TW201308704A - Production method of organic photovoltaic element - Google Patents

Production method of organic photovoltaic element Download PDF

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TW201308704A
TW201308704A TW101114680A TW101114680A TW201308704A TW 201308704 A TW201308704 A TW 201308704A TW 101114680 A TW101114680 A TW 101114680A TW 101114680 A TW101114680 A TW 101114680A TW 201308704 A TW201308704 A TW 201308704A
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thiophene
conjugated polymer
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organic
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Atsuhiro Nakahara
Takuya Inagaki
Takashi Sugioka
Akio Fujita
Hiroyuki Ogi
Thomas P Russell
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Kuraray Co
Univ Massachusetts
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • 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

Abstract

A feature of the present invention is that, a method for producing an organic photovoltaic element with an organic photo-active layer comprising a conjugated block copolymer comprising a polymer A block containing a thiophene group and a polymer B block containing a thiophene group, or a polymer composition comprising a conjugated polymer A containing a thiophene group and a conjugated polymer B containing a thiophene group, wherein the difference between the melting points of the polymers being 10 DEG C or more, and a fullerene derivative, and wherein the method includes a process of exposing an organic photo-active layer to a vapor of solvent having a surface tension between a surface tension of the conjugated polymer (A or B) containing a thiophene group and a surface tension of the fullerene derivative.

Description

有機光伏元件之製造方法 Method for manufacturing organic photovoltaic element

本發明關於一種有機光伏元件之製造方法。 The present invention relates to a method of manufacturing an organic photovoltaic element.

太陽能電池因其環境友善性且為重要的能量來源而引起注目。目前太陽能電池中的有機光伏元件用半導體材料係使用如單晶矽、多晶矽、非晶矽、及化合物半導體之無機物質。高成本的主要因素為在真空中高溫製造半導體薄膜之程序。因而現已研究使用共軛聚合物、有機半導體(如有機結晶)、或有機染料作為半導體材料之有機太陽能電池，且預期簡化其製造方法。有機太陽能電池因為其可藉輥對輥塗覆大量製造而引起注目作為低成本太陽能電池。 Solar cells are attracting attention because of their environmental friendliness and important energy sources. At present, semiconductor materials for organic photovoltaic elements in solar cells use inorganic substances such as single crystal germanium, polycrystalline germanium, amorphous germanium, and compound semiconductors. The main factor of high cost is the process of manufacturing a semiconductor film at a high temperature in a vacuum. Thus, an organic solar cell using a conjugated polymer, an organic semiconductor such as an organic crystal, or an organic dye as a semiconductor material has been studied, and it is expected to simplify its manufacturing method. Organic solar cells are attracting attention as low-cost solar cells because they can be manufactured by roll-to-roll coating.

有機太陽能電池係以將有機光活性層***兩個不同電極之間的方式所構成。有機光活性層通常包含共軛聚合物及富勒烯衍生物之混合物。至於代表性實例則為含有聚(3-己基噻吩)作為共軛聚合物及[6,6]-苯基-C61-丁酸甲酯(PCBM)作為富勒烯衍生物之組成物(Mayer,A.C.；Scully,S.R.；Hardin,B.E.；Rowell,M.W.；McGehee,M.D.Mater.Today2007,10,28-33；及Gunes,S.；Neugebauer,H.；Sariciftci,N.S.Chem.Rev.2007,107,1324-1338)。 Organic solar cells are constructed by inserting an organic photoactive layer between two different electrodes. The organic photoactive layer typically comprises a mixture of a conjugated polymer and a fullerene derivative. A representative example is a composition containing a poly(3-hexylthiophene) as a conjugated polymer and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as a fullerene derivative (Mayer, AC; Scully, SR; Hardin, BE; Rowell, MW; McGehee, MD Mater. Today 2007, 10, 28-33; and Gunes, S.; Neugebauer, H.; Sariciftci, NS Chem. Rev. 2007, 107, 1324 -1338).

有機太陽能電池之挑戰為改良電力轉換效率，具體而言，據報電力轉換效率改良係藉由改變有機光活性層之形態而達成。例如一種以熱或溶劑蒸汽處理之方法、 一種設計用於溶解共軛聚合物及富勒烯的溶劑之方法、一種添加高沸點化合物之方法、以及一種降低光活化層用溶劑的溶劑蒸發速率之方法(WO 2004/025746號專利；JP 2009-260324 A號專利；Nature Materials 4,864-868 2005；Journal of Applied Polymer Science，第111卷，1799-1804(2009)；及J.Phys.Chem.C 2009,113,17579-17584)。 The challenge of organic solar cells is to improve power conversion efficiency. Specifically, it has been reported that power conversion efficiency improvement is achieved by changing the form of the organic photoactive layer. For example, a method of treating with heat or solvent vapor, A method for dissolving a solvent for a conjugated polymer and fullerene, a method for adding a high boiling point compound, and a method for reducing a solvent evaporation rate of a solvent for a photoactivated layer (WO 2004/025746 Patent; JP 2009) -260324 A patent; Nature Materials 4, 864-868 2005; Journal of Applied Polymer Science, Vol. 111, 1799-1804 (2009); and J. Phys. Chem. C 2009, 113, 17579-17584).

此外，至於另一種改良電力轉換效率之方法，據報該電力轉換效率改良係嚐試以共軛嵌段共聚物控制形態(WO 2009/056496號專利；JP 2007-211237 A及JP 2008-223015 A號專利；JP第4126019號專利；Macromolecules,2009,42(18)，第7008-7015頁；Macromolecules,2010,43,3306-3313；Organic Electronics 10(2009)1541-1548；Soft Matter,2009,5,4219-4230；以及Adv.Mater.2010,22,763-768)。 Further, as another method for improving the power conversion efficiency, it is reported that the power conversion efficiency improvement is attempted to control the form with a conjugated block copolymer (WO 2009/056496 patent; JP 2007-211237 A and JP 2008-223015 A). Patent; JP No. 4,216,019; Macromolecules, 2009, 42 (18), pages 7008-7015; Macromolecules, 2010, 43, 3306-3313; Organic Electronics 10 (2009) 1541-1548; Soft Matter, 2009, 5, 4219-4230; and Adv. Mater. 2010, 22, 763-768).

然而，在使用共軛嵌段共聚物的情形，由於通常不僅難以控制富勒烯衍生物及共軛共聚物之形態，其亦難以控制共軛嵌段共聚物本身之形態。因此並無明確的指引，且該手法僅適用於一般的熱退火。其不預期熱退火嵌段共聚物固有地形成奈米尺寸形態，因此電力轉換效率未必高。 However, in the case of using a conjugated block copolymer, since it is usually difficult to control not only the form of the fullerene derivative and the conjugated copolymer, it is difficult to control the form of the conjugated block copolymer itself. Therefore there is no clear guidance and this method is only applicable to general thermal annealing. It is not expected that the thermally annealed block copolymer inherently forms a nano-sized form, and thus the power conversion efficiency is not necessarily high.

本發明之一目的為提供一種藉由控制包括共軛嵌段共聚物或共軛聚合物摻合物、及富勒烯衍生物之有機光 活性層的形態，而具有高電力轉換效率，可以短時間處理，且具經濟性的製造有機光伏元件之方法。本發明之另一目的為提供一種包含有機光活性層之有機光伏元件，其係如上所述而處理且具有高電力轉換效率。 It is an object of the present invention to provide an organic light by controlling a conjugated block copolymer or a conjugated polymer blend, and a fullerene derivative. The form of the active layer, which has high power conversion efficiency, can be processed in a short time, and has an economical method of manufacturing an organic photovoltaic element. Another object of the present invention is to provide an organic photovoltaic element comprising an organic photoactive layer which is treated as described above and which has high power conversion efficiency.

本發明可提供一種包含有機光活性層之有機光伏元件，其係經由經濟上有利及簡短的製造方法而具有高電力轉換效率。 The present invention can provide an organic photovoltaic element comprising an organic photoactive layer which has high power conversion efficiency via an economically advantageous and short manufacturing method.

依照本發明之有機光伏元件係至少具有陽極及陰極，且在電極之間包括有機光活性層。第1圖為顯示依照本發明之有機光伏元件的一個實例之示意圖。在第1圖中，符號1表示基板，符號2表示陽極，符號3表示有機光活性層，及符號4表示陰極。在某些型式之電極中，符號2表示陰極及符號4表示陽極。 The organic photovoltaic element according to the invention has at least an anode and a cathode and an organic photoactive layer between the electrodes. Fig. 1 is a schematic view showing an example of an organic photovoltaic element in accordance with the present invention. In Fig. 1, reference numeral 1 denotes a substrate, reference numeral 2 denotes an anode, reference numeral 3 denotes an organic photoactive layer, and reference numeral 4 denotes a cathode. In some types of electrodes, the symbol 2 indicates the cathode and the symbol 4 indicates the anode.

有機光活性層係至少包括含噻吩基之共軛聚合物A、含噻吩基之共軛聚合物B、及富勒烯衍生物。 The organic photoactive layer includes at least a thiophene-containing conjugated polymer A, a thienyl-containing conjugated polymer B, and a fullerene derivative.

[I]含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B [I] thiophene-containing conjugated polymer A and thiophene-containing conjugated polymer B

用於本發明之含噻吩基之共軛聚合物為包含未取代或經取代噻吩基之共軛聚合物。該取代基係包括碳數為1至18之烷基、碳數為1至18之烷氧基、芳基、鹵素、羥基、氫硫基、羰基、胺基、醚基等；亦可為其組合。 The thiophene-containing conjugated polymer used in the present invention is a conjugated polymer containing an unsubstituted or substituted thienyl group. The substituent includes an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group, a halogen group, a hydroxyl group, a thiol group, a carbonyl group, an amine group, an ether group, etc.; combination.

其他單體單元亦可共聚合至不降低有機光伏元件之性能的程度。至於其他單體單元，任何單體單元均可接受，只要該單體單元在與噻吩基共聚合時形成(1)實質上 結構為使雙鍵及單鍵可交錯地排列之聚合物，(2)實質上結構為使雙鍵及單鍵可以夾置氮原子的方式排列之聚合物，或(3)實質上結構為使雙鍵及單鍵可交錯地排列，且雙鍵及單鍵可以夾置氮原子的方式排列之聚合物。更具體而言，其他單體單元係選自由以下所組成的群組：未取代或經取代茀二基、未取代或經取代苯并茀二基、未取代或經取代二苯并呋喃二基、未取代或經取代二苯并噻吩二基、未取代或經取代咔唑二基、未取代或經取代噻吩二基、未取代或經取代呋喃二基、未取代或經取代吡咯二基、未取代或經取代苯并噻二唑二基、未取代或經取代伸苯基伸乙烯基二基、未取代或經取代噻吩伸乙烯基二基、及未取代或經取代三苯基胺二基。除非有機光伏元件之性能退化，否則聚合噻吩基以外的單體之含量並未特別地限制，但是通常該含量較佳為1至30質量%之範圍，且更佳為1至10質量%之範圍。 Other monomer units can also be copolymerized to the extent that the performance of the organic photovoltaic element is not reduced. As for other monomer units, any monomer unit is acceptable as long as the monomer unit is formed by copolymerization with a thienyl group (1) substantially The structure is a polymer in which a double bond and a single bond are alternately arranged, (2) a polymer having a structure in which a double bond and a single bond can be sandwiched with a nitrogen atom, or (3) a substantially A polymer in which a double bond and a single bond are alternately arranged, and a double bond and a single bond are arranged so as to sandwich a nitrogen atom. More specifically, the other monomer units are selected from the group consisting of unsubstituted or substituted indenyldiyl, unsubstituted or substituted benzoindolediyl, unsubstituted or substituted dibenzofurandiyl , unsubstituted or substituted dibenzothiophenediyl, unsubstituted or substituted carbazolediyl, unsubstituted or substituted thiophenediyl, unsubstituted or substituted furandiyl, unsubstituted or substituted pyrrolidinyl, Unsubstituted or substituted benzothiadiazolediyl, unsubstituted or substituted phenyl extended vinyl diyl, unsubstituted or substituted thiophene vinyl diyl, and unsubstituted or substituted triphenylamine diyl . The content of the monomer other than the polymeric thienyl group is not particularly limited unless the performance of the organic photovoltaic element deteriorates, but usually the content is preferably in the range of 1 to 30% by mass, and more preferably in the range of 1 to 10% by mass. .

由誘發相分離及控制形態的觀點，含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B必須具有彼此不同的結構。已知通常兩種聚合物或嵌段共聚物之混合物因結構差異而造成相分離。在此所引用的名詞「結構差異」係包括不僅主鏈之結構差異，亦及側鏈以及有無官能基之結構差異。 From the viewpoint of inducing phase separation and controlling morphology, the thiophene group-containing conjugated polymer A and the thienyl group-containing conjugated polymer B must have mutually different structures. It is known that usually a mixture of two polymers or block copolymers causes phase separation due to structural differences. The term "structural difference" as used herein includes not only the structural differences of the main chain, but also the structural differences of the side chains and the presence or absence of functional groups.

由電洞移動率的觀點，較佳為含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B均為半晶聚合物。在含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B均為半晶聚合物時，該半晶聚合物係具有熔點，但是由誘發相 分離的觀點，較佳為含噻吩基之共軛聚合物A的熔點與含噻吩基之共軛聚合物B的熔點彼此相差10℃以上。相差10℃以上則可僅將含噻吩基之共軛聚合物A或含噻吩基之共軛聚合物B結晶；因而造成相分離；然後將另一共軛聚合物結晶。含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B的熔點並未特別地限制，但是由所獲得的有機薄膜之結構安定性的觀點，較佳熔點為室溫或以上。 From the viewpoint of the hole mobility, it is preferred that the thiophene group-containing conjugated polymer A and the thienyl group-containing conjugated polymer B are both semicrystalline polymers. When the thiophene-containing conjugated polymer A and the thienyl-containing conjugated polymer B are both semi-crystalline polymers, the semi-crystalline polymer has a melting point but is derived from an induced phase. From the viewpoint of separation, it is preferred that the melting point of the thiophene group-containing conjugated polymer A and the melting point of the thienyl group-containing conjugated polymer B differ from each other by 10 ° C or more. When the difference is 10 ° C or more, only the thiophene group-containing conjugated polymer A or the thienyl group-containing conjugated polymer B may be crystallized; thus, phase separation is caused; and then another conjugated polymer is crystallized. The melting point of the thiophene group-containing conjugated polymer A and the thienyl group-containing conjugated polymer B is not particularly limited, but from the viewpoint of structural stability of the obtained organic film, the melting point is preferably room temperature or higher.

含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B的具體實例為含有未取代噻吩作為主鏈之共軛聚合物、含有碳數為4至18之3-烷基噻吩作為主鏈之共軛聚合物、含有碳數為4至18之3-烷氧基噻吩作為主鏈之共軛聚合物、含有碳數為4至18之3-鹵烷基噻吩作為主鏈之共軛聚合物、含有碳數為4至18之3-鹵烷氧基噻吩作為主鏈之共軛聚合物、含有3-(6-羥基己基)噻吩作為主鏈之共軛聚合物、含有3-(6-溴己基)噻吩作為主鏈之共軛聚合物、含有3-己基氫硫基噻吩作為主鏈之共軛聚合物、含有3-(2’-(2”-甲氧基乙氧基)乙氧基)噻吩作為主鏈之共軛聚合物、含有3-苯氧基甲基噻吩作為主鏈之共軛聚合物、含有3-(6-己基氫硫基)噻吩作為主鏈之共軛聚合物、及這些共軛聚合物之共軛無規共聚物與共軛嵌段共聚物。 Specific examples of the thiophene-containing conjugated polymer A and the thiophene-containing conjugated polymer B are a conjugated polymer containing an unsubstituted thiophene as a main chain, and a 3-alkylthiophene having a carbon number of 4 to 18 as a A conjugated polymer of a main chain, a conjugated polymer having a carbon number of 4 to 18 and a 3-alkoxythiophene as a main chain, and a 3-haloalkylthiophene having 4 to 18 carbon atoms as a main chain a conjugated polymer, a conjugated polymer containing a 4-haloalkoxythiophene having 4 to 18 carbon atoms as a main chain, a conjugated polymer containing 3-(6-hydroxyhexyl)thiophene as a main chain, and containing 3- (6-bromohexyl)thiophene as a conjugated polymer of a main chain, a conjugated polymer containing 3-hexylthiothiophene as a main chain, and containing 3-(2'-(2"-methoxyethoxy) Ethoxy)thiophene as a main chain conjugated polymer, 3-phenoxymethylthiophene as a main chain conjugated polymer, and 3-(6-hexylhydrothio)thiophene as a main chain A conjugated polymer, and a conjugated random copolymer of these conjugated polymers and a conjugated block copolymer.

含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B的數量平均分子量均未特別地限制，但是由電洞移動率及機械性質的觀點，較佳為600至1,000,000克/莫耳之範圍，更佳為5,000至500,000克/莫耳之範圍，且仍更佳為10,000至200,000克/莫耳之範圍。數量平均分子量在此表 示根據凝膠滲透層析術之聚苯乙烯等致物分子量。 The number average molecular weight of the thiophene-containing conjugated polymer A and the thienyl group-containing conjugated polymer B is not particularly limited, but is preferably from 600 to 1,000,000 g/m from the viewpoint of hole mobility and mechanical properties. The range of the ear is more preferably in the range of 5,000 to 500,000 g/mole, and still more preferably in the range of 10,000 to 200,000 g/mole. Number average molecular weight in this table The molecular weight of the polystyrene or the like according to gel permeation chromatography is shown.

由於欲將含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B以混合狀態誘發相分離及控制形態之目的，其可使用含噻吩基之共軛聚合物A與含噻吩基之共軛聚合物B的聚合物摻合物、以及包含含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B的共軛嵌段共聚物。較佳為使用包含含噻吩基之共軛聚合物A及含噻吩基之共軛聚合物B的共軛嵌段共聚物。嵌段共聚物在此係包括二嵌段共聚物、三嵌段共聚物及多嵌段共聚物。 Since the thiophene group-containing conjugated polymer A and the thienyl group-containing conjugated polymer B are intended to induce phase separation and control morphology in a mixed state, a thiophene-containing conjugated polymer A and a thienyl group may be used. A polymer blend of conjugated polymer B, and a conjugated block copolymer comprising a thiophene-containing conjugated polymer A and a thienyl-containing conjugated polymer B. It is preferred to use a conjugated block copolymer comprising a conjugated polymer A containing a thienyl group and a conjugated polymer B containing a thienyl group. Block copolymers herein include diblock copolymers, triblock copolymers, and multiblock copolymers.

在本發明中，在有機光活性層中，含噻吩基之共軛聚合物A與含噻吩基之共軛聚合物B的總重量較佳為5至90質量%之範圍，且更佳為10至70質量%之範圍。如果總重量過小或過大，則可能無法獲得高轉換效率。 In the present invention, the total weight of the thiophene-containing conjugated polymer A and the thienyl group-containing conjugated polymer B in the organic photoactive layer is preferably in the range of 5 to 90% by mass, and more preferably 10 Up to 70% by mass. If the total weight is too small or too large, high conversion efficiency may not be obtained.

在本發明中，含於有機光活性層中的含噻吩基之共軛聚合物A與含噻吩基之共軛聚合物B的質量比並未特別地限制，但是較佳為95：5至5：95之範圍，且更佳為90：10至10：90之範圍。較佳為產生比另一高之電力轉換效率的含噻吩基之共軛聚合物A或含噻吩基之共軛聚合物B係含有較多。 In the present invention, the mass ratio of the thiophene group-containing conjugated polymer A and the thienyl group-containing conjugated polymer B contained in the organic photoactive layer is not particularly limited, but is preferably 95:5 to 5 Range of 95, and more preferably in the range of 90:10 to 10:90. It is preferred that the thiophene group-containing conjugated polymer A or the thienyl group-containing conjugated polymer B having a higher power conversion efficiency is contained more.

[II]富勒烯衍生物 [II] fullerene derivatives

富勒烯衍生物係指C60、C70、C84、及其衍生物。至於富勒烯衍生物之具體結構則為以下結構。 Fullerene derivatives refer to C60, C70, C84, and derivatives thereof. As for the specific structure of the fullerene derivative, the following structure is obtained.

在含噻吩基之共軛聚合物A與含噻吩基之共軛聚合物B為總共100重量份時，有機光活性層中的富勒烯衍生物份量較佳為10至1,000重量份之範圍，且更佳為50至500重量份之範圍。 When the thiophene group-containing conjugated polymer A and the thienyl group-containing conjugated polymer B are 100 parts by weight in total, the amount of the fullerene derivative in the organic photoactive layer is preferably in the range of 10 to 1,000 parts by weight. More preferably, it is in the range of 50 to 500 parts by weight.

混合含噻吩基之共軛聚合物A、含噻吩基之共軛聚合物B、及富勒烯衍生物之方法並未特別地限制，但是較佳 為一種在將其按所欲比例加入溶劑之後，藉加熱、攪拌及超音波照射之一或兩種或以上的組合，將其溶於溶劑之方法。 The method of mixing the thiophene group-containing conjugated polymer A, the thienyl group-containing conjugated polymer B, and the fullerene derivative is not particularly limited, but is preferably. It is a method of dissolving it in a solvent by adding one or a combination of two or more of heat, agitation and ultrasonic irradiation after it is added to a solvent in a desired ratio.

在混合含噻吩基之共軛聚合物A、含噻吩基之共軛聚合物B、及富勒烯衍生物時所使用的溶劑並未特別地限制，只要能將大部分溶於該溶劑中。具體實例為醚，如四氫呋喃；鹵素溶劑，如二氯甲烷與氯仿；芳香族溶劑，如苯、甲苯、鄰二甲苯、氯苯、鄰二氯苯、及吡啶。 The solvent to be used in mixing the thiophene group-containing conjugated polymer A, the thienyl group-containing conjugated polymer B, and the fullerene derivative is not particularly limited as long as it can be mostly dissolved in the solvent. Specific examples are ethers such as tetrahydrofuran; halogen solvents such as dichloromethane and chloroform; aromatic solvents such as benzene, toluene, o-xylene, chlorobenzene, o-dichlorobenzene, and pyridine.

有機光活性層之膜厚通常為1nm至1μm之範圍，較佳為2nm至1,000nm之範圍，更佳為5nm至500nm之範圍，且仍更佳為20nm至300nm之範圍。如果光活性層厚度太薄則光吸收不足，反之如果太厚，則載子幾乎不會到達電極。 The film thickness of the organic photoactive layer is usually in the range of 1 nm to 1 μm, preferably in the range of 2 nm to 1,000 nm, more preferably in the range of 5 nm to 500 nm, and still more preferably in the range of 20 nm to 300 nm. If the thickness of the photoactive layer is too thin, the light absorption is insufficient, and if it is too thick, the carrier hardly reaches the electrode.

[III]電極 [III] electrode

在依照本發明之有機光伏元件中，較佳為陽極2或陰極4係具有光滲透力。電極之光滲透力並未特別地限制，只要為入射光到達有機光活性層3且發生電動勢之程度。電極之厚度可為任何厚度，只要該厚度為確保光滲透力及導電性之程度，但是較佳為20nm至300nm之範圍，雖然其係依照電極材料而改變。關於其他電極，光滲透力在此並非始終必要，只要該電極係具有導電性，且該厚度並未特別地限制。 In the organic photovoltaic element according to the present invention, it is preferred that the anode 2 or the cathode 4 has a light penetrating power. The light penetrating power of the electrode is not particularly limited as long as the incident light reaches the organic photoactive layer 3 and the electromotive force is generated. The thickness of the electrode may be any thickness as long as the thickness is a degree of ensuring light penetration and conductivity, but is preferably in the range of 20 nm to 300 nm, although it varies depending on the electrode material. Regarding the other electrodes, the light penetrating power is not always necessary here as long as the electrode is electrically conductive, and the thickness is not particularly limited.

關於電極材料，其較佳為使用具有高作業函數之導電性材料作為一電極，且使用具有低作業函數之導電性材料作為其他電極。使用具有高作業函數之導電性材料的電極為陽極。至於具有高作業函數之導電性材料，除 了金屬，如金、鉑、鉻、與鎳，較佳為使用具有透明性之銦或錫的金屬氧化物，或組合金屬氧化物，如氧化銦錫(ITO)、氧化銦鋅(IZO)、與摻氟氧化錫(FTO)。在此較佳為用於陽極2之導電性材料係與有機光活化層3歐姆接觸。此外，在使用後述電洞傳輸層的情形，較佳為用於陽極2之導電性材料係與電洞傳輸層歐姆接觸。 As the electrode material, it is preferable to use a conductive material having a high work function as an electrode, and a conductive material having a low work function as another electrode. An electrode using a conductive material having a high work function is an anode. As for conductive materials with high operating functions, Metals such as gold, platinum, chromium, and nickel are preferably used as metal oxides of transparent indium or tin, or combined metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), With fluorine doped tin oxide (FTO). Here, it is preferred that the conductive material for the anode 2 is in ohmic contact with the organic photoactive layer 3. Further, in the case of using the hole transport layer described later, it is preferable that the conductive material for the anode 2 is in ohmic contact with the hole transport layer.

使用具有低作業函數之導電性材料的電極為陰極，且鹼金屬或鹼土金屬，更具體而言為使用鋰、鎂、鈣、或鋇作為具有低作業函數之導電性材料。此外，亦較佳為使用錫、銀或鋁。此外，亦較佳為使用包含含有以上金屬之合金或包含以上金屬之積層體的電極。另外，亦可藉由將金屬氟化物，如氟化鋰或氟化銫，引入陰極4與電子傳輸層之間的界面而增加電流。在此較佳為用於陰極4之導電性材料係與有機光活化層3歐姆接觸。此外，在使用電子傳輸層時，較佳為用於陰極4之導電性材料係與電子傳輸層歐姆接觸。 An electrode using a conductive material having a low work function is used as a cathode, and an alkali metal or an alkaline earth metal, more specifically, lithium, magnesium, calcium, or barium is used as a conductive material having a low work function. Further, it is also preferred to use tin, silver or aluminum. Further, it is also preferred to use an electrode including an alloy containing the above metal or a laminate including the above metal. Alternatively, current can be increased by introducing a metal fluoride such as lithium fluoride or cesium fluoride into the interface between the cathode 4 and the electron transport layer. Here, it is preferred that the conductive material for the cathode 4 is in ohmic contact with the organic photoactive layer 3. Further, when the electron transport layer is used, it is preferred that the conductive material for the cathode 4 is in ohmic contact with the electron transport layer.

[IV]基板 [IV] substrate

基板1可為任何材料，只要其可形成電極且在形成有機光活化層時不產生變化。例如可藉任意方法使用由如無鹼玻璃或石英玻璃之無機材料所製造的膜或板、如鋁之金屬膜、或有機材料，如聚酯、聚碳酸酯、聚烯烴、聚醯胺、聚醯亞胺、聚苯硫醚、聚對二甲苯、環氧樹脂、或含氟樹脂。在使用不透明基板時，對立電極(即遠離基板之電極)必須為透明或半透明。基板之膜厚並未特別地限制，但是通常為1μm至10mm之範圍。 The substrate 1 may be any material as long as it can form an electrode and does not change when the organic photoactive layer is formed. For example, a film or sheet made of an inorganic material such as alkali-free glass or quartz glass, a metal film such as aluminum, or an organic material such as polyester, polycarbonate, polyolefin, polyamide, or poly can be used by any method. Yttrium, polyphenylene sulfide, parylene, epoxy resin, or fluorine-containing resin. When an opaque substrate is used, the counter electrode (ie, the electrode remote from the substrate) must be transparent or translucent. The film thickness of the substrate is not particularly limited, but is usually in the range of 1 μm to 10 mm.

此外，為了改良基板之潤濕力、及有機層與基板間界面處黏附性，較佳為藉物理方法將表面清潔及重組，如UV臭氧處理、電暈放電處理、或電漿處理。此外，以矽烷偶合劑、鈦酸酯型偶合劑、或自組式單層對固態基板的表面施加化學修改之方法同樣有效。 Further, in order to improve the wetting force of the substrate and the adhesion at the interface between the organic layer and the substrate, it is preferred to physically clean and recombine the surface, such as UV ozone treatment, corona discharge treatment, or plasma treatment. Further, a method of applying chemical modification to the surface of the solid substrate by a decane coupling agent, a titanate type coupling agent, or a self-assembled single layer is also effective.

在本發明中可在陽極2與有機光活性層3之間形成電洞傳輸層。至於用於形成電洞傳輸層之材料，其較佳為使用導電性聚合物，如聚噻吩衍生物、聚對伸苯基伸乙烯基衍生物、或聚茀衍生物，或顯示P-型半導體特徵之低分子有機化合物，如酞青衍生物(H2Pc、CuPc、ZnPc等)或卟啉衍生物。具體而言，其較佳為使用聚伸乙二氧基噻吩(PEDOT)、或將聚苯乙烯磺酸酯(PSS)加入PEDOT所製造的基板。電洞傳輸層之厚度較佳為5nm至600nm之範圍，且更佳為20nm至300nm之範圍。 A hole transport layer can be formed between the anode 2 and the organic photoactive layer 3 in the present invention. As the material for forming the hole transport layer, it is preferred to use a conductive polymer such as a polythiophene derivative, a polyparaphenylene vinyl derivative, or a polyfluorene derivative, or to exhibit a P-type semiconductor characteristic. Low molecular organic compounds such as indigo derivatives (H2Pc, CuPc, ZnPc, etc.) or porphyrin derivatives. Specifically, it is preferably a substrate produced by using polyethylene dioxythiophene (PEDOT) or polystyrene sulfonate (PSS) added to PEDOT. The thickness of the hole transport layer is preferably in the range of 5 nm to 600 nm, and more preferably in the range of 20 nm to 300 nm.

[V]形成膜之方法 [V] method of forming a film

至於形成有機光活化層之方法，其可使用已知方法，如旋塗法、流延法、微米凹版塗覆法、凹版塗覆法、狹縫模具塗覆法、棒式塗覆法、輥式塗覆法、浸塗法、噴塗法、網版印刷法、彈性印刷法、平版印刷法、噴墨印刷法、噴嘴塗覆法、或毛細管塗覆法。 As for the method of forming the organic photoactive layer, a known method such as a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a slit die coating method, a bar coating method, a roll can be used. Coating method, dip coating method, spray coating method, screen printing method, elastic printing method, lithography method, inkjet printing method, nozzle coating method, or capillary coating method.

[VI]溶劑處理 [VI] Solvent treatment

本發明之一個特點為在形成有機光活性層之後，將有機光活性層之薄膜在25℃暴露於表面張力為含噻吩基之共軛聚合物(A或B)的表面張力與富勒烯衍生物的表面張力之間的溶劑蒸汽。含噻吩基之共軛聚合物(A或B)的 表面張力為，其一含噻吩基之共軛聚合物的表面張力對富勒烯衍生物的表面張力之差異較另一聚合物的表面張力為大。在大部分的情形，富勒烯衍生物的表面張力係大於含噻吩基之共軛聚合物(A或B)的表面張力。在此情形，含噻吩基之共軛聚合物(A或B)的表面張力為含噻吩基之共軛聚合物(A或B)的較小表面張力。施加溶劑處理則可誘發含噻吩基之共軛聚合物與富勒烯衍生物之間的奈米程度之小規模相分離。降低相分離尺寸則可增加含噻吩基之共軛聚合物與富勒烯衍生物之間的界面面積，因而戲劇性地提高電力轉換效率。此外，施加溶劑則含噻吩基之共軛聚合物及富勒烯衍生物的相分離域各對基板垂直地導向，因此可能形成接近最適合電洞及電子傳輸之結構的形態。 A feature of the present invention is that after forming an organic photoactive layer, the film of the organic photoactive layer is exposed to a surface tension of a thiophene-containing conjugated polymer (A or B) at 25 ° C and fullerene-derived. Solvent vapor between the surface tension of the object. Thiophene-containing conjugated polymer (A or B) The surface tension is such that the surface tension of the thiophene-containing conjugated polymer has a larger surface tension to the fullerene derivative than the surface tension of the other polymer. In most cases, the surface tension of the fullerene derivative is greater than the surface tension of the thiophene-containing conjugated polymer (A or B). In this case, the surface tension of the thiophene-containing conjugated polymer (A or B) is a small surface tension of the thiophene-containing conjugated polymer (A or B). The application of a solvent treatment induces a small-scale phase separation of the degree of nanolinity between the thiophene-containing conjugated polymer and the fullerene derivative. Reducing the phase separation size increases the interfacial area between the thiophene-containing conjugated polymer and the fullerene derivative, thus dramatically increasing the power conversion efficiency. Further, when a solvent is applied, the phase separation domains of the thiophene-containing conjugated polymer and the fullerene derivative are vertically guided to the substrate, and thus it is possible to form a structure close to the structure most suitable for the hole and electron transport.

此外，其可任意地選擇用於溶劑處理之溶劑。如JP 2009-260324 A號專利所例示，設計溶劑以溶解聚合物及富勒烯衍生物之方法無法使用聚合物與富勒烯衍生物之溶解度不良的溶劑，且並非始終形成最適合的形態。另一方面，使用依照本發明之溶劑處理則可使用最適合控制有機光活性層的形態之任意溶劑，且對溶劑處理用溶劑之選擇並無限制。 Further, it can be arbitrarily selected as a solvent for solvent treatment. As exemplified in JP 2009-260324 A, the solvent for designing a solvent to dissolve a polymer and a fullerene derivative cannot use a solvent having a poor solubility of a polymer and a fullerene derivative, and does not always form an optimum form. On the other hand, any solvent which is most suitable for controlling the form of the organic photoactive layer can be used by the solvent treatment according to the present invention, and the choice of the solvent for solvent treatment is not limited.

此外，在JP 2009-260324 A號專利所揭示的方法中，控制形態之溶劑並非始終具有良好的膜形成力，且可能無法同時獲得膜表面良好之有機光活性層形成及形態控制。藉本發明方法則可獨立地獲得膜形成及形態控制，因此不發生上述問題。 Further, in the method disclosed in JP 2009-260324 A, the solvent of the controlled form does not always have a good film forming force, and it may not be possible to simultaneously obtain a good organic photoactive layer formation and morphology control of the film surface. Film formation and morphology control can be independently obtained by the method of the present invention, so that the above problems do not occur.

本發明方法之溶劑處理用溶劑必須為表面張力在含噻吩基之共軛聚合物A或B的表面張力與富勒烯衍生物的表面張力之間的溶劑。如果使用表面張力在以上表面張力之外的溶劑，則需要長溶劑處理時間且溶劑處理不具經濟性，或者無法獲得改良電力轉換效率之效果。此外，由於表面張力係依溫度改變，故考量溶劑處理環境之溫度的表面張力為必要的。 The solvent for solvent treatment of the method of the present invention must be a solvent having a surface tension between the surface tension of the thiophene-containing conjugated polymer A or B and the surface tension of the fullerene derivative. If a solvent having a surface tension other than the above surface tension is used, a long solvent treatment time is required and solvent treatment is not economical, or an effect of improving power conversion efficiency cannot be obtained. In addition, since the surface tension varies depending on the temperature, it is necessary to consider the surface tension of the temperature of the solvent treatment environment.

此溶劑並未特別地限制，只要其滿足以上條件，且可選自由例如以下所組成的群組：脂族烴溶劑，如正戊烷、正己烷與環己烷；鹵化烴溶劑，如二氯甲烷、1,2-二氯乙烷與氯仿；芳族烴溶劑，如苯、甲苯與二甲苯；鹵化芳族溶劑，如氯苯、鄰二氯苯與溴苯；氧化溶劑，如丙酮、四氫呋喃、二氧陸圜、乙酸乙酯、甲氧苯、與苯甲酸甲酯；及含氮溶劑，如乙腈、三乙胺與吡啶。這些容劑可單獨地或以二種或以上的組合使用。在二種或以上的組合的情形，其可從成分的表面張力計算組成物的表面張力。此外，在溶劑的表面張力為未知時，其可藉已知方法測量表面張力，如不濡液滴法(sessile drop method)或威式法(Wilhelmy method)。 The solvent is not particularly limited as long as it satisfies the above conditions, and may be selected, for example, from the group consisting of aliphatic hydrocarbon solvents such as n-pentane, n-hexane and cyclohexane; halogenated hydrocarbon solvents such as dichloro Methane, 1,2-dichloroethane and chloroform; aromatic hydrocarbon solvents such as benzene, toluene and xylene; halogenated aromatic solvents such as chlorobenzene, o-dichlorobenzene and bromobenzene; oxidizing solvents such as acetone, tetrahydrofuran , dioxin, ethyl acetate, methoxybenzene, and methyl benzoate; and a nitrogen-containing solvent such as acetonitrile, triethylamine and pyridine. These agents may be used singly or in combination of two or more. In the case of a combination of two or more, it is possible to calculate the surface tension of the composition from the surface tension of the component. Further, when the surface tension of the solvent is unknown, it is possible to measure the surface tension by a known method such as a sessile drop method or a Wilhelmy method.

通常含噻吩基之共軛聚合物溶劑的表面張力在大部分的情形為20至27mN/m2之範圍，及富勒烯衍生物的表面張力在大部分的情形為34至37mN/m2之範圍(Synthetic Metals 157(2007)726-732；Langmuir 2006,22,9287-9294：Macromolecules 2007,40,8291-8301；及Organic Electronics 11(2010)899-904)，因此較佳為在本發明中 使用在25℃表面張力係介於其中，為27至37mN/m2之範圍的溶劑。至於此種溶劑則為二氯甲烷(27.2mN/m2)、1,2-二氯乙烷(31.9mN/m2)、苯(28.2mN/m2)、甲苯(27.9mN/m2)、鄰二甲苯(29.8mN/m2)、氯苯(33.0mN/m2)、溴苯(35.2mN/m2)、鄰二氯苯(35.6mN/m2)、及甲氧苯(35.1mN/m2)。表面張力值係基於J.Phys.Chem.Ref.Data,1,841,1972，或於1998年，John A.Dean所編著，McGraw-Hill Professional所出版的“Lange’s Handbook of Chemistry 15th edition”中所述值而敘述。 The surface tension of the thiophene-containing conjugated polymer solvent is usually in the range of 20 to 27 mN/m 2 in most cases, and the surface tension of the fullerene derivative is 34 to 37 mN/m 2 in most cases. Range (Synthetic Metals 157 (2007) 726-732; Langmuir 2006, 22, 9287-9294: Macromolecules 2007, 40, 8291-8301; and Organic Electronics 11 (2010) 899-904), and thus preferably in the present invention A solvent having a surface tension of 25 to 37 in a range of 27 to 37 mN/m 2 was used. The solvent is dichloromethane (27.2 mN/m 2 ), 1,2-dichloroethane (31.9 mN/m 2 ), benzene (28.2 mN/m 2 ), toluene (27.9 mN/m 2 ). , o-xylene (29.8mN/m 2 ), chlorobenzene (33.0mN/m 2 ), bromobenzene (35.2mN/m 2 ), o-dichlorobenzene (35.6mN/m 2 ), and methoxybenzene (35.1) mN/m 2 ). The surface tension values are based on the values described in J. Phys. Chem. Ref. Data, 1, 841, 1972, or "Lange's Handbook of Chemistry 15th edition", published by John A. Dean, 1998, McGraw-Hill Professional. And narrative.

用於本發明之溶劑的沸點並未特別地限制，但是由必須暴露於溶劑蒸汽的觀點，如果沸點太高則蒸汽壓降低且幾乎無法獲得效果。在此情形，亦可提高溶劑處理之大氣溫度。 The boiling point of the solvent used in the present invention is not particularly limited, but from the viewpoint that it is necessary to be exposed to the solvent vapor, if the boiling point is too high, the vapor pressure is lowered and the effect is hardly obtained. In this case, the atmospheric temperature of the solvent treatment can also be increased.

暴露於溶劑蒸汽時之大氣溫度並未特別地限制，但是由處理容易性的觀點，較佳為不低於室溫且不高於溶劑沸點。通常採用較接近室溫之溫度。 The atmospheric temperature at the time of exposure to the solvent vapor is not particularly limited, but from the viewpoint of ease of handling, it is preferably not lower than room temperature and not higher than the boiling point of the solvent. Temperatures closer to room temperature are usually used.

本發明所應用的溶劑處理並未特別地限制，只要可將有機薄膜暴露於溶劑蒸汽中。例如可使用將有機薄膜以不觸及溶劑的方式引入含有溶劑之容器中之方法，或將由溶劑起泡所產生的溶劑蒸汽與如空氣或氮之氣體一起輸送且暴露有機薄膜之方法。 The solvent treatment to which the present invention is applied is not particularly limited as long as the organic film can be exposed to solvent vapor. For example, a method of introducing an organic film into a container containing a solvent without touching a solvent, or a method of transporting a solvent vapor generated by foaming of a solvent together with a gas such as air or nitrogen and exposing the organic film may be used.

在本發明中，較佳為在溶劑蒸汽中之暴露時間短，因為其具經濟性。使用表面張力為以上範圍之溶劑則可縮短溶劑處理時間及實現經濟性程序。處理時間較佳為1秒至30分鐘之範圍，更佳為5秒至20分鐘之範圍，且仍更 佳為10秒至10分鐘之範圍。 In the present invention, it is preferred that the exposure time in the solvent vapor is short because it is economical. The use of a solvent having a surface tension of the above range can shorten the solvent treatment time and achieve an economical procedure. The treatment time is preferably in the range of 1 second to 30 minutes, more preferably in the range of 5 seconds to 20 minutes, and still more It is preferably in the range of 10 seconds to 10 minutes.

如果含噻吩基之共軛聚合物及富勒烯衍生物的表面張力為未知，則其可藉由測量接觸角而計算。即可使用已知的測量方法，如使用數種表面張力不同的液體，測量對欲測量的含噻吩基之共軛聚合物及富勒烯衍生物的接觸角，及應用蔡斯門(Zismann)作圖而獲得臨界表面張力之方法；或計算表面張力之Owens-Wendt法，其係測量兩種其中已知非極性分散力分量γd及極性氫鍵分量γh之液體的接觸角。 If the surface tension of the thiophene-containing conjugated polymer and the fullerene derivative is unknown, it can be calculated by measuring the contact angle. Known measurement methods can be used, such as using several liquids with different surface tensions, measuring the contact angle of the thiophene-containing conjugated polymer and fullerene derivative to be measured, and applying Zesmann A method of obtaining a critical surface tension by drawing; or an Owens-Wendt method for calculating surface tension, which measures a contact angle of two liquids in which a nonpolar dispersion force component γ d and a polar hydrogen bond component γ h are known.

依照本發明之有機光伏元件可進一步具有無機層。至於含於無機層之材料則為例如金屬氧化物，如氧化鈦、氧化錫、氧化鋅、氧化鐵、氧化鎢、氧化鋯、氧化鉿、氧化鍶、氧化銦、氧化鈰、氧化釔、氧化鑭、氧化釩、氧化鈮、氧化鉭、氧化鎵、氧化鎳、鈦酸鍶、鈦酸鋇、鈮酸鉀、與鉭酸鈉；金屬鹵化物，如碘化銀、溴化銀、碘化銅、溴化銅、與氟化鋰；金屬硫化物，如硫化鋅、硫化鈦、硫化銦、硫化鉍、硫化鎘、硫化鋯、硫化鉭、硫化鉬、硫化銀、硫化銅、硫化錫、硫化鎢、與硫化銻；金屬砷化物，如砷化鎘、砷化鋯、砷化鋅、砷化鈦、砷化銦、砷化鎢、砷化鉬、砷化鉍、與砷化鉛；金屬碲化物，如碲化鎘、碲化鎢、碲化鉬、碲化鋅、與碲化鉍；金屬磷化物，如磷化鋅、磷化鎵、磷化銦、與磷化鎘；砷化鎵；硒化銅-銦；硫化銅-銦；矽；及鍺。此外，二種或以上的這些物質之混合物亦可接受。至於該混合物，例如其為氧化鋅與氧化錫之混合物及氧化錫與氧 化鈦之混合物。 The organic photovoltaic element according to the invention may further have an inorganic layer. The material contained in the inorganic layer is, for example, a metal oxide such as titanium oxide, tin oxide, zinc oxide, iron oxide, tungsten oxide, zirconium oxide, hafnium oxide, tantalum oxide, indium oxide, antimony oxide, antimony oxide or antimony oxide. , vanadium oxide, cerium oxide, cerium oxide, gallium oxide, nickel oxide, barium titanate, barium titanate, potassium citrate, and sodium citrate; metal halides such as silver iodide, silver bromide, copper iodide, bromination Copper, and lithium fluoride; metal sulfides such as zinc sulfide, titanium sulfide, indium sulfide, antimony sulfide, cadmium sulfide, zirconium sulfide, antimony sulfide, molybdenum sulfide, silver sulfide, copper sulfide, tin sulfide, tungsten sulfide, and vulcanization金属; metal arsenide, such as arsenic arsenide, arsenic arsenide, zinc arsenide, titanium arsenide, indium arsenide, tungsten arsenide, molybdenum arsenide, antimony arsenide, and lead arsenide; metal telluride, such as germanium Cadmium, tungsten telluride, molybdenum telluride, zinc telluride, and antimony telluride; metal phosphides such as zinc phosphide, gallium phosphide, indium phosphide, and cadmium phosphide; gallium arsenide; copper selenide Indium; copper sulfide-indium; antimony; and antimony. In addition, mixtures of two or more of these materials are also acceptable. As for the mixture, for example, it is a mixture of zinc oxide and tin oxide and tin oxide and oxygen a mixture of titanium.

依照本發明之有機光伏元件可應用於各種利用光電轉換功能、光學整流功能(光電二極體)、及其他功能之光電轉換裝置。例如該有機光伏元件可用於光伏電池、電子裝置(光學感應器、光學開關、光電晶體等)、光學記憶材料(光學記憶體等)等。 The organic photovoltaic element according to the present invention can be applied to various photoelectric conversion devices using photoelectric conversion functions, optical rectification functions (photodiodes), and other functions. For example, the organic photovoltaic element can be used for photovoltaic cells, electronic devices (optical sensors, optical switches, photovoltaic crystals, etc.), optical memory materials (optical memories, etc.), and the like.

[實施例] [Examples]

本發明在以下參考實施例而進一步詳細解釋，但是不限於這些實施例。 The invention is explained in further detail below with reference to the examples, but is not limited to the examples.

[含有噻吩基之共軛嵌段共聚物(P1)之合成] [Synthesis of a conjugated block copolymer (P1) containing a thienyl group]

在將充分乾燥的玻璃回收燒瓶A充分地以氬取代之後，添加45質量份之THF及0.054質量份之聚合觸媒NiCl2(dppp)。同時在另一乾燥的玻璃回收燒瓶B中添加29質量份之THF、2.8質量份之2-溴-3-己基-5-碘噻吩、及3.5質量份之2.0M溴化異丙基鎂溶液，且在0℃攪拌30分鐘。然後將該已反應溶液加入回收燒瓶A中且在35℃聚合90分鐘。連續地將在另一乾燥的玻璃回收燒瓶C中添加16質量份之THF、1.4質量份之2-溴-3-(2-乙基)己基-5-碘噻吩、及1.7質量份之2.0M溴化異丙基鎂溶液所製造，且在0℃將其反應30分鐘的溶液加入回收燒瓶A中，及反應7小時。在反應後添加4質量份之1.0M氯化第三丁基鎂的THF溶液且攪拌1小時，再添加100質量份之5M氫氯酸且攪拌1小時，然後中止聚合。然後以900質量份之氯仿萃取，以200質量份之碳酸氫鈉及200質量份之蒸餾水清洗，濃縮，乾燥，及固化。將所獲得的黑色及紫色固態物 質溶於56質量份之氯仿，在600質量份之丙酮中再沉澱，及充分地乾燥，如此獲得共軛嵌段共聚物(聚合物名稱：聚[(3-己基噻吩)-嵌段-(3-(2-乙基己基)噻吩)](P1)。所獲得的含有噻吩基之共軛嵌段共聚物(P1)的重量平均分子量為21,600克/莫耳，及其數量平均分子量為17,900克/莫耳。聚(3-己基噻吩)嵌段之含量為79莫耳%。 After the sufficiently dried glass recovery flask A was sufficiently substituted with argon, 45 parts by mass of THF and 0.054 parts by mass of a polymerization catalyst NiCl 2 (dppp) were added. At the same time, 29 parts by mass of THF, 2.8 parts by mass of 2-bromo-3-hexyl-5-iodothiophene, and 3.5 parts by mass of 2.0 M isopropylmagnesium bromide solution were added to another dried glass recovery flask B. It was stirred at 0 ° C for 30 minutes. The reacted solution was then added to the recovery flask A and polymerized at 35 ° C for 90 minutes. 16 parts by mass of THF, 1.4 parts by mass of 2-bromo-3-(2-ethyl)hexyl-5-iodothiophene, and 1.7 parts by mass of 2.0 M were continuously added to another dried glass recovery flask C. A solution of isopropylmagnesium bromide was prepared, and a solution which was reacted at 0 ° C for 30 minutes was added to the recovery flask A, and the reaction was carried out for 7 hours. After the reaction, 4 parts by mass of a 1.0 M solution of butylmagnesium chloride in THF was added and stirred for 1 hour, and then 100 parts by mass of 5 M hydrochloric acid was added and stirred for 1 hour, and then the polymerization was terminated. Then, it was extracted with 900 parts by mass of chloroform, washed with 200 parts by mass of sodium hydrogencarbonate and 200 parts by mass of distilled water, concentrated, dried, and solidified. The obtained black and purple solid matter was dissolved in 56 parts by mass of chloroform, reprecipitated in 600 parts by mass of acetone, and sufficiently dried to obtain a conjugated block copolymer (polymer name: poly[(3- hexylthiophene) - block - (3- (2-ethylhexyl) thiophene)] (P1) containing the obtained thienyl conjugated block copolymer (P1) of the weight average molecular weight 21,600 g / mole And its number average molecular weight was 17,900 g/mol. The content of the poly(3-hexylthiophene) block was 79 mol%.

關於在各上述程序所獲得的材料及經由以下程序所製造的材料，該聚合物之物理性質係如下測量。 Regarding the materials obtained in each of the above procedures and the materials produced through the following procedures, the physical properties of the polymer were measured as follows.

○重量平均分子量及數量平均分子量 ○ Weight average molecular weight and number average molecular weight

數量平均分子量及重量平均分子量各係根據凝膠滲透層析術(GPC)所測量，按聚苯乙烯致物換算而獲得。在此使用由Tosoh Corporation所製造的HLC-8320GPC作為GPC裝置，且使用二個串接之由Tosoh Corporation所製造的TSKgel SuperMultipore HZ-Ms作為管柱。 The number average molecular weight and the weight average molecular weight are each obtained by gel permeation chromatography (GPC) in terms of polystyrene conversion. Here, HLC-8320GPC manufactured by Tosoh Corporation was used as a GPC device, and two TSKgel SuperMultipore HZ-Ms manufactured by Tosoh Corporation in series were used as a column.

[含有噻吩基之共軛嵌段共聚物(P2)之合成] [Synthesis of a conjugated block copolymer (P2) containing a thienyl group]

在將充分乾燥的玻璃回收燒瓶A充分地以氬取代之後，添加45質量份之THF及0.054質量份之聚合觸媒NiCl2(dppp)。同時在另一乾燥的玻璃回收燒瓶B中添加27質量份之THF、2.2質量份之2-溴-3-己基-5-碘噻吩、及3.2質量份之2.0M溴化異丙基鎂溶液，且在0℃攪拌30分鐘。然後將該已反應溶液加入回收燒瓶A中且在35℃聚合90分鐘。連續地將在另一乾燥的玻璃回收燒瓶C中添加18質量份之THF、1.6質量份之2-溴-3-(2-乙基)己基-5-碘噻吩、及2.2質量份之2.0M溴化異丙基鎂溶液所製造，且在0℃將其反應30分鐘的溶液加入回收燒瓶A中，及反應7小時 。在反應後添加4質量份之1.0M氯化第三丁基鎂的THF溶液且攪拌1小時，再添加100質量份之5M氫氯酸且攪拌1小時，然後中止聚合。然後以900質量份之氯仿萃取，以200質量份之碳酸氫鈉及200質量份之蒸餾水清洗，濃縮，乾燥，及固化。將所獲得的黑色及紫色固態物質溶於56質量份之氯仿，在600質量份之丙酮中再沉澱，及充分地乾燥，如此獲得含有噻吩之共軛嵌段共聚物(聚合物名稱：聚[(3-己基噻吩)-嵌段-(3-(2-乙基己基)噻吩)](P2)。所獲得的含有噻吩基之共軛嵌段共聚物(P2)的重量平均分子量為24,500克/莫耳，及其數量平均分子量為21,300克/莫耳。聚(3-己基噻吩)嵌段之含量為68莫耳%。 After the sufficiently dried glass recovery flask A was sufficiently substituted with argon, 45 parts by mass of THF and 0.054 parts by mass of a polymerization catalyst NiCl 2 (dppp) were added. At the same time, 27 parts by mass of THF, 2.2 parts by mass of 2-bromo-3-hexyl-5-iodothiophene, and 3.2 parts by mass of 2.0 M isopropylmagnesium bromide solution were added to another dried glass recovery flask B. It was stirred at 0 ° C for 30 minutes. The reacted solution was then added to the recovery flask A and polymerized at 35 ° C for 90 minutes. 18 parts by mass of THF, 1.6 parts by mass of 2-bromo-3-(2-ethyl)hexyl-5-iodothiophene, and 2.2 parts by mass of 2.0 M were continuously added to another dried glass recovery flask C. A solution of isopropylmagnesium bromide was prepared, and a solution which was reacted at 0 ° C for 30 minutes was added to the recovery flask A, and the reaction was carried out for 7 hours. After the reaction, 4 parts by mass of a 1.0 M solution of butylmagnesium chloride in THF was added and stirred for 1 hour, and then 100 parts by mass of 5 M hydrochloric acid was added and stirred for 1 hour, and then the polymerization was terminated. Then, it was extracted with 900 parts by mass of chloroform, washed with 200 parts by mass of sodium hydrogencarbonate and 200 parts by mass of distilled water, concentrated, dried, and solidified. The obtained black and purple solid matter was dissolved in 56 parts by mass of chloroform, reprecipitated in 600 parts by mass of acetone, and sufficiently dried to obtain a conjugated block copolymer containing thiophene (polymer name: poly[ (3-hexylthiophene) -block- (3-(2-ethylhexyl)thiophene)] (P2). The obtained thiophene-containing conjugated block copolymer (P2) has a weight average molecular weight of 24,500 g. / Mohr, and its number average molecular weight is 21,300 g / mol. The content of the poly(3-hexylthiophene) block is 68 mol%.

[含噻吩基之共軛聚合物(P3)之合成] [Synthesis of thiophene-containing conjugated polymer (P3)]

在將充分乾燥的玻璃回收燒瓶充分地以氬取代之後，在其中添加33質量份之THF及0.04質量份之聚合觸媒NiCl2(dppp)。同時，在另一乾燥的三頸燒瓶中添加33質量份之THF、2.8質量份之2-溴-3-己基-5-碘噻吩、及4.0質量份之2.0M溴化異丙基鎂溶液，且在0℃攪拌30分鐘。然後將該已反應溶液加入前者燒瓶中，並且在35℃聚合90分鐘。連續地添加3質量份之1.0M氯化第三丁基鎂的THF溶液且攪拌3小時，再添加50質量份之5M氫氯酸且攪拌1小時，然後中止聚合。然後以680質量份之氯仿萃取，以150質量份之碳酸氫鈉及150質量份之蒸餾水清洗，濃縮，乾燥，及固化。將所獲得的黑色及紫色固態物質溶於42質量份之氯仿，在450質量份之丙酮中再沉澱，及充分地乾燥，如此獲得含有噻吩之共軛聚合物(聚合物名 稱：聚(3-己基噻吩))(P3)。所獲得的含噻吩基之共軛聚合物(P3)的重量平均分子量為28,400克/莫耳，及其數量平均分子量為24,100克/莫耳。 After the sufficiently dried glass recovery flask was sufficiently substituted with argon, 33 parts by mass of THF and 0.04 parts by mass of a polymerization catalyst NiCl 2 (dppp) were added thereto. Meanwhile, 33 parts by mass of THF, 2.8 parts by mass of 2-bromo-3-hexyl-5-iodothiophene, and 4.0 parts by mass of 2.0 M isopropylmagnesium bromide solution were added to another dry three-necked flask. It was stirred at 0 ° C for 30 minutes. The reacted solution was then added to the former flask and polymerized at 35 ° C for 90 minutes. 3 parts by mass of a 1.0 M solution of butylmagnesium chloride in THF was continuously added and stirred for 3 hours, and 50 parts by mass of 5 M hydrochloric acid was further added and stirred for 1 hour, and then the polymerization was terminated. Then, it was extracted with 680 parts by mass of chloroform, washed with 150 parts by mass of sodium hydrogencarbonate and 150 parts by mass of distilled water, concentrated, dried, and solidified. The obtained black and purple solid matter was dissolved in 42 parts by mass of chloroform, reprecipitated in 450 parts by mass of acetone, and sufficiently dried to obtain a conjugated polymer containing thiophene (polymer name: poly(3- Hexylthiophene)) (P3). The obtained thiophene-containing conjugated polymer (P3) had a weight average molecular weight of 28,400 g/mol and a number average molecular weight of 24,100 g/mole.

[含有噻吩基之共軛無規共聚物(P4)之合成] [Synthesis of a conjugated random copolymer (P4) containing a thienyl group]

在將充分乾燥的玻璃回收燒瓶A充分地以氬取代之後，添加22質量份之THF及0.03質量份之聚合觸媒NiCl2(dppp)。同時，在另一乾燥的玻璃回收燒瓶B中添加16質量份之THF、1.3質量份之2-溴-3-己基-5-碘噻吩、及1.3質量份之2.0M溴化異丙基鎂溶液，且在0℃下攪拌30分鐘。此外，在另一乾燥的玻璃回收燒瓶C中添加7質量份之THF、0.6質量份之2,5-二溴-3-(6-(2-四氫呋喃氧基)己基)噻吩、及1.6質量份之1.0M溴化異丙基鎂溶液，且在65℃反應2小時。在反應後將回收燒瓶B及C中的溶液加入回收燒瓶A中，及聚合2小時。在反應後添加2質量份之1.0M氯化第三丁基鎂的THF溶液且攪拌1小時，再添加50質量份之5M氫氯酸且攪拌1小時，然後中止聚合。然後以450質量份之氯仿萃取，以100質量份之碳酸氫鈉及100質量份之蒸餾水清洗，濃縮，乾燥，及固化。將所獲得的黑色及紫色固態物質溶於28質量份之氯仿，在300質量份之丙酮中再沉澱，及充分地乾燥，如此獲得含有噻吩之共軛無規共聚物(聚合物名稱：聚[(3-己基噻吩)-共-(3-(6-羥基)噻吩)])(P4)。所獲得的含有噻吩基之共軛無規共聚物(P4)的重量平均分子量為23,100克/莫耳，及其數量平均分子量為20,200克/莫耳。3-(6-羥基)噻吩單元之含量為17莫耳%。 After the sufficiently dried glass recovery flask A was sufficiently substituted with argon, 22 parts by mass of THF and 0.03 parts by mass of a polymerization catalyst NiCl 2 (dppp) were added. Meanwhile, 16 parts by mass of THF, 1.3 parts by mass of 2-bromo-3-hexyl-5-iodothiophene, and 1.3 parts by mass of a 2.0 M isopropylmagnesium bromide solution were added to another dried glass recovery flask B. And stirred at 0 ° C for 30 minutes. Further, 7 parts by mass of THF, 0.6 parts by mass of 2,5-dibromo-3-(6-(2-tetrahydrofuranyloxy)hexyl)thiophene, and 1.6 parts by mass are added to another dried glass recovery flask C. The 1.0 M solution of isopropylmagnesium bromide was reacted at 65 ° C for 2 hours. After the reaction, the solutions in the recovery flasks B and C were added to the recovery flask A, and polymerization was carried out for 2 hours. After the reaction, 2 parts by mass of a 1.0 M solution of butylmagnesium chloride in THF was added and stirred for 1 hour, and 50 parts by mass of 5 M hydrochloric acid was further added and stirred for 1 hour, and then the polymerization was terminated. Then, it was extracted with 450 parts by mass of chloroform, washed with 100 parts by mass of sodium hydrogencarbonate and 100 parts by mass of distilled water, concentrated, dried, and solidified. The obtained black and purple solid matter was dissolved in 28 parts by mass of chloroform, reprecipitated in 300 parts by mass of acetone, and sufficiently dried to obtain a conjugated random copolymer containing thiophene (polymer name: poly[ (3-hexylthiophene) -co- (3-(6-hydroxy)thiophene)]) (P4). The obtained thiophene-containing conjugated random copolymer (P4) had a weight average molecular weight of 23,100 g/mol and a number average molecular weight of 20,200 g/mole. The content of the 3-(6-hydroxy)thiophene unit was 17 mol%.

[含有噻吩基之共軛無規共聚物(P5)之合成] [Synthesis of a conjugated random copolymer (P5) containing a thienyl group]

在將充分乾燥的玻璃回收燒瓶充分地以氬取代之後，在其中添加33質量份之THF及0.04質量份之聚合觸媒NiCl2(dppp)。同時，在另一乾燥的三頸燒瓶中添加33質量份之THF、2.5質量份之2-溴-3-己基-5-碘噻吩、0.3質量份之2-溴-3-(2-乙基)己基-5-碘噻吩、及4.0質量份之2.0M溴化異丙基鎂溶液，且在0℃攪拌30分鐘。然後將該已反應溶液加入前者燒瓶中且在35℃下聚合7小時。連續地添加3質量份之1.0M氯化第三丁基鎂的THF溶液且攪拌3小時，再添加50質量份之5M氫氯酸且攪拌1小時，然後中止聚合。然後以680質量份之氯仿萃取，以150質量份之碳酸氫鈉及150質量份之蒸餾水清洗，濃縮，乾燥，及固化。將所獲得的黑色及紫色固態物質溶於42質量份之氯仿，在450質量份之丙酮中再沉澱，及充分地乾燥，如此獲得含有噻吩之共軛聚合物(聚合物名稱：聚[(3-己基噻吩)-共-(3-(2-乙基己基)噻吩))(P5)。所獲得的含噻吩基之共軛聚合物(P5)的重量平均分子量為26,500克/莫耳，及其數量平均分子量為22,300克/莫耳。(3-(2-乙基己基)噻吩)單元之含量為8莫耳%。 After the sufficiently dried glass recovery flask was sufficiently substituted with argon, 33 parts by mass of THF and 0.04 parts by mass of a polymerization catalyst NiCl 2 (dppp) were added thereto. Meanwhile, 33 parts by mass of THF, 2.5 parts by mass of 2-bromo-3-hexyl-5-iodothiophene, and 0.3 parts by mass of 2-bromo-3-(2-ethyl group) were added to another dry three-necked flask. Hexyl-5-iodothiophene, and 4.0 parts by mass of a 2.0 M solution of isopropylmagnesium bromide, and stirred at 0 ° C for 30 minutes. The reacted solution was then added to the former flask and polymerized at 35 ° C for 7 hours. 3 parts by mass of a 1.0 M solution of butylmagnesium chloride in THF was continuously added and stirred for 3 hours, and 50 parts by mass of 5 M hydrochloric acid was further added and stirred for 1 hour, and then the polymerization was terminated. Then, it was extracted with 680 parts by mass of chloroform, washed with 150 parts by mass of sodium hydrogencarbonate and 150 parts by mass of distilled water, concentrated, dried, and solidified. The obtained black and purple solid matter was dissolved in 42 parts by mass of chloroform, reprecipitated in 450 parts by mass of acetone, and sufficiently dried to obtain a conjugated polymer containing thiophene (polymer name: poly[(3) -hexylthiophene) -co- (3-(2-ethylhexyl)thiophene)) (P5). The obtained thiophene-containing conjugated polymer (P5) had a weight average molecular weight of 26,500 g/mol and a number average molecular weight of 22,300 g/mole. The content of the (3-(2-ethylhexyl)thiophene) unit was 8 mol %.

以上程序中之純化方法係如下。 The purification method in the above procedure is as follows.

○聚合物之純化 ○ purification of polymer

將由Shimadzu公司所製造的高性能液態層析儀LC-10A用於純化，其係使用GPC管柱。在此使用串接的Shodex GPC K-LG及Shodex GPC K-2006M作為管柱。此外使用RID-10A作為偵測器。 A high performance liquid chromatograph LC-10A manufactured by Shimadzu Corporation was used for purification using a GPC column. Here, Shodex GPC K-LG and Shodex GPC K-2006M are used in series as a column. Also use RID-10A as a detector.

用於本實施例的含噻吩基之共軛聚合物及富勒烯衍生物的表面張力係示於表1。表面張力係藉Owens-Wendt法由水與乙醇之接觸角計算。其在10處測量接觸角且使用平均值。 The surface tension of the thiophene group-containing conjugated polymer and the fullerene derivative used in the present Example is shown in Table 1. The surface tension is calculated from the contact angle of water and ethanol by the Owens-Wendt method. It measures the contact angle at 10 and uses the average.

用於本實施例的含噻吩基之共軛聚合物的熔點係示於表1。熔點係藉差式掃描熱度計(DSC)測量。一旦將溫度從50℃提高到270℃而將熱記錄重設之後，將聚合物冷卻至-50℃，然後再度加熱至270℃。在全部的情形，溫度均以10℃/分鐘之速率升降。 The melting point of the thiophene group-containing conjugated polymer used in the present embodiment is shown in Table 1. The melting point is measured by a differential scanning calorimeter (DSC). Once the temperature was reset from 50 ° C to 270 ° C, the polymer was cooled to -50 ° C and then heated again to 270 ° C. In all cases, the temperature was raised and lowered at a rate of 10 ° C / minute.

實施例1 Example 1 (組成物1之製造) (Manufacture of composition 1)

在40℃將16.0質量份之作為含噻吩基之共軛聚合物的含有噻吩基之共軛嵌段共聚物(P1)、12.8質量份之作為富勒烯衍生物的[6,6]-苯基C61-丁酸甲酯(PCBM)(由Frontier Carbon公司所製造的E100H)、及1,100質量份之作為溶劑的氯苯混合12小時。連續地將該混合物冷卻至20℃之室溫且以孔度為45μm之PTFE過濾器過濾，如此製造組成物1。 16.0 parts by mass of a thiophene-containing conjugated block copolymer (P1) as a thiophene group-containing conjugated polymer, and 12.8 parts by mass of [6,6]-benzene as a fullerene derivative at 40 ° C The base C61-methyl butyrate (PCBM) (E100H manufactured by Frontier Carbon Co., Ltd.) and 1,100 parts by mass of chlorobenzene as a solvent were mixed for 12 hours. The mixture was continuously cooled to room temperature of 20 ° C and filtered through a PTFE filter having a pore size of 45 μm, thereby preparing Composition 1.

(有機太陽能電池之製造及評估) (Manufacture and evaluation of organic solar cells)

將藉濺射法而附著150nm厚的ITO膜(電阻值為10Ω/□)之玻璃基板以UV臭氧處理進行表面處理歷時15分鐘。藉旋塗法塗布PEDOT：PSS水性溶液(由H.C.Starck GmbH所製造的CLEVIOS PH500)而在基板上形成40nm厚的膜作為電洞傳輸層。以加熱板將基板在140℃加熱及乾燥20分鐘，且連續地藉旋塗法塗以組成物1，如此獲得有 機太陽能電池之有機光活性層(膜厚約100nm)A1。 A glass substrate to which a 150 nm-thick ITO film (resistance value: 10 Ω/□) was attached by sputtering was subjected to surface treatment by UV ozone treatment for 15 minutes. A PEDOT:PSS aqueous solution (CLEVIOS PH500 manufactured by H.C. Starck GmbH) was applied by spin coating to form a 40 nm thick film as a hole transport layer on the substrate. The substrate was heated and dried at 140 ° C for 20 minutes with a hot plate, and continuously coated with the composition 1 by spin coating, thus obtained The organic photoactive layer (film thickness about 100 nm) A1 of the solar cell.

(溶劑處理) (solvent treatment)

將200μl之氯苯(表面張力：33.0mN/m2)置於容積為300ml之有蓋玻璃容器的底部，將高約4公分之玻璃板置於該有蓋玻璃容器中，且將容器封蓋。將有機光活性層A1置於玻璃容器中之該玻璃板上，且立即將容器封蓋，然後在25℃之室溫將有機光活性層A1暴露於氯苯蒸汽中歷時5分鐘。在經過5分鐘之後，將有機光活性層A1從容器取出且在室溫真空乾燥。 200 μl of chlorobenzene (surface tension: 33.0 mN/m 2 ) was placed at the bottom of a covered glass container having a volume of 300 ml, and a glass plate having a height of about 4 cm was placed in the covered glass container, and the container was capped. The organic photoactive layer A1 was placed on the glass plate in a glass container, and the container was immediately capped, and then the organic photoactive layer A1 was exposed to chlorobenzene vapor at room temperature of 25 ° C for 5 minutes. After 5 minutes passed, the organic photoactive layer A1 was taken out from the container and dried under vacuum at room temperature.

然後將氟化鋰蒸汽沉積在有機光活性層上成為1nm之膜厚，且連續地以真空蒸汽沉積設備將鋁蒸汽沉積在氟化鋰層上成為100nm之膜厚。蒸汽沉積之真空程度始終為1×10-4至3×10-4Pa。此外，所獲得的有機太陽能電池之形狀為直徑5.64mm之正圓形，及其有效面積為0.25cm2。在氮大氣下將有機太陽能電池從真空蒸汽沉積設備取出，且以300W太陽模擬器(由Newport公司所製造的91160型：AM1.5G過濾器，100mW/cm2之光強度)照射，及測量在將施加電壓從-1伏變成+1伏時之電流值。光強度係以標準電池(由BUNKOUKEIKI公司所製造的BS-520)調整。將此情況之短路電流密度Jsc(在施加電壓為0伏時之電流密度值)比較未施加溶劑處理之情況。 Then, lithium fluoride vapor was deposited on the organic photoactive layer to a film thickness of 1 nm, and aluminum vapor was continuously deposited on the lithium fluoride layer by a vacuum vapor deposition apparatus to have a film thickness of 100 nm. The degree of vacuum of vapor deposition is always from 1 × 10 -4 to 3 × 10 -4 Pa. Further, the obtained organic solar cell was shaped into a true circular shape having a diameter of 5.64 mm and an effective area of 0.25 cm 2 . The organic solar cell was taken out from the vacuum vapor deposition apparatus under a nitrogen atmosphere, and irradiated with a 300 W solar simulator (Model 91160 manufactured by Newport: AM 1.5 G filter, light intensity of 100 mW/cm 2 ), and measured at The current value when the applied voltage is changed from -1 volt to +1 volt. The light intensity was adjusted with a standard battery (BS-520 manufactured by BUNKOUKEIKI Co., Ltd.). The short-circuit current density Jsc (current density value at the applied voltage of 0 volts) in this case was compared with the case where no solvent treatment was applied.

Jsc改良率=(施加溶劑處理之Jsc)/(未施加溶劑處理之Jsc)×100(%) Jsc improvement rate = (Jsc applied solvent treatment) / (Jsc without solvent treatment) × 100 (%)

實施例2 Example 2

以如實施例1的相同方式製造有機太陽能電池，除了 使用200μl之甲苯(27.9mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 1, except that 200 μl of toluene (27.9 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例3 Example 3

以如實施例1的相同方式製造有機太陽能電池，除了使用200μl之鄰二甲苯(29.8mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 1, except that 200 μl of o-xylene (29.8 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例4 Example 4

以如實施例1的相同方式製造有機太陽能電池，除了使用200μl之1,2-二氯乙烷(31.9mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 1, except that 200 μl of 1,2-dichloroethane (31.9 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例5 Example 5

以如實施例1的相同方式製造有機太陽能電池，除了使用200μl之甲氧苯(35.1mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 1, except that 200 μl of methoxybenzene (35.1 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例1 Comparative example 1

以如實施例1的相同方式製造有機太陽能電池，除了使用200μl之丙酮(23.5mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 1, except that 200 μl of acetone (23.5 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例2 Comparative example 2

以如比較例1的相同方式製造有機太陽能電池，除了溶劑處理係在25℃之室溫施加60分鐘。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 1, except that the solvent treatment was applied at room temperature of 25 ° C for 60 minutes. The results are shown in Table 2.

實施例6(組成物2) Example 6 (composition 2)

以如實施例1之組成物1的相同方式獲得組成物2，除了使用16.0質量份之含有噻吩基之共軛嵌段共聚物(P2)代替含有噻吩基之共軛嵌段共聚物(P1)作為共軛聚合物。 Composition 2 was obtained in the same manner as in Composition 1 of Example 1, except that 16.0 parts by mass of a thiophene-containing conjugated block copolymer (P2) was used instead of the thiophene-containing conjugated block copolymer (P1). As a conjugated polymer.

以如實施例1的相同方式獲得有機太陽能電池之有機光活性層(膜厚約100nm)A2，除了使用組成物2代替組成物1。以如實施例1的相同方式，使用A2且以氯苯施加溶劑處理而製造有機太陽能電池。結果係示於表2。 An organic photoactive layer (film thickness of about 100 nm) A2 of the organic solar cell was obtained in the same manner as in Example 1, except that the composition 2 was used instead of the composition 1. An organic solar cell was fabricated in the same manner as in Example 1 using A2 and applying a solvent treatment with chlorobenzene. The results are shown in Table 2.

實施例7 Example 7

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之甲苯(27.9mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of toluene (27.9 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例8 Example 8

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之鄰二甲苯(29.8mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of o-xylene (29.8 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例9 Example 9

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之鄰二氯苯(35.6mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of o-dichlorobenzene (35.6 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例10 Example 10

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之1,2-二氯乙烷(31.9mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of 1,2-dichloroethane (31.9 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例11 Example 11

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之甲氧苯(35.1mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of methoxybenzene (35.1 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例3 Comparative example 3

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之丙酮(23.5mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of acetone (23.5 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例4 Comparative example 4

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之乙酸乙酯(23.4mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of ethyl acetate (23.4 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例5 Comparative Example 5

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之環己烷(24.7mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of cyclohexane (24.7 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例6 Comparative Example 6

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之乙二醇(48.0mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of ethylene glycol (48.0 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例7 Comparative Example 7

以如實施例6的相同方式製造有機太陽能電池，除了使用200μl之水(72.0mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that 200 μl of water (72.0 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例8 Comparative Example 8

以如實施例6的相同方式製造有機太陽能電池，除了在150℃施加熱處理歷時5分鐘而代替施加溶劑處理。該熱處理係在氮大氣下將有機光活性層A2置於加熱板上時施加。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that the heat treatment was applied at 150 ° C for 5 minutes instead of applying a solvent treatment. This heat treatment is applied when the organic photoactive layer A2 is placed on a hot plate under a nitrogen atmosphere. The results are shown in Table 2.

比較例9 Comparative Example 9

以如實施例6的相同方式製造有機太陽能電池，除了在150℃施加熱處理歷時30分鐘而代替施加溶劑處理。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 6, except that the heat treatment was applied at 150 ° C for 30 minutes instead of applying a solvent treatment. The results are shown in Table 2.

比較例10(組成物3) Comparative Example 10 (composition 3)

以如實施例1之組成物1的相同方式獲得組成物3，除了使用16.0質量份之含噻吩基之共軛聚合物(P3)代替含有噻吩基之共軛嵌段共聚物(P1)作為含噻吩基之共軛聚合物。 Composition 3 was obtained in the same manner as in Composition 1 of Example 1, except that 16.0 parts by mass of a thiophene-containing conjugated polymer (P3) was used instead of the thiophene-containing conjugated block copolymer (P1) as a A conjugated polymer of a thienyl group.

以如實施例1的相同方式獲得有機太陽能電池之有機光活性層(膜厚約100nm)A3，除了使用組成物3代替組成物1。以如實施例1的相同方式，使用A3且以氯苯施加溶劑處理而製造有機太陽能電池。結果係示於表2。 An organic photoactive layer (film thickness of about 100 nm) A3 of the organic solar cell was obtained in the same manner as in Example 1, except that the composition 3 was used instead of the composition 1. An organic solar cell was produced in the same manner as in Example 1 using A3 and applying a solvent treatment with chlorobenzene. The results are shown in Table 2.

比較例11 Comparative Example 11

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之甲苯(27.9mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of toluene (27.9 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例12 Comparative Example 12

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之鄰二甲苯(29.8mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of o-xylene (29.8 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例13 Comparative Example 13

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之鄰二氯苯(35.6mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of o-dichlorobenzene (35.6 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例14 Comparative Example 14

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之1,2-二氯乙烷(31.9mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of 1,2-dichloroethane (31.9 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例15 Comparative Example 15

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之甲氧苯(35.1mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of methoxybenzene (35.1 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例16 Comparative Example 16

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之丙酮(23.5mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of acetone (23.5 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例17 Comparative Example 17

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之乙酸乙酯(23.4mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of ethyl acetate (23.4 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例18 Comparative Example 18

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之環己烷(24.7mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of cyclohexane (24.7 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例19 Comparative Example 19

以如比較例10的相同方式製造有機太陽能電池，除了使用200μl之乙二醇(48.0mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of ethylene glycol (48.0 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例20 Comparative Example 20

以如比較例10的相同方式製造有機太陽能電池，除 了使用200μl之水(72.0mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 10 except that 200 μl of water (72.0 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例12(組成物4) Example 12 (composition 4)

以如實施例1之組成物1的相同方式獲得組成物4，除了使用11.2質量份之含噻吩基之共軛聚合物(P3)及4.8質量份之含有噻吩基之共軛無規共聚物(P4)，代替含有噻吩基之共軛嵌段共聚物(P1)作為含噻吩基之共軛聚合物。 The composition 4 was obtained in the same manner as in the composition 1 of Example 1, except that 11.2 parts by mass of the thiophene-containing conjugated polymer (P3) and 4.8 parts by mass of the thiophene-containing conjugated random copolymer ( P4), instead of the conjugated block copolymer (P1) containing a thienyl group as a conjugated polymer containing a thienyl group.

以如實施例1的相同方式獲得有機太陽能電池之有機光活性層(膜厚約100nm)A4，除了使用組成物4代替組成物1。以如實施例1的相同方式，使用A4且以氯苯施加溶劑處理而製造有機太陽能電池。結果係示於表2。 An organic photoactive layer (film thickness of about 100 nm) A4 of the organic solar cell was obtained in the same manner as in Example 1, except that the composition 4 was used instead of the composition 1. An organic solar cell was fabricated in the same manner as in Example 1 using A4 and applying a solvent treatment with chlorobenzene. The results are shown in Table 2.

實施例13 Example 13

以如實施例12的相同方式製造有機太陽能電池，除了使用200μl之甲苯(27.9mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 12 except that 200 μl of toluene (27.9 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例14 Example 14

以如實施例12的相同方式製造有機太陽能電池，除了使用200μl之鄰二甲苯(29.8mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 12 except that 200 μl of o-xylene (29.8 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例15 Example 15

以如實施例12的相同方式製造有機太陽能電池，除了使用200μl之鄰二氯苯(35.6mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 12 except that 200 μl of o-dichlorobenzene (35.6 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例16 Example 16

以如實施例12的相同方式製造有機太陽能電池，除了使用200μl之甲氧苯(35.1mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 12 except that 200 μl of methoxybenzene (35.1 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例21 Comparative Example 21

以如實施例12的相同方式製造有機太陽能電池，除了使用200μl之丙酮(23.5mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 12 except that 200 μl of acetone (23.5 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例22 Comparative Example 22

以如實施例12的相同方式製造有機太陽能電池，除了使用200μl之環己烷(24.7mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Example 12 except that 200 μl of cyclohexane (24.7 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例23(組成物5) Comparative Example 23 (composition 5)

以如實施例1之組成物1的相同方式獲得組成物5，除了使用11.2質量份之含噻吩基之共軛聚合物(P3)、及4.8質量份之含有噻吩基之共軛無規共聚物(P5)，代替含有噻吩基之共軛嵌段共聚物(P1)作為含噻吩基之共軛聚合物。 The composition 5 was obtained in the same manner as in the composition 1 of Example 1, except that 11.2 parts by mass of the thiophene-containing conjugated polymer (P3) and 4.8 parts by mass of the thiophene-containing conjugated random copolymer were used. (P5), instead of the thiophene-containing conjugated block copolymer (P1) as a thiophene-containing conjugated polymer.

以如實施例1的相同方式獲得有機太陽能電池之有機光活性層(膜厚約100nm)A5，除了使用組成物5代替組成物1。以如實施例1的相同方式，使用A5且以氯苯施加溶劑處理而製造有機太陽能電池。結果係示於表2。 An organic photoactive layer (film thickness of about 100 nm) A5 of the organic solar cell was obtained in the same manner as in Example 1, except that the composition 5 was used instead of the composition 1. An organic solar cell was fabricated in the same manner as in Example 1 using A5 and applying a solvent treatment with chlorobenzene. The results are shown in Table 2.

比較例24 Comparative Example 24

以如比較例23的相同方式製造有機太陽能電池，除了使用200μl之甲苯(27.9mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 23 except that 200 μl of toluene (27.9 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

比較例25 Comparative Example 25

以如比較例23的相同方式製造有機太陽能電池，除了使用200μl之鄰二甲苯(29.8mN/m2)代替氯苯作為溶劑處理用溶劑。結果係示於表2。 An organic solar cell was fabricated in the same manner as in Comparative Example 23 except that 200 μl of o-xylene (29.8 mN/m 2 ) was used instead of chlorobenzene as a solvent for solvent treatment. The results are shown in Table 2.

實施例1至11以及比較例1至7顯示已證驗，在溶劑處理用溶劑的表面張力為27至37之範圍時，有機光伏元件之Jsc明顯地改良。同時比較例1及2顯示，有機光伏元件之Jsc因溶劑處理時間延長而改良，即使是在表面張力為較佳範圍以外時。然而，其由於溶劑處理花費60分鐘之長時間而不具經濟性。比較例8及9顯示，有機光伏元件之Jsc亦因熱處理而改良，但是處理時間短則效果有限。比較例10至20顯示，在使用僅一種含噻吩基之共軛聚合物時溶劑處理的效果低，但是使用兩種熔點彼此相差10℃的含噻吩基之共軛聚合物則可獲得高Jsc改良率。實施例12至16以及比較例21及22顯示，在摻合兩種熔點彼此相差10℃的含噻吩基之共軛聚合物代替含有噻吩基之共軛嵌段共聚物時，亦可獲得Jsc明顯改良之有機光伏元件。比較例23、24及25顯示，使用兩種熔點彼此相差小於10℃的含噻吩基之共軛聚合物則Jsc改良率低。 Examples 1 to 11 and Comparative Examples 1 to 7 show that the Jsc of the organic photovoltaic element is remarkably improved when the surface tension of the solvent for solvent treatment is in the range of 27 to 37. At the same time, Comparative Examples 1 and 2 show that the Jsc of the organic photovoltaic element is improved by the prolonged solvent treatment time, even when the surface tension is outside the preferred range. However, it is not economical because the solvent treatment takes 60 minutes. Comparative Examples 8 and 9 show that the Jsc of the organic photovoltaic element is also improved by heat treatment, but the treatment time is short and the effect is limited. Comparative Examples 10 to 20 show that the effect of solvent treatment is low when only one thiophene-containing conjugated polymer is used, but a high-Jsc-modified conjugated polymer having two melting points different from each other by 10 ° C can be obtained. rate. Examples 12 to 16 and Comparative Examples 21 and 22 show that Jsc can also be obtained by blending a thiophene-containing conjugated polymer having a melting point of 10 ° C from each other instead of a thiophene-containing conjugated block copolymer. Improved organic photovoltaic components. Comparative Examples 23, 24 and 25 show that the use of two thiophene-containing conjugated polymers having melting points which differ from each other by less than 10 ° C has a low Jsc improvement rate.

1‧‧‧基板 1‧‧‧Substrate

2‧‧‧陽極 2‧‧‧Anode

3‧‧‧有機光活性層 3‧‧‧Organic photoactive layer

4‧‧‧陰極 4‧‧‧ cathode

第1圖為顯示依照本發明之有機光伏元件的一個實例之示意圖。 Fig. 1 is a schematic view showing an example of an organic photovoltaic element in accordance with the present invention.

Claims (4)

一種製造具有有機光活性層的有機光伏元件之方法，其係包含：一種包括含噻吩基之聚合物A嵌段與含噻吩基之聚合物B嵌段的共軛嵌段共聚物，或一種包括含噻吩基之共軛聚合物A與含噻吩基之共軛聚合物B的聚合物組成物，其中聚合物之間的熔點差為10℃以上，以及富勒烯衍生物，及其中該方法係包括將有機光活性層暴露於表面張力為介於含噻吩基之共軛聚合物(A或B)的表面張力與富勒烯衍生物的表面張力之間的溶劑蒸汽之程序。 A method of producing an organic photovoltaic element having an organic photoactive layer, comprising: a conjugated block copolymer comprising a thiophene-containing polymer A block and a thienyl-containing polymer B block, or a a polymer composition of a thiophene-containing conjugated polymer A and a thiophene-containing conjugated polymer B, wherein a difference in melting point between the polymers is 10 ° C or more, and a fullerene derivative, and the method system thereof The procedure of exposing the organic photoactive layer to a solvent vapor having a surface tension between the surface tension of the thiophene-containing conjugated polymer (A or B) and the surface tension of the fullerene derivative is included. 如申請專利範圍第1項之製造有機光伏元件之方法，其中該有機光活性層係在25℃暴露於表面張力為27至37mN/m2之範圍的溶劑蒸汽。 A method of producing an organic photovoltaic element according to claim 1, wherein the organic photoactive layer is exposed to a solvent vapor having a surface tension of from 27 to 37 mN/m 2 at 25 °C. 一種製造有機光伏元件之方法，其中將如申請專利範圍第1項之有機光活性層暴露於溶劑蒸汽歷時1秒至30分鐘之範圍。 A method of producing an organic photovoltaic element, wherein the organic photoactive layer as in claim 1 of the patent application is exposed to a solvent vapor for a period of from 1 second to 30 minutes. 一種有機光伏元件，其係藉如申請專利範圍第1項之方法製造。 An organic photovoltaic element manufactured by the method of claim 1 of the patent application.
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