained orange oil was recrystallized from ethanol to obtain the compound (1-p) as a pale yellow solid (710 mg, yield 52%). The measurement result of 1 H-NMR of the compound (1-p) is shown below.
1 H-NMR (270 MHz, CDCl 3 ): 7.68 (s, 2H), 7.31 (d, J = 3.2 Hz, 2H), 6.90 (d, J = 3.2 Hz, 2H), 2.87 (d, J = 6.2 Hz, 4H), 1.69 (m, 2H), 1.40-1.30 (m, 16H), 1.0-0.9 (m, 12H), 0.39 (s, 18H) ppm.
化合物(1−i)71mg(0.15mmol)および化合物(1−p)136mg(0.15mmol)をトルエン(和光純薬工業(株)製)4mlおよびジメチルホルムアミド(和光純薬工業(株)製)1mlに溶解させたところに、テトラキストリフェニルホスフィンパラジウム(東京化成工業(株)製)5mgを加え、窒素雰囲気下、100℃で15時間撹拌した。次いで、ブロモベンゼン(東京化成工業(株)製)15mgを加え、100℃にて1時間撹拌した。次いで、トリブチル(2−チエニル)すず(東京化成工業(株)製)40mgを加え、100℃にてさらに1時間撹拌した。撹拌終了後、反応混合物を室温まで冷却し、メタノール100mlに注いだ。析出した固体をろ取し、メタノール、水、アセトンの順に洗浄した。次いでソックスレー抽出器を用いてアセトン、ヘキサンの順で洗浄した。次に、得られた固体をクロロホルムに溶解させ、セライト(ナカライテスク(株)製)、次いでシリカゲルカラム(遊離液、クロロホルム)に通した後、溶媒を減圧留去した。得られた固体を再度クロロホルムに溶解させた後、メタノールに再沈殿し、化合物A−1(85mg)を得た。重量平均分子量は25,000、数平均分子量は16,000であった。 Compound (1-i) 71 mg (0.15 mmol) and compound (1-p) 136 mg (0.15 mmol) in toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 4 ml and dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) ) 5 mg of tetrakistriphenylphosphine palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution dissolved in 1 ml, and the mixture was stirred at 100 ° C. for 15 hours in a nitrogen atmosphere. Next, 15 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 100 ° C. for 1 hour. Subsequently, 40 mg of tributyl (2-thienyl) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C. for 1 hour. After completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was collected by filtration and washed with methanol, water, and acetone in this order. Subsequently, it wash | cleaned in order of acetone and hexane using the Soxhlet extractor. Next, the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (free solution, chloroform), and then the solvent was distilled off under reduced pressure. The obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound A-1 (85 mg). The weight average molecular weight was 25,000 and the number average molecular weight was 16,000.
[実施例1]
水5μLとエタノール0.5mLを酢酸亜鉛二水和物10mgの入ったサンプル瓶の中に加え、100℃で熱溶解させることで、酸化亜鉛前駆体溶液Aを調整した。PVAをごく少量の水に溶解させた後、エタノールで1g/Lとなるよう希釈し、溶液Bを得た。
[Example 1]
A zinc oxide precursor solution A was prepared by adding 5 μL of water and 0.5 mL of ethanol into a sample bottle containing 10 mg of zinc acetate dihydrate and thermally dissolving at 100 ° C. PVA was dissolved in a very small amount of water and then diluted with ethanol to 1 g / L to obtain a solution B.
1,8−ジヨードオクタンを2体積%の割合で混合したCF溶媒0.2mLを、A−1 0.9mg、[70]PCBM(ソレーヌ社製)1.1mgの入ったサンプル瓶の中に加え、超音波洗浄機(井内盛栄堂(株)製US−2、出力120W)中で30分間超音波照射することにより溶液Cを得た。 In a sample bottle containing 0.2 mg of CF solvent mixed with 2% by volume of 1,8-diiodooctane, 0.9 mg of A-1 and 1.1 mg of [70] PCBM (Soleine). In addition, the solution C was obtained by ultrasonic irradiation for 30 minutes in an ultrasonic cleaner (US-2 manufactured by Inoue Seieido Co., Ltd., output 120 W).
スパッタリング法により陰極となるITO透明導電層を125nm堆積させたガラス基板を38mm×46mmに切断した後、ITOをフォトリソグラフィー法により38mm×13mmの長方形状にパターニングした。得られた基板の光透過率を日立分光光度計U−3010で測定した結果、400nm〜900nmの全ての波長領域において85%以上であった。この基板をアルカリ洗浄液(フルウチ化学(株)製、“セミコクリーン”EL56)で10分間超音波洗浄した後、超純水で洗浄した。この基板を30分間UV/オゾン処理した後に、上記の溶液Aをガラス基板上に滴下し、スピンコートした後、ホットプレート上で100℃,30分間加熱することで約30nm厚の電子取出し層を製膜した。基板と上記の溶液B、溶液Cを窒素雰囲気としたグローブボックス中)に移し、溶液Cを電子取出し層上に滴下し、スピンコートした後、減圧乾燥することで膜厚130nmの光電変換層を形成した。溶液Bを光電変換層上に滴下し、スピンコートした後、ホットプレート上で80℃,5分間加熱することで多価アルコール層を形成した。その後、大気下へ取り出すことなく、基板と正孔取出し層用マスクを真空蒸着装置内に設置して、装置内の真空度を1×10−3Pa以下になるまで排気し、抵抗加熱法によって三酸化タングステンを10nm蒸着し、酸化タングステン層を形成した。続いて陽極となる銀層を100nmの厚さに蒸着した。本実施形態においては、正孔取出し層は多価アルコール層と酸化タングステン層からなる。作製した素子の上下の電極から引き出し電極を取り出し、帯状のITO層と銀層が重なり合う部分の面積が5mm×5mmである光起電力素子を作製した。 A glass substrate on which a 125 nm ITO transparent conductive layer serving as a cathode was deposited by sputtering was cut into 38 mm × 46 mm, and then ITO was patterned into a 38 mm × 13 mm rectangular shape by photolithography. As a result of measuring the light transmittance of the obtained substrate with Hitachi spectrophotometer U-3010, it was 85% or more in all wavelength regions of 400 nm to 900 nm. The substrate was subjected to ultrasonic cleaning with an alkali cleaning solution (“Semico Clean” EL56, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, and then cleaned with ultrapure water. After the substrate was UV / ozone treated for 30 minutes, the above solution A was dropped on the glass substrate, spin-coated, and then heated on a hot plate at 100 ° C. for 30 minutes to form an electron extraction layer having a thickness of about 30 nm. A film was formed. The substrate and the above solution B and solution C are transferred into a nitrogen atmosphere), and the solution C is dropped on the electron extraction layer, spin-coated, and dried under reduced pressure to form a 130 nm thick photoelectric conversion layer. Formed. Solution B was dropped onto the photoelectric conversion layer, spin-coated, and then heated on a hot plate at 80 ° C. for 5 minutes to form a polyhydric alcohol layer. Then, without taking out to the atmosphere, the substrate and the hole extraction layer mask were placed in a vacuum deposition apparatus, and the degree of vacuum in the apparatus was evacuated to 1 × 10 −3 Pa or less. Tungsten trioxide was evaporated to 10 nm to form a tungsten oxide layer. Subsequently, a silver layer serving as an anode was deposited to a thickness of 100 nm. In the present embodiment, the hole extraction layer includes a polyhydric alcohol layer and a tungsten oxide layer. The extraction electrodes were taken out from the upper and lower electrodes of the manufactured element, and a photovoltaic element having an area where the band-like ITO layer and the silver layer overlap each other was 5 mm × 5 mm was manufactured.
このようにして作製された光起電力素子の上下の電極をヒューレット・パッカード社製ピコアンメーター/ボルテージソース4140Bに接続して、大気下でITO層側から白色光(AM1.5;100mW/cm2)を照射し続け、印加電圧を−1Vから+2Vまで変化させたときの電流値を測定した。測定後、直ちに素子をグローブボックス内へ移し、100℃のホットプレート上で2時間加熱した。その後、大気下に取り出して、再度、同様の測定を行った。得られた電流値より光電変換効率(η)を算出した結果、光電変換効率の保持率は96%であった。 The upper and lower electrodes of the photovoltaic device thus produced were connected to a picoammeter / voltage source 4140B manufactured by Hewlett-Packard Co., and white light (AM1.5; 100 mW / cm from the ITO layer side in the atmosphere). 2 ) was continuously irradiated, and the current value was measured when the applied voltage was changed from -1V to + 2V. Immediately after the measurement, the device was transferred into a glove box and heated on a hot plate at 100 ° C. for 2 hours. Then, it took out in air | atmosphere and performed the same measurement again. As a result of calculating the photoelectric conversion efficiency (η) from the obtained current value, the retention rate of the photoelectric conversion efficiency was 96%.
[実施例2]
PVAに代えてソルビトールを用いた他は実施例1と全く同様にして光起電力素子を作製して、測定を行った。100℃で2時間加熱後の光電変換効率の保持率は91%であった。
[Example 2]
A photovoltaic device was produced in the same manner as in Example 1 except that sorbitol was used instead of PVA, and measurement was performed. The retention rate of photoelectric conversion efficiency after heating at 100 ° C. for 2 hours was 91%.
[比較例1]
溶液Bの塗布を行わなかった他は実施例1と全く同様にして光起電力素子を作製して、同様に測定を行った。100℃で2時間加熱後の光電変換効率の保持率は86%であった。
[Comparative Example 1]
A photovoltaic element was produced in the same manner as in Example 1 except that the solution B was not applied, and the measurement was performed in the same manner. The retention of photoelectric conversion efficiency after heating at 100 ° C. for 2 hours was 86%.
[比較例2]
ヘキサデカノールを濃度が1g/Lとなるようにエタノールに加え、溶液Dを得た。溶液Bに代えて溶液Dを用いた他は実施例1と全く同様にして光起電力素子を作製して、測定を行った。100℃で2時間加熱後の光電変換効率の保持率は79%であった。
[Comparative Example 2]
Hexadecanol was added to ethanol so that the concentration was 1 g / L to obtain a solution D. A photovoltaic device was produced in the same manner as in Example 1 except that the solution D was used in place of the solution B, and measurement was performed. The retention of photoelectric conversion efficiency after heating at 100 ° C. for 2 hours was 79%.
実施例と比較例の結果を表1にまとめた。実施例1および2と比較例1および2の対比から、本発明により光起電力素子の耐熱性能を向上させることができることが分かる。 The results of Examples and Comparative Examples are summarized in Table 1. From comparison between Examples 1 and 2 and Comparative Examples 1 and 2, it can be seen that the heat resistance of the photovoltaic device can be improved by the present invention.
1 基板
2 陰極
3 光電変換層
4 正孔取出し層
5 陽極
1
Claims (7)
The photovoltaic element according to claim 6, wherein the inorganic oxide is an oxide of a metal selected from the group consisting of tungsten, molybdenum, vanadium, and nickel.
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