TW201406811A - Electron donative organic material, material for photovoltaic element using the same and photovoltaic element - Google Patents
Electron donative organic material, material for photovoltaic element using the same and photovoltaic element Download PDFInfo
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- TW201406811A TW201406811A TW102118339A TW102118339A TW201406811A TW 201406811 A TW201406811 A TW 201406811A TW 102118339 A TW102118339 A TW 102118339A TW 102118339 A TW102118339 A TW 102118339A TW 201406811 A TW201406811 A TW 201406811A
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- BBNQQADTFFCFGB-UHFFFAOYSA-N purpurin Chemical class C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 150000003967 siloles Chemical group 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
Description
本發明係關於一種電子供給性有機材料、使用其之光伏元件用材料及使用其之光伏元件。 The present invention relates to an electron-donating organic material, a material for a photovoltaic element using the same, and a photovoltaic element using the same.
太陽能電池係作為對環境具優越之電能源，對於現在日益嚴重之能量問題而言，作為有力之解決對策正備受矚目。目前將單晶矽、多晶矽、非晶質矽、化合物半導體等之無機物作為太陽能電池之光伏元件的半導體材料使用。但是，由於使用無機半導體所製得的太陽能電池成本高，尚未廣泛普及至一般家庭。作為成本高的主因係在於真空且高溫下製造半導體薄膜之程序。因此，作為製程簡化所期待的半導體材料，已有人探討使用共軛系聚合物或有機結晶等之有機半導體或有機色素的有機太陽能電池。 As a powerful electric energy source for the environment, the solar cell system is attracting attention as a powerful solution to the increasingly serious energy problem. Inorganic materials such as single crystal germanium, polycrystalline germanium, amorphous germanium, and compound semiconductor are currently used as semiconductor materials for photovoltaic elements of solar cells. However, since solar cells made using inorganic semiconductors have high cost, they have not been widely spread to ordinary households. The main reason for the high cost is the process of manufacturing a semiconductor film under vacuum and at a high temperature. Therefore, an organic solar cell using an organic semiconductor or an organic dye such as a conjugated polymer or an organic crystal has been studied as a semiconductor material which is expected to be simplified in the process.
但是，與使用習知無機半導體之太陽能電池作一比較，使用共軛系聚合物等之有機太陽能電池的光電轉換效率低係最大的課題，尚未達到實用化。使用習 知之共軛系聚合物的有機太陽能電池之光電轉換效率低，其主要係因如下之原因所造成：陽光之吸收效率低；形成了因陽光所生成的電子與電洞難以分離的所謂激子(exciton)之束縛狀態；由於容易形成捕獲載體(電子、電洞)之阱，故所生成的載體容易被阱所捕獲，載體之移動度低等。 However, compared with the solar cell using a conventional inorganic semiconductor, the organic solar cell using a conjugated polymer or the like has a problem that the photoelectric conversion efficiency is the largest, and has not yet been put into practical use. Use The organic solar cell of the conjugated polymer has low photoelectric conversion efficiency, which is mainly caused by the following reasons: the absorption efficiency of sunlight is low; the so-called excitons which are difficult to separate electrons and holes generated by sunlight are formed ( The constrained state of exciton); since the trap of the trapping carrier (electrons, holes) is easily formed, the generated carrier is easily trapped by the trap, and the mobility of the carrier is low.
藉由迄今之有機半導體所得之光電轉換元件能夠被分類成使電子供給性有機材料(p型有機半導體)與功函數小的金屬接合的肖特基(Schottky)型、使電子接受性有機材料(n型有機半導體)與電子供給性有機材料(p型有機半導體)接合的異接合型等。由於該等元件係僅接合部之有機層(數分子層程度)有助於光電流生成，故光電轉換效率低，使其提高已成為課題。 The photoelectric conversion element obtained by the organic semiconductor of the prior art can be classified into a Schottky type in which an electron-donating organic material (p-type organic semiconductor) is bonded to a metal having a small work function, and an electron-accepting organic material ( An n-type organic semiconductor) is a heterojunction type bonded to an electron-donating organic material (p-type organic semiconductor). Since these elements are only the organic layer (the degree of the molecular layer) of the joint portion contribute to the generation of the photocurrent, the photoelectric conversion efficiency is low, and the improvement thereof has become a problem.
作為光電轉換效率提高之一種方法，可列舉：混合電子接受性有機材料(n型有機半導體)與電子供給性有機材料(p型有機半導體)，使有助於光電轉換之接合面增加的體積異接合型(例如，參閱非專利文獻1)。其中，有人提案一種光電轉換材料，其係將共軛系聚合物作為電子供給性有機材料(p型有機半導體)使用，除了將具有n型半導體特性之導電性高分子作為電子接受性有機材料使用之外，也使用C60等之富勒烯或富勒烯衍生物的光電轉換材料(例如，參閱非專利文獻2)。 As a method for improving the photoelectric conversion efficiency, a mixed electron-accepting organic material (n-type organic semiconductor) and an electron-donating organic material (p-type organic semiconductor) can be used to increase the volume difference of the bonding surface which contributes to photoelectric conversion. A joint type (for example, see Non-Patent Document 1). Among them, a photoelectric conversion material has been proposed which uses a conjugated polymer as an electron-donating organic material (p-type organic semiconductor), except that a conductive polymer having an n-type semiconductor property is used as an electron-accepting organic material. In addition, a photoelectric conversion material of a fullerene or a fullerene derivative such as C 60 is also used (for example, see Non-Patent Document 2).
為了有效地吸收遍及陽光光譜廣範圍之放射能量而使光電轉換效率提高，有人提案一種電子供給性有機材料，其係藉由將電子供給性基與電子吸引性基導 入主鏈骨架而窄化能帶間隙(例如，參閱非專利文獻3、4)。也有人提案一種能帶間隙窄的電子供給性有機材料，其係將具有醯亞胺基之噻吩吡咯-4,6-二酮(Thienopyrrole-4,6-dione)骨架或噻吩異吲哚-5,7-二酮(Thienoisoindole-5,7-dione)骨架作為該電子吸引性基，組合寡噻吩骨架或環戊二噻吩骨架、苯并二噻吩骨架作為電子供給性基(例如，參閱專利文獻1、非專利文獻4至16)。 In order to effectively absorb the radiation energy over a wide range of sunlight spectra and improve the photoelectric conversion efficiency, an electron-donating organic material has been proposed, which is based on electron-donating groups and electron-attracting substrates. The band skeleton is narrowed into the main chain skeleton (for example, see Non-Patent Documents 3 and 4). It has also been proposed to provide an electron-donating organic material with a narrow gap, which is a Thienopyrrole-4,6-dione skeleton or a thiopheneisoindole-5 having a quinone imine group. As the electron-attracting group, a Thienoisoindole-5 (7-dione) skeleton is combined with an oligothiophene skeleton, a cyclopentadithiophene skeleton, and a benzodithiophene skeleton as an electron-donating group (for example, see Patent Document 1) Non-patent documents 4 to 16).
專利文獻1 WO2011/063534號公報 Patent Document 1 WO2011/063534
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於組合作為上述電子吸引性基之噻吩吡咯二酮骨架、作為電子供給性基之寡噻吩骨架或環戊二噻吩骨架、苯并二噻吩骨架而成之能帶間隙窄的電子供給性有機材料(例如，專利文獻1、非專利文獻5至15)中，缺乏對於成為必要塗布發電層的有機溶劑之溶解性，為了使該溶解性提高，將烷基側鏈導入噻吩吡咯二酮骨架之氮上。然而，認為導入無載體輸送能力之過多的烷基將會使電子供給性有機材料之載體移動度降低。 An electron-donating organic material having a narrow band gap formed by combining a thiophenyrroledione skeleton as the electron-attracting group, an oligothiophene skeleton or a cyclopentadithiophene skeleton or an benzodithiophene skeleton as an electron-donating group ( For example, in Patent Document 1 and Non-Patent Documents 5 to 15), the solubility in an organic solvent which is required to coat a power generation layer is lacking, and in order to improve the solubility, an alkyl side chain is introduced into the nitrogen of the thiophenyrroledione skeleton. . However, it is believed that the introduction of an excess of alkyl groups without carrier transport will result in reduced carrier mobility of the electron-donating organic material.
將丁基、己基、辛基、十二烷基等之直鏈結構(專利文獻1、非專利文獻5至13)或2-乙基己基、3,7-二甲基己基、2-丁基辛基等之分枝鏈結構(專利文獻1、非專利文獻6、8至10、14)被作為氮上之烷基使用。還有，丁基等之較短的烷基，由於無法確保對於有機溶劑之充分溶解性，也降低與富勒烯所代表的電子接受性材料之相溶性，未能獲得足夠的光電轉換效率(非專利文獻9)。 A linear structure of butyl, hexyl, octyl, dodecyl or the like (Patent Document 1, Non-Patent Documents 5 to 13) or 2-ethylhexyl, 3,7-dimethylhexyl, 2-butyl A branched chain structure of octyl or the like (Patent Document 1, Non-Patent Documents 6, 8 to 10, and 14) is used as an alkyl group on nitrogen. Further, a shorter alkyl group such as a butyl group cannot reduce the compatibility with an electron accepting material represented by fullerene because of insufficient solubility in an organic solvent, and sufficient photoelectric conversion efficiency cannot be obtained ( Non-patent document 9).
還有，將習知烷基導入噻吩吡咯二酮骨架之能帶間隙窄的電子供給性有機材料，使得最高佔據分子軌域(HOMO)準位變淺，太陽能電池特性之釋放電壓將會降低。 Further, an electron-donating organic material having a narrow band gap of a conventional alkyl group introduced into a thiophene pyrrolidone skeleton causes a maximum occupied molecular orbital (HOMO) level to be shallow, and a solar cell characteristic release voltage is lowered.
亦即，使用將習知烷基側鏈導入氮上之具有噻吩吡咯二酮骨架之電子供給性有機材料而成的光伏元件，對於有機溶劑之溶解性、高載體移動度及深HOMO化中任一項皆為不夠充分，僅可獲得低的光電轉換效率。本發明係以提供光電轉換效率高的光伏元件作為目的，並提供全部符合對於有機溶劑之溶解性、高載體移動度及深HOMO化之電子供給性有機材料。 That is, a photovoltaic element obtained by introducing a conventional alkyl side chain into an electron-donating organic material having a thiophenyrroledione skeleton on a nitrogen, is suitable for solubility in an organic solvent, high carrier mobility, and deep HOMO. One is not enough, only low photoelectric conversion efficiency can be obtained. The present invention has an object of providing a photovoltaic element having high photoelectric conversion efficiency, and provides an electron supply organic material which all conforms to solubility in an organic solvent, high carrier mobility, and deep HOMO.
針對噻吩吡咯二酮骨架上之取代基而探討各式各樣結構的結果，發現為了符合對有機溶劑之溶解性、高載體移動度及深HOMO化中任一項，若將芳基或雜芳基導入氮上的話為佳。 The results of various structures were investigated for the substituents on the thiophene pyrrolidone skeleton, and it was found that in order to satisfy the solubility in organic solvents, high carrier mobility, and deep HOMO, if aryl or heteroaryl It is preferred that the base is introduced into the nitrogen.
亦即，本發明係含有在通式(1)所表示的氮上導入芳基或雜芳基之噻吩吡咯二酮結構單元之電子供給性有機材料、及使用其之光伏元件。 In other words, the present invention relates to an electron-donating organic material containing a thiophenyrroledione structural unit in which an aryl group or a heteroaryl group is introduced to a nitrogen represented by the formula (1), and a photovoltaic element using the same.
(該通式(1)中，R1係表示可被取代的芳基或可被取代的雜芳基)。 (In the formula (1), R 1 represents an aryl group which may be substituted or a heteroaryl group which may be substituted).
根據本發明，能夠提供一種光電轉換效率高的光伏元件。 According to the present invention, it is possible to provide a photovoltaic element having high photoelectric conversion efficiency.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧正極 2‧‧‧ positive
3‧‧‧有機半導體層 3‧‧‧Organic semiconductor layer
4‧‧‧負極 4‧‧‧negative
5‧‧‧具有電子供給性有機材料之層 5‧‧‧layers with electron-donating organic materials
6‧‧‧具有電子接受性有機材料之層 6‧‧‧layers with electron-accepting organic materials
第1圖係顯示本發明之光伏元件之一形態的示意圖。 Figure 1 is a schematic view showing one of the forms of the photovoltaic element of the present invention.
第2圖係顯示本發明之光伏元件另一形態的示意圖。 Figure 2 is a schematic view showing another embodiment of the photovoltaic element of the present invention.
本發明之電子供給性有機材料係含有通式(1)所表示的結構單元：
(該通式(1)中，R1係表示可被取代的芳基或可被取代的雜芳基)。 (In the formula (1), R 1 represents an aryl group which may be substituted or a heteroaryl group which may be substituted).
藉由在該噻吩吡咯二酮骨架的氮上所導入的芳基或雜芳基，被認為能夠使共軛聚合物之平面性部分崩壞，且使相對於有機溶劑之溶解性與高的載體移動度能夠並存。於此，所謂使共軛聚合物之平面性部分崩壞，係意指由於共軛聚合物之主鏈骨架與噻吩吡咯二酮骨架之氮上所導入的芳基或雜芳基之間的扭曲，保持主鏈骨架之π共軛平面之狀態下，在共軛聚合物全體之平面性將會稍微降低。還有，藉由使電子吸引性基配置於氮上之芳基或雜芳基上，被認為能夠加強共軛聚合物之HOMO準位(也有使其深HOMO化之情形)。 By the aryl or heteroaryl group introduced on the nitrogen of the thiophene pyrrolidone skeleton, it is considered that the planar portion of the conjugated polymer is collapsed, and the solubility with respect to the organic solvent is high and the carrier is high. Mobility can coexist. Here, the fact that the planar portion of the conjugated polymer is collapsed means that the distortion between the main chain skeleton of the conjugated polymer and the aryl or heteroaryl group introduced on the nitrogen of the thiophenyrroledione skeleton is caused. In the state in which the π conjugate plane of the main chain skeleton is maintained, the planarity of the entire conjugated polymer is slightly lowered. Further, by disposing the electron attracting group on the aryl or heteroaryl group on the nitrogen, it is considered that the HOMO level of the conjugated polymer can be enhanced (there is also a case where the HOMO is deepened).
於此，所謂芳基，例如表示苯基、萘基、聯苯基、菲基、蒽基、聯三苯基、芘基、茀基、苝基等之芳香族烴基。為了保持電子供給性有機材料之高的載體移動度，分子尺寸小的苯基特別適用。 Here, the aryl group means, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthrenyl group, an anthracenyl group, a terphenyl group, a fluorenyl group, a fluorenyl group or a fluorenyl group. In order to maintain high carrier mobility of the electron-donating organic material, a phenyl group having a small molecular size is particularly suitable.
又，所謂雜芳基，例如表示噻吩基、呋喃基、吡咯基、咪唑基、吡唑基、唑基、吡啶基、吡唑基、嘧啶基、喹啉基、異喹啉基、喹啉基、吖啶基、吲哚 基、咔唑基、苯并呋喃基、二苯并呋喃基、苯并噻吩基、二苯并噻吩基、苯并二噻吩基、矽咯(silole group)、苯并矽咯、二苯并矽咯等之具有碳以外之原子的雜芳香族環基。為了保持載體移動度，雜芳基之碳數較佳為2以上8以下。於此，所謂雜芳基之碳數係設為表示芳香環中所含之碳數，作為取代基係設為即使含有非芳香族碳，也不含於雜芳基之碳數中。 Further, the heteroaryl group means, for example, a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, Azyl, pyridyl, pyrazolyl, pyrimidinyl, quinolyl, isoquinolinyl, quin Alkyl, acridinyl, fluorenyl, oxazolyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothiophenyl, benzodithienyl, silole group, a heteroaromatic ring group having an atom other than carbon, such as benzofluorene or dibenzopyrrole. In order to maintain the degree of carrier mobility, the carbon number of the heteroaryl group is preferably 2 or more and 8 or less. Here, the carbon number of the heteroaryl group is a number of carbons contained in the aromatic ring, and the substituent is not contained in the carbon number of the heteroaryl group even if it contains a non-aromatic carbon.
芳基或雜芳基具有取代基之情形，作為芳基或雜芳基之取代基，可列舉：烷基(R1S1)或烷氧基(R1S2)、鹵素(R1S3)。還有，雖然鹵素並非基團，但於本發明中，將其當作基團之1種(以下，其他結構式上之取代基也設為相同)。又，將苯基作為芳基使用之情形，取代基之位置較佳為鄰位或間位，因為能夠在苯基與主鏈結構發生適度之扭曲，不會導入過多之烷基側鏈而能夠使共軛聚合物的溶解性提高。 Aryl or heteroaryl group having a substituent of the case, as the aryl group or heteroaryl group of the substituent include: an alkyl group (R 1S1) alkoxy or (R 1S2), halo (R 1S3). Further, although halogen is not a group, in the present invention, it is regarded as one type of a group (hereinafter, the substituents on the other structural formulas are also the same). Further, in the case where a phenyl group is used as an aryl group, the position of the substituent is preferably an ortho or meta position because it can be moderately distorted in the structure of the phenyl group and the main chain, and an excessive alkyl side chain can not be introduced. The solubility of the conjugated polymer is improved.
於此，所謂烷基(R1S1)，例如為甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基之飽和脂肪族烴，可為直鏈狀、分枝狀或環狀，不論未取代或已被取代皆可。作為被取代之情形的取代基例子，可列舉：烷氧基、鹵素。為了確保電子供給性有機材料充分的載體移動度，烷基(R1S1)之碳數較佳為6以下。於此，在烷基(R1S1)之碳數中，數目中不含在烷基之取代基上所含之碳。為了加強共軛聚合物之HOMO準位，作為烷基(R1S1)之取代基特別適合使用氟。 Here, the alkyl group (R 1S1 ) is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecane. The saturated aliphatic hydrocarbon may be linear, branched or cyclic, whether unsubstituted or substituted. Examples of the substituent which is substituted may be an alkoxy group or a halogen. In order to ensure sufficient carrier mobility of the electron-donating organic material, the carbon number of the alkyl group (R 1S1 ) is preferably 6 or less. Here, in the carbon number of the alkyl group (R 1S1 ), the carbon contained in the substituent of the alkyl group is not included in the number. In order to enhance the HOMO level of the conjugated polymer, fluorine is particularly suitable as a substituent for the alkyl group (R 1S1 ).
又，所謂烷氧基(R1S2)，表示使例如甲氧基、乙氧基、丙氧基、丁氧基等之使醚鍵介於中間而鍵結脂肪族烴基之基，不論烷氧基(R1S2)之脂肪族烴基係未取代或具有取代基皆可。作為具有取代基之情形的取代基，可列舉：上述芳基或上述雜芳基、鹵素。烷氧基(R1S2)之較佳的碳數範圍係與上述烷基(R1S1)之情形相同，較佳為6以下。還有該情形下，烷氧基(R1S2)之碳數中，數目中不含在脂肪族羥基之取代基上所含之碳。 Further, the alkoxy group (R 1S2 ) means a group in which an aliphatic hydrocarbon group is bonded to an intermediate such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, regardless of the alkoxy group. The aliphatic hydrocarbon group of (R 1S2 ) may be unsubstituted or have a substituent. Examples of the substituent having a substituent include the above aryl group, the above heteroaryl group, and halogen. The preferred carbon number range of the alkoxy group (R 1S2 ) is the same as that of the above alkyl group (R 1S1 ), and is preferably 6 or less. Also in this case, the carbon number of the alkoxy group (R 1S2 ) does not contain the carbon contained in the substituent of the aliphatic hydroxyl group.
又，可適應於本發明之鹵素(R1S3)係氟、氯、溴、碘中任一種。於該等之中，氟係藉由作為芳基或雜芳基之取代基而導入，由於能夠加強電子供給性有機材料HOMO準位，而特別適合被使用。 Further, the halogen (R 1S3 ) which is suitable for the present invention is any one of fluorine, chlorine, bromine and iodine. Among these, fluorine is introduced as a substituent of an aryl group or a heteroaryl group, and is particularly suitable for use because it can enhance the HOMO level of the electron-donating organic material.
含有該通式(1)所表示的結構之電子供給性有機材料較佳為由通式(2)所表示的結構所構成者。 The electron-donating organic material containing the structure represented by the above formula (1) is preferably composed of the structure represented by the formula (2).
(該通式(2)中，X係表示能夠保持共軛結構之2價鍵結基。n係表示聚合度，其係表示2以上1,000以下之範圍)。 (In the general formula (2), X represents a divalent bond group capable of maintaining a conjugated structure. n represents a degree of polymerization, and represents a range of 2 or more and 1,000 or less).
藉由將n設為2以上1,000以下，由於能夠提高電子供給性有機材料之載體移動度，再者在上述體積異接 合薄膜中使有效之載體通道形成，故能夠提高光電轉換效率。從合成上之容易性，n較佳為小於100。聚合度能夠以重複單元之分子量(計算值)除重量平均分子量而求得。重量平均分子量能夠利用GPC(凝膠滲透層析儀)而測定，換算成聚苯乙烯之標準試料後求得。 By setting n to 2 or more and 1,000 or less, since the carrier mobility of the electron-donating organic material can be improved, the above-described volume is different. In the film, an effective carrier channel is formed, so that the photoelectric conversion efficiency can be improved. From the ease of synthesis, n is preferably less than 100. The degree of polymerization can be determined by dividing the molecular weight (calculated value) of the repeating unit by the weight average molecular weight. The weight average molecular weight can be measured by GPC (gel permeation chromatography), and is obtained by converting into a standard sample of polystyrene.
又，該通式(2)中，X能夠保持共軛結構之2價鍵結基。於此，所謂能夠保持共軛結構之2價鍵結基係指其本身具有共軛結構且2處鍵結位置兩側的共軛結構使該鍵結基介於中間而可連續的鍵結基。作為如此之鍵結基X，可列舉：寡噻吩、苯并二噻吩、環戊二噻吩等之噻吩衍生物，其中，為了能夠窄化能帶間隙、且保持高的載體移動度，更佳使用下列通式(3)所表示的苯并二噻吩或環戊二噻吩。 Further, in the above formula (2), X can maintain a divalent bond group of a conjugated structure. Here, the divalent bonding group capable of maintaining the conjugated structure means that the conjugated structure itself has a conjugated structure on both sides of the bonding site, and the bonding group is intermediate and the continuous bonding group is . As such a bonding group X, a thiophene derivative such as oligothiophene, benzodithiophene or cyclopentadithiophene can be mentioned, and in order to narrow the band gap and maintain a high carrier mobility, it is more preferable to use The benzodithiophene or cyclopentadithiophene represented by the following general formula (3).
(通式(3)中，R2至R5可相同亦可不同，其係表示可被取代的烷基、烷氧基、芳基、或雜芳基)。 (In the formula (3), R 2 to R 5 may be the same or different and represent an alkyl group, an alkoxy group, an aryl group or a heteroaryl group which may be substituted.
針對烷基、烷氧基、芳基、雜芳基，除了較佳的碳數範圍之外，則如上所述。為了保持共軛聚合物之載體移動度，特佳使用R2至R5為碳數12以下之烷基或烷氧基。 With respect to the alkyl group, alkoxy group, aryl group, heteroaryl group, as described above, in addition to the preferred carbon number range. In order to maintain the carrier mobility of the conjugated polymer, it is particularly preferable to use an alkyl group or an alkoxy group having R 2 to R 5 of 12 or less carbon atoms.
作為含有該通式(1)所表示的結構之電子供給性有機材料，具體而言，可列舉如下之結構。基於與該通式(2)之情形同樣的理由，下列結構式中之n較佳為2以上1,000以下之範圍。 Specific examples of the electron-donating organic material containing the structure represented by the above formula (1) include the following structures. For the same reason as in the case of the general formula (2), n in the following structural formula is preferably in the range of 2 or more and 1,000 or less.
還有，含有通式(1)所表示的結構單元之電子供給性有機材料，可利用例如在該非專利文獻5所記載的聚合方法、或在該非專利文獻8所記載的聚合方法而獲得。 In addition, the electron-donating organic material containing the structural unit represented by the general formula (1) can be obtained, for example, by the polymerization method described in Non-Patent Document 5 or the polymerization method described in Non-Patent Document 8.
含有本發明之通式(1)所表示的結構單元之電子供給性有機材料係顯示p型半導體特性之材料，作為光伏元件用材料係適合使用於光伏元件中之有機半導體層。含有本發明之通式(1)所表示的結構單元之電子供給性有機材料係可作成僅由(i-1)本身所構成的光伏元件用材料而使用，亦可與(i-2)其他之電子供給性有機材料合併使用後作成光伏元件用材料而使用，亦可與顯示(ii)n型半導體特性之電子接受性有機材料組合後作成光伏元件用材料而使用。其中，由於可獲得更高的光電轉換效率，較佳為與電子接受性有機材料組合(該(ii)之形態)。還有，於該(ii)之形態中，亦可與在(i-2)之形態的其他電子供給性有機材料合併使用。還有，針對使用該等光伏元件用材料之有機半導體層及光伏元件之具體形態係敘述於後。 The electron-donating organic material containing the structural unit represented by the general formula (1) of the present invention is a material exhibiting p-type semiconductor characteristics, and is suitable as an organic semiconductor layer for use in a photovoltaic element as a material for a photovoltaic element. The electron-donating organic material containing the structural unit represented by the general formula (1) of the present invention can be used as a material for photovoltaic elements composed only of (i-1) itself, and can also be used with (i-2) other The electron-donating organic material is used in combination as a material for a photovoltaic element, and may be used as a material for a photovoltaic element in combination with an electron-accepting organic material exhibiting (ii) n-type semiconductor characteristics. Among them, since a higher photoelectric conversion efficiency can be obtained, it is preferably combined with an electron-accepting organic material (the form of (ii)). Further, in the form of (ii), it may be used in combination with other electron-donating organic materials in the form of (i-2). Further, specific examples of the organic semiconductor layer and the photovoltaic element using the materials for photovoltaic elements will be described later.
與含有通式(1)所表示的結構單元之電子供給性有機材料與其他電子供給性有機材料合併使用而作為光伏元件用材料使用之情形(該(i-2)之形態)下，作為能夠合併使用之其他電子供給性有機材料，例如，可列舉：聚噻吩系聚合物、苯并噻二唑-噻吩系衍生物、苯并噻二唑-噻吩系共聚物、聚對伸苯伸乙烯系聚合物、聚對伸苯系聚合物、聚茀系聚合物、聚吡咯系聚合物、聚苯胺系聚合物、聚乙炔系聚合物、聚伸噻吩伸乙烯系聚合物等之共軛系聚合物；或H2酞青素(H2Pc)、銅酞青素(CuPc)、鋅酞青素(ZnPc)等之酞青素衍生物；紫質(porphyrin)衍生物、N,N’-二苯基-N,N’-二(3-甲基苯 基)-4,4’-二苯基-1,1’-二胺(TPD)、N,N’-二萘基-N,N’-二苯基-4,4’-二苯基-1,1’-二胺(NPD)等之三芳基胺衍生物；4,4’-二(咔唑-9-基)聯苯(CBP)等之咔唑衍生物；寡噻吩衍生物(三噻吩、四噻吩、六噻吩、八噻吩等)等之低分子有機化合物。 In the case where the electron-donating organic material containing the structural unit represented by the general formula (1) is used in combination with another electron-donating organic material and used as a material for a photovoltaic element (the form of (i-2)), Other electron-donating organic materials used in combination include, for example, a polythiophene-based polymer, a benzothiadiazole-thiophene-based derivative, a benzothiadiazole-thiophene-based copolymer, and a poly-p-phenylene-extended ethylene compound. A conjugated polymer such as a polymer, a polyparaphenylene polymer, a polyfluorene polymer, a polypyrrole polymer, a polyaniline polymer, a polyacetylene polymer, or a polythiophene ethylene polymer ; a phthalocyanine pigment or H 2 (H 2 Pc), copper phthalocyanine pigment (CuPc), zinc phthalocyanine pigment (of ZnPc), etc. phthalocyanine derivatives; rhodopsin (porphyrins adsorbed) derivative, N, N'- two Phenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine (TPD), N,N'-dinaphthyl-N,N a triarylamine derivative such as '-diphenyl-4,4'-diphenyl-1,1'-diamine (NPD); 4,4'-bis(carbazol-9-yl)biphenyl ( a carbazole derivative such as CBP); an oligothiophene derivative (trithiophene, tetrathiophene, hexathiophene, octathiophene, etc.) The low molecular weight organic compounds.
於含有通式(1)所表示的結構單元之電子供給性有機材料中，在與顯示n型半導體特性之電子接受性有機材料組合而作為光伏元件用材料使用之情形(該(ii)之形態)下，作為能夠組合的電子接受性有機材料，例如，可列舉：1,4,5,8-萘四羧基二酐(NTCDA)、3,4,9,10-苝四羧基二酐(PTCDA)、3,4,9,10-苝四羧基雙苯并咪唑(PTCBI)、N,N’-二辛基-3,4,9,10-萘四羧基二醯亞胺(PTCDI-C8H)、2-(4-聯苯基)-5-(4-三級丁基苯基)-1,3,4-二唑(PBD)、2,5-二(1-萘基)-1,3,4-二唑(BND)等之唑衍生物；3-(4-聯苯基)-4-苯基-5-(4-三級丁基苯基)-1,2,4-***(TAZ)等之***衍生物；啡啉衍生物；氧化膦衍生物；富勒烯(以C60、C70、C76、C78、C82、C84、C90、C94為主之未取代物、[6,6]-苯基C61丁酸甲酯([6,6]-PCBM)、[5,6]-苯基C61丁酸甲酯([5,6]-PCBM)、[6,6]-苯基C61丁酸己酯([6,6]-PCBH)、[6,6]-苯基C61丁酸十二烷酯([6,6]-PCBD)、苯基C71丁酸甲酯(PC70BM)、苯基C85丁酸甲酯(PC84BM)等)；碳奈米管(CNT)；將氰基導入聚對伸苯伸乙烯系聚合物的衍生物(CN-PPV)等。其中，由於富勒烯化合物係電荷分離速度與電子移動速度快，較適合被使用。於富勒烯化合物之 中，由於C70衍生物(上述PC70BM等)係具優越之光吸收特性，由於可獲得更高的光電轉換效率，故較佳。 In the case of an electron-donating organic material containing a structural unit represented by the general formula (1), it is used as a material for a photovoltaic element in combination with an electron-accepting organic material exhibiting n-type semiconductor characteristics (form of (ii) In the following, as the electron accepting organic material which can be combined, for example, 1,4,5,8-naphthalenetetracarboxy dianhydride (NTCDA), 3,4,9,10-decanetetracarboxylic dianhydride (PTCDA) , 3,4,9,10-decyltetracarboxybenzimidazole (PTCBI), N,N'-dioctyl-3,4,9,10-naphthalenetetracarboxydiimide (PTCDI-C8H) ,2-(4-biphenyl)-5-(4-tri-butylphenyl)-1,3,4- Diazole (PBD), 2,5-di(1-naphthyl)-1,3,4- Diazole (BND), etc. An azole derivative; a triazole derivative such as 3-(4-biphenyl)-4-phenyl-5-(4-tributylphenyl)-1,2,4-triazole (TAZ); Phenanthroline derivatives; phosphine oxide derivatives; fullerenes (unsubstituted by C 60 , C 70 , C 76 , C 78 , C 82 , C 84 , C 90 , C 94 , [6,6] -Phenyl C61 butyrate methyl ester ([6,6]-PCBM), [5,6]-phenyl C61 butyrate methyl ester ([5,6]-PCBM), [6,6]-phenyl C61 Hexyl butyrate ([6,6]-PCBH), [6,6]-phenyl C61 butyrate ([6,6]-PCBD), phenyl C71 butyrate (PC 70 BM) ), phenyl C85 methyl butyrate (PC 84 BM), etc.; carbon nanotubes (CNT); a cyano group introduced into a polyparaphenylene vinylene derivative (CN-PPV). Among them, since the fullerene compound has a charge separation rate and a fast electron moving speed, it is preferably used. Among the fullerene compounds, since the C 70 derivative (the above PC 70 BM or the like) has excellent light absorption characteristics, it is preferable because higher photoelectric conversion efficiency can be obtained.
於含有通式(1)所表示的結構單元之電子供給性有機材料中，與顯示n型半導體特性之電子接受性有機材料組合而作為光伏元件用材料使用之情形(該(ii)之形態)中，雖然電子供給性有機材料與電子接受性有機材料之含率(重量分率)並未被特別限定，電子供給性有機材料：電子接受性有機材料之重量分率較佳為1：99至99：1之範圍，更佳為10：90至90：10之範圍，進一步較佳為20：80至60：40之範圍。 In the case of an electron-donating organic material containing a structural unit represented by the general formula (1), it is used as a material for a photovoltaic element in combination with an electron-accepting organic material exhibiting n-type semiconductor characteristics (form of (ii)) In the present invention, although the content (weight fraction) of the electron-donating organic material and the electron-accepting organic material is not particularly limited, the electron-accepting organic material: the electron-accepting organic material preferably has a weight fraction of 1:99 to The range of 99:1 is more preferably in the range of 10:90 to 90:10, further preferably in the range of 20:80 to 60:40.
於含有通式(1)所表示的結構單元之電子供給性有機材料中，針對與顯示n型半導體特性之電子接受性有機材料組合而作為光伏元件用材料使用之情形(該(ii)之形態)的有機半導體層之較佳的形態係敘述於後，有將電子供給性有機材料與電子接受性有機材料混合後使用的形態、與積層後使用的形態。作為採取混合後使用的形態之情形的混合方法，並非被特別限定者，以所要之比例添加於溶劑中之後，可列舉：1種或組合複數種之加熱、攪拌、超音波照射等之方法而使其溶解於溶劑中之方法。在混合後使用的形態之情形的電子供給性有機材料：電子接受性有機材料之重量分率係如上所述，積層電子供給性有機材料與電子接受性有機材料後使用的形態之情形(包含二層以上的積層構造之情形)係意指所積層的層全體之電子供給性有機材料與電子接受性有機材料的含有比例。 In the case of an electron-donating organic material containing a structural unit represented by the general formula (1), it is used as a material for a photovoltaic element in combination with an electron-accepting organic material exhibiting n-type semiconductor characteristics (form of (ii) The preferred embodiment of the organic semiconductor layer is described below, and is a form in which an electron-donating organic material and an electron-accepting organic material are mixed and used, and a form used after lamination. The mixing method in the case of adopting the form to be used after mixing is not particularly limited, and after adding it to the solvent in a desired ratio, one or a combination of a plurality of methods such as heating, stirring, and ultrasonic irradiation may be mentioned. A method of dissolving it in a solvent. The electron-donating organic material in the case of the form to be used after the mixing: the weight fraction of the electron-accepting organic material is as described above, and the form in which the laminated electron-donating organic material and the electron-accepting organic material are used (including two The case of the laminated structure of the layer or more means the content ratio of the electron-donating organic material and the electron-accepting organic material of the layer of the laminated layer.
為了使光電轉換效率更提高，電子供給性有機材料及/或電子接受性有機材料較佳成為如載體之阱的雜質含量要越微量越好，在電子供給性有機材料及/或電子接受性有機材料之製程中，較佳為極力去除。於本發明中，去除含有該通式(1)所表示的結構單元之電子供給性有機材料或電子接受性有機材料之雜質的精製方法並未被特別限定，能夠利用管柱層析法、再結晶法、昇華法、再沉澱法、索氏(Soxhlet)萃取法、藉由GPC所得之分子量分割法、過濾法、離子交換法、螯合法等；於一般低分子有機材料之精製中，較佳利用管柱層析法、再結晶法、昇華法。另一方面，高分子量物之精製中，去除低分子量成分之情形下，較佳利用再沉澱法或索氏萃取法，藉由GPC所得之分子量分割法；去除金屬成分之情形下，較佳利用再沉澱法或螯合法、離子交換法。該等方法之中，亦可組合複數種。 In order to improve the photoelectric conversion efficiency, the electron-donating organic material and/or the electron-accepting organic material preferably becomes a trap such as a carrier, and the impurity content is as small as possible, in an electron-donating organic material and/or an electron-accepting organic material. In the process of the material, it is preferred to remove as much as possible. In the present invention, the method for purifying the impurities of the electron-donating organic material or the electron-accepting organic material containing the structural unit represented by the above formula (1) is not particularly limited, and column chromatography can be used. Crystallization, sublimation, reprecipitation, Soxhlet extraction, molecular weight fractionation by GPC, filtration, ion exchange, chelation, etc.; in the purification of general low molecular organic materials, preferably Column chromatography, recrystallization, sublimation. On the other hand, in the purification of a high molecular weight substance, in the case of removing a low molecular weight component, it is preferable to use a molecular weight division method by GPC by a reprecipitation method or a Soxhlet extraction method, and a metal component is preferably used in the case of removing a metal component. Reprecipitation or chelation, ion exchange. Among these methods, a plurality of types may be combined.
接著，針對本發明之光伏元件加以說明。本發明之光伏元件至少具有正極與負極，該等之間具有含有本發明之光伏元件用材料的有機半導體層。第1圖係顯示本發明之光伏元件之一例的示意圖。於第1圖中，符號1係基板、符號2係正極、符號3係含有本發明之光伏元件用材料之有機半導體層、符號4係負極。 Next, the photovoltaic element of the present invention will be described. The photovoltaic element of the present invention has at least a positive electrode and a negative electrode with an organic semiconductor layer containing the material for a photovoltaic element of the present invention. Fig. 1 is a schematic view showing an example of a photovoltaic element of the present invention. In the first drawing, the symbol 1 is a substrate, the symbol 2 is a positive electrode, and the symbol 3 is an organic semiconductor layer containing a material for a photovoltaic element of the present invention, and a symbol 4 negative electrode.
有機半導體層3係含有本發明之光伏元件用材料。亦即，包含含有通式(1)所表示的結構單元之電子供給性有機材料。於此，在含有通式(1)所表示的結構單元之電子供給性有機材料中，與顯示n型半導體特性之 電子接受性有機材料組合而使用之情形(該(ii)之形態)，該等有機材料係有混合後使用的形態與積層後使用的形態，較佳為混合後使用的形態。亦即，由於藉由混合電子供給性有機材料與電子接受性有機材料而成為能增加有助於光電轉換效率之電子供給性有機材料與電子接受性有機材料之接合面的體積異接合型光伏元件，故較佳。在該體積異接合型之有機發電層中，含有通式(1)所表示的結構單元之電子供給性有機材料與電子接受性有機材料較佳為以奈米尺寸相分離。雖然該相分離結構之領域尺寸並非受特別限定者，但通常為1nm以上50nm以下。 The organic semiconductor layer 3 contains the material for photovoltaic elements of the present invention. That is, an electron-donating organic material containing a structural unit represented by the general formula (1) is contained. Here, in the electron-donating organic material containing the structural unit represented by the general formula (1), and exhibiting the characteristics of the n-type semiconductor In the case where the electron-accepting organic materials are used in combination (the form of (ii)), the organic materials are those which are used after mixing and those which are used after lamination, and are preferably used after mixing. That is, by mixing the electron-donating organic material and the electron-accepting organic material, it becomes a volume-junction type photovoltaic element capable of increasing the bonding surface of the electron-donating organic material and the electron-accepting organic material contributing to the photoelectric conversion efficiency. Therefore, it is better. In the volume-different type organic power generation layer, the electron-donating organic material containing the structural unit represented by the general formula (1) and the electron-accepting organic material are preferably phase-separated in a nanometer size. Although the domain size of the phase separation structure is not particularly limited, it is usually 1 nm or more and 50 nm or less.
又，組合顯示n型半導體特性之電子接受性有機材料與含有通式(1)所表示的結構單元之電子供給性有機材料而使用之情形(該(ii)之形態)之另一對應的電子供給性有機材料與電子接受性有機材料所積層之情形，含有顯示p型半導體特性之電子供給性有機材料之層較佳為正極側；含有顯示n型半導體特性之電子接受性有機材料之層較佳為負極側。將如此情形之光伏元件一例顯示於第2圖。符號5係含有電子供給性有機材料之層，其中該電子供給性有機材料係含有通式(1)所表示的結構單元；符號6係含有電子接受性有機材料之層。有機半導體層較佳為5nm至500nm之厚度，更佳為30nm至300nm。所積層之情形，含有本發明之電子供給性有機材料之層較佳為具有上述厚度中之1nm至400nm之厚度，更佳為15nm至150nm。 In addition, another electron corresponding to the case where the electron-accepting organic material having the n-type semiconductor property and the electron-donating organic material containing the structural unit represented by the general formula (1) are used in combination (the form of (ii)) In the case where a supply organic material and an electron-accepting organic material are laminated, a layer containing an electron-donating organic material exhibiting p-type semiconductor characteristics is preferably a positive electrode side; and a layer containing an electron-accepting organic material exhibiting an n-type semiconductor property is more preferable Good for the negative side. An example of a photovoltaic element in this case is shown in Fig. 2. Symbol 5 is a layer containing an electron-donating organic material containing a structural unit represented by the general formula (1); and a symbol 6 containing a layer containing an electron-accepting organic material. The organic semiconductor layer is preferably from 5 nm to 500 nm in thickness, more preferably from 30 nm to 300 nm. In the case of the laminated layer, the layer containing the electron-donating organic material of the present invention preferably has a thickness of from 1 nm to 400 nm in the above thickness, more preferably from 15 nm to 150 nm.
於本發明之光伏元件中，較佳為正極2或負極4中任一種具有光穿透性。若電極之光穿透性為使入射光到達有機半導體層3而產生電動勢之程度的話，並未被特別限定。於此，所謂電極係表示正極或負極。又，在本發明之光穿透性係利用[穿透光強度(W/m2)/入射光強度(W/m2)]×100(%)所求得之值。若電極之厚度為具有光穿透性與導電性之範圍的話即可，雖然視電極材料而異，但較佳為20nm至300nm。還有，若另一側電極具有導電性的話，則光穿透性未必需要，厚度也未被特別限定。 In the photovoltaic element of the present invention, it is preferred that either of the positive electrode 2 or the negative electrode 4 has light permeability. The light transmittance of the electrode is not particularly limited as long as the incident light reaches the organic semiconductor layer 3 to generate an electromotive force. Here, the electrode system means a positive electrode or a negative electrode. Further, in the light transmittance system of the present invention, the value obtained by [transmitting light intensity (W/m 2 ) / incident light intensity (W/m 2 )] × 100 (%) is used. The thickness of the electrode may be in the range of light transmittance and conductivity, and although it varies depending on the electrode material, it is preferably from 20 nm to 300 nm. Further, if the other side electrode is electrically conductive, the light transmittance is not necessarily required, and the thickness is not particularly limited.
作為電極材料，較佳為在一側電極使用功函數大的導電性材料，在另一側電極使用功函數小的導電性材料。使用功函數大的導電性材料之電極成為正極。作為該功函數大的導電性材料，除了金、鉑、鉻、鎳等金屬之外，較佳使用具有透明性的銦、錫、鉬等之金屬氧化物、複合金屬氧化物(銦錫氧化物(ITO)、銦鋅氧化物(IZO)等)。於此，正極2所用之導電性材料較佳為與有機半導體層3歐姆接合者。還有，於使用後述之電洞輸送層之情形下，正極2所用之導電性材料較佳使用與電洞輸送層歐姆接合者。 As the electrode material, a conductive material having a large work function is preferably used for one electrode, and a conductive material having a small work function is used for the other electrode. An electrode using a conductive material having a large work function becomes a positive electrode. As the conductive material having a large work function, in addition to metals such as gold, platinum, chromium, and nickel, metal oxides such as indium, tin, and molybdenum having transparency, and composite metal oxides (indium tin oxide) are preferably used. (ITO), indium zinc oxide (IZO), etc.). Here, the conductive material used for the positive electrode 2 is preferably an ohmic bond with the organic semiconductor layer 3. Further, in the case of using a hole transport layer to be described later, the conductive material used for the positive electrode 2 is preferably used in an ohmic manner with the hole transport layer.
使用功函數小的導電性材料之電極成為負極，作為該功函數小的導電性材料係使用鹼金屬或鹼土金屬，具體而言，鋰、鎂、鈣等。又，較佳使用錫或銀、鋁。還有，也較佳使用由上述金屬所構成的合金或由上述金屬積層體所構成的電極。又，藉由將氟化鋰或氟化 銫等之金屬氟化物導入負極4與電子輸送層之界面，使取出電流提高也為可能。於此，負極4中所用之導電性材料較佳為與有機半導體層3歐姆接合者。 An electrode using a conductive material having a small work function becomes a negative electrode, and an alkali metal or an alkaline earth metal is used as the conductive material having a small work function, specifically, lithium, magnesium, calcium, or the like. Further, tin or silver or aluminum is preferably used. Further, an alloy composed of the above metal or an electrode composed of the above metal laminate is preferably used. Also, by using lithium fluoride or fluorination It is also possible to introduce a metal fluoride such as ruthenium into the interface between the negative electrode 4 and the electron transporting layer to increase the extraction current. Here, the conductive material used in the negative electrode 4 is preferably an ohmic bond with the organic semiconductor layer 3.
按照光電轉換材料之種類或用途，基板1能夠使用可積層電極材料或有機半導體層的基板，例如無鹼玻璃、石英玻璃等之無機材料；利用任意之方法而由聚酯、聚碳酸酯、聚茀、聚醯胺、聚醯亞胺、聚硫醚、聚對二甲苯、環氧樹脂或氟系樹脂等之有機材料所製作的薄膜或板。又，使光從基板側射入而使用之情形，較佳為在上述所示之各基板中預先具有80%左右之光穿透性。 According to the type or use of the photoelectric conversion material, the substrate 1 can use a substrate in which an electrode material or an organic semiconductor layer can be laminated, for example, an inorganic material such as alkali-free glass or quartz glass; and polyester, polycarbonate, or poly by any method. A film or sheet made of an organic material such as hydrazine, polyamine, polyimide, polythioether, parylene, epoxy resin or fluorine resin. Further, in the case where light is incident from the substrate side, it is preferable to have a light transmittance of about 80% in advance in each of the substrates described above.
於本發明中，亦可在正極2與有機半導體層3之間設置電洞輸送層。作為形成電洞輸送層之材料，較佳使用聚噻吩系聚合物、聚對伸苯伸乙烯系聚合物、聚茀系聚合物等之導電性高分子；或酞青素衍生物(H2Pc、CuPc、ZnPc等)、紫質衍生物等之p型半導體特性之低分子有機化合物。特佳使用聚噻吩系聚合物之聚伸乙二氧基噻吩(PEDOT)或在PEDOT中添加有聚苯乙烯磺酸酯(PSS)者。電洞輸送層較佳為5nm至600nm之厚度，更佳為30nm至200nm。 In the present invention, a hole transport layer may be provided between the positive electrode 2 and the organic semiconductor layer 3. As a material for forming the hole transport layer, a conductive polymer such as a polythiophene polymer, a polyparaphenylene vinyl polymer or a polyfluorene polymer; or an anthraquinone derivative (H 2 Pc) is preferably used. , low molecular organic compounds of p-type semiconductor properties such as CuPc, ZnPc, etc., and a purple derivative. It is particularly preferable to use polyethylene terephthalate (PEDOT) of polythiophene-based polymer or polystyrene sulfonate (PSS) in PEDOT. The hole transport layer is preferably from 5 nm to 600 nm, more preferably from 30 nm to 200 nm.
又，本發明之光伏元件亦可將電子輸送層設置於有機半導體層3與負極4之間。作為形成電子輸送層之材料，並非被特別限定者，較佳使用如上述之電子接受性有機材料(NTCDA、PTCDA、PTCDI-C8H、唑衍生物、***衍生物、啡啉衍生物、氧化膦衍生物、富勒 烯化合物、CNT、CN-PPV等)而顯示n型半導體特性之有機材料。電子輸送層較佳為5nm至600nm之厚度，更佳為30nm至200nm。 Further, the photovoltaic element of the present invention may be provided between the organic semiconductor layer 3 and the negative electrode 4 with an electron transport layer. As a material for forming the electron transport layer, it is not particularly limited, and it is preferable to use an electron accepting organic material (NTCDA, PTCDA, PTCDI-C8H, etc.) as described above. An organic material exhibiting n-type semiconductor characteristics, such as an azole derivative, a triazole derivative, a phenanthroline derivative, a phosphine oxide derivative, a fullerene compound, CNT, or CN-PPV. The electron transport layer is preferably from 5 nm to 600 nm, more preferably from 30 nm to 200 nm.
又，本發明之光伏元件亦可使1個以上之中間電極介於中間，積層2層以上之有機半導體層而形成串聯接合。例如，可列舉：基板/正極/第1有機半導體層/中間電極/第2有機半導體層/負極的積層結構。將如此之結構也稱為串聯結構。藉由作成如此之串聯結構，能夠使釋放電壓提高。還有，可將上述電洞輸送層設置於正極與第1有機半導體層之間、及中間電極與第2有機半導體層之間；亦可將上述電子輸送層設置於第1有機半導體層與中間電極之間、及第2有機半導體層與負極之間。 Further, in the photovoltaic device of the present invention, one or more intermediate electrodes may be interposed therebetween, and two or more organic semiconductor layers may be laminated to form a series connection. For example, a laminated structure of a substrate/positive electrode/first organic semiconductor layer/intermediate electrode/second organic semiconductor layer/negative electrode can be cited. Such a structure is also referred to as a series structure. By making such a series structure, the release voltage can be increased. Further, the hole transport layer may be provided between the positive electrode and the first organic semiconductor layer and between the intermediate electrode and the second organic semiconductor layer; or the electron transport layer may be disposed in the middle of the first organic semiconductor layer Between the electrodes and between the second organic semiconductor layer and the negative electrode.
如此串聯結構之情形，有機半導體層之至少1層含有本發明之光伏元件用材料，於其他層中，為了不使短路電流降低，所謂含有通式(1)所表示的結構單元之電子供給性有機材料較佳為含有能帶間隙不同的電子供給性有機材料。作為如此之情形下所用之電子供給性有機材料，例如，可列舉：上述之聚噻吩系聚合物、苯并噻二唑-噻吩系衍生物、苯并噻二唑-噻吩系共聚物、聚對伸苯伸乙烯系聚合物、聚對伸苯系聚合物、聚茀系聚合物、聚吡咯系聚合物、聚苯胺系聚合物、聚乙炔系聚合物、聚伸噻吩伸乙烯系聚合物等之共軛系聚合物；或酞青素衍生物、紫質衍生物、三芳基胺衍生物、咔唑衍生物、寡噻吩衍生物等之低分子有機化合物。 In the case of such a series structure, at least one layer of the organic semiconductor layer contains the material for photovoltaic elements of the present invention, and in other layers, in order to prevent the short-circuit current from being lowered, the electron supply property of the structural unit represented by the general formula (1) is contained. The organic material preferably contains an electron-donating organic material having a different band gap. Examples of the electron-donating organic material used in such a case include the above-mentioned polythiophene-based polymer, benzothiadiazole-thiophene-based derivative, benzothiadiazole-thiophene-based copolymer, and poly-pair. Benzene extended ethylene polymer, polyparaphenylene polymer, polyfluorene polymer, polypyrrole polymer, polyaniline polymer, polyacetylene polymer, polythiophene vinyl polymer, etc. A conjugated polymer; or a low molecular organic compound such as an anthraquinone derivative, a purpurin derivative, a triarylamine derivative, a carbazole derivative, or an oligothiophene derivative.
又，作為此處所用之中間電極用材料，較佳為具有高的導電性者，例如，可列舉：上述之金、鉑、鉻、鎳、鋰、鎂、鈣、錫、銀、鋁等之金屬；或具有透明性的銦、錫、鉬等之金屬氧化物、複合金屬氧化物(銦錫氧化物(ITO)、銦鋅氧化物(IZO)等)；由上述金屬所構成的合金或上述金屬積層體、聚伸乙二氧基噻吩(PEDOT)或在PEDOT中添加有聚苯乙烯磺酸酯(PSS)者等。中間電極較佳為具有光穿透性，也利用如光穿透性低的金屬之材料，藉由薄化膜厚而大多為能夠確保充分的光穿透性之情形。 Moreover, as a material for the intermediate electrode used herein, it is preferable to have high conductivity, and examples thereof include gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, aluminum, and the like. a metal oxide or a metal oxide such as indium, tin or molybdenum having a transparency; a composite metal oxide (indium tin oxide (ITO), indium zinc oxide (IZO), etc.); an alloy composed of the above metal or the above A metal laminate, a polyethylene dioxythiophene (PEDOT) or a polystyrene sulfonate (PSS) added to PEDOT. The intermediate electrode is preferably light-transmitting, and is also made of a material having a low light-transmitting property, and is often thinned to have a sufficient light transmittance.
接著，針對本發明之光伏元件之製作方法，舉例加以說明。利用濺鍍法等，在基板上形成ITO等之透明電極(此情形下，相當於正極)。接著，將含有通式(1)所表示的結構單元之電子供給性有機材料、及必要時含有電子接受性有機材料之光電轉換元件用材料溶解於溶劑中而作成溶液，塗布於透明電極上而形成有機半導體層。 Next, a method of fabricating the photovoltaic element of the present invention will be described by way of example. A transparent electrode such as ITO (in this case, a positive electrode) is formed on the substrate by a sputtering method or the like. Then, an electron-donating organic material containing a structural unit represented by the general formula (1) and a material for a photoelectric conversion element containing an electron-accepting organic material are dissolved in a solvent to prepare a solution, which is applied onto a transparent electrode. An organic semiconductor layer is formed.
此時所用之溶劑較佳為有機溶劑，例如，可列舉：甲醇、乙醇、丁醇、甲苯、二甲苯、鄰氯苯酚、丙酮、乙酸乙酯、乙二醇、四氫呋喃、二氯甲烷、氯仿、二氯乙烷、氯苯、二氯苯、三氯苯、氯萘、二甲基甲醯胺、二甲基亞碸、N-甲基吡咯啶酮、γ-丁內酯等。亦可使用2種以上該等有機溶劑。 The solvent used at this time is preferably an organic solvent, and examples thereof include methanol, ethanol, butanol, toluene, xylene, o-chlorophenol, acetone, ethyl acetate, ethylene glycol, tetrahydrofuran, dichloromethane, and chloroform. Dichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, dimethylformamide, dimethylhydrazine, N-methylpyrrolidone, γ-butyrolactone, and the like. Two or more of these organic solvents can also be used.
混合含有通式(1)所表示的結構單元之電子供給性有機材料及電子接受性有機材料而形成有機半導 體層之情形，以所要之比例而將含有通式(1)所表示的結構單元之電子供給性有機材料與電子接受性有機材料添加於溶劑中，利用加熱、攪拌、超音波照射等之方法而使其溶解、作成溶液，塗布於透明電極上。此情形下，藉由混合2種以上之溶劑後使用，也能夠使光伏元件之光電轉換效率提高。此係如上所述，電子供給性有機材料與電子接受性有機材料以奈米尺寸所相分離的結構適合於提高轉換效率，因而能夠藉由溶劑而形成如此之相分離構造。如此之情形下所組合的溶劑能夠根據所用之電子供給性有機材料與電子接受性有機材料之種類而選擇最適之組合種類。使用含有通式(1)所表示的結構單元之電子供給性有機材料之情形，作為組合的較佳溶劑，可列舉：上述中之氯仿與氯苯。此情形下，各溶劑之混合體積比例較佳為氯仿：氯苯=5：95至95：5之範圍，進一步較佳為10：90至90：10之範圍。 An electron-donating organic material and an electron-accepting organic material containing a structural unit represented by the general formula (1) are mixed to form an organic semi-conductive In the case of the bulk layer, the electron-donating organic material containing the structural unit represented by the general formula (1) and the electron-accepting organic material are added to the solvent at a desired ratio, and the method of heating, stirring, ultrasonic irradiation or the like is used. It was dissolved, prepared as a solution, and applied to a transparent electrode. In this case, by mixing two or more kinds of solvents and using them, the photoelectric conversion efficiency of the photovoltaic element can also be improved. As described above, the structure in which the electron-donating organic material and the electron-accepting organic material are separated by the nanometer size is suitable for improving the conversion efficiency, and thus such a phase-separated structure can be formed by a solvent. The solvent to be combined in such a case can be selected according to the kind of the electron-donating organic material and the electron-accepting organic material to be used. In the case of using an electron-donating organic material containing a structural unit represented by the formula (1), preferred examples of the combination include chloroform and chlorobenzene in the above. In this case, the mixing volume ratio of each solvent is preferably in the range of chloroform:chlorobenzene = 5:95 to 95:5, and further preferably in the range of 10:90 to 90:10.
又，積層含有通式(1)所表示的結構單元之電子供給性有機材料及電子接受性有機材料而形成有機半導體層之情形，例如於塗布電子供給性有機材料之溶液而形成具有電子供給性有機材料的層後，塗布電子接受性有機材料溶液而形成層。於此，電子供給性有機材料及電子接受性有機材料溶液係於分子量為1,000以下左右的低分子量物之情形下，也能夠利用蒸鍍法而形成層。 Further, when an electron-donating organic material and an electron-accepting organic material having a structural unit represented by the general formula (1) are laminated to form an organic semiconductor layer, for example, a solution of an electron-donating organic material is applied to form an electron supply property. After the layer of the organic material, a solution of the electron-accepting organic material is applied to form a layer. Here, in the case where the electron-donating organic material and the electron-accepting organic material solution are in a low molecular weight product having a molecular weight of about 1,000 or less, a layer can be formed by a vapor deposition method.
於有機半導體層之形成中，可利用旋轉塗布、刮刀塗布、狹縫塗布、網板印刷塗布、桿塗布、澆鑄塗布、印刷轉印法、浸漬提高法、噴墨法、噴霧法、 真空蒸餾法等之中任一種方法，若按照膜厚控制或定向控制等所欲獲得的有機半導體層特性而選擇形成之方法的話即可。例如，於進行旋轉塗布之情形下，含有通式(1)所表示的結構單元之電子供給性有機材料及電子接受性有機材料較佳為1至20g/l之濃度(相對於包含具有通式(1)所表示的結構之電子供給性有機材料、電子接受性有機材料與溶劑之溶液體積而言，具有通式(1)所表示的結構之電子供給性有機材料與電子接受性有機材料之重量)，藉由作成該濃度，能夠容易地獲得厚度5至200nm之均質的有機半導體層。 In the formation of the organic semiconductor layer, spin coating, doctor blade coating, slit coating, screen printing coating, rod coating, casting coating, printing transfer method, immersion enhancement method, inkjet method, spray method, Any of the vacuum distillation methods and the like may be selected in accordance with the characteristics of the organic semiconductor layer to be obtained by film thickness control or orientation control. For example, in the case of spin coating, the electron-donating organic material and the electron-accepting organic material containing the structural unit represented by the general formula (1) are preferably in a concentration of from 1 to 20 g/l (relative to the inclusion of the general formula) (1) The electron-donating organic material having the structure represented by the general formula (1) and the electron-accepting organic material in the solution volume of the electron-donating organic material, the electron-accepting organic material, and the solvent represented by the structure. By making this concentration, a homogeneous organic semiconductor layer having a thickness of 5 to 200 nm can be easily obtained.
對於所形成的有機半導體層而言，為了去除溶劑，亦可於減壓下或惰性氣體環境中(氮或氬氣體環境中)等進行退火處理。退火處理之較佳溫度為40℃至300℃，更佳為50℃至200℃。又，藉由進行施加熱之退火處理，所積層的層將在界面相互滲透，所接觸的實施面積將會增加，能夠使短路電流增大。該退火處理亦可於負極形成後進行。 The organic semiconductor layer to be formed may be annealed under reduced pressure or in an inert gas atmosphere (in a nitrogen or argon atmosphere) or the like in order to remove the solvent. The annealing temperature is preferably from 40 ° C to 300 ° C, more preferably from 50 ° C to 200 ° C. Further, by performing annealing treatment by applying heat, the layers of the layers will penetrate each other at the interface, and the area of contact to be contacted will increase, and the short-circuit current can be increased. This annealing treatment can also be carried out after the formation of the negative electrode.
接著，藉由真空蒸鍍法或濺鍍法而在有機半導體層上形成Al等之金屬電極(此情形下，相當於負極)。較佳為使用低分子有機材料而真空蒸鍍至電子輸送層之情形，接著，持續保持真空狀態下而形成。 Next, a metal electrode such as Al (in this case, a negative electrode) is formed on the organic semiconductor layer by a vacuum deposition method or a sputtering method. It is preferably a case where a low molecular organic material is vacuum-deposited to the electron transport layer, and then formed under a continuous vacuum state.
於將電洞輸送層設置於正極與有機半導體層之間之情形下，利用旋轉塗布法、桿塗布法、藉刮刀所進行的澆鑄法等，在正極上塗布所要之p型有機半導體材料(PEDOT等)後，利用真空恆溫槽或熱板等而去除溶 劑，形成電洞輸送層。於使用酞青素衍生物或紫質衍生物等低分子有機材料之情形下，採取利用真空蒸鍍機之真空蒸鍍法也為可能。 When the hole transport layer is provided between the positive electrode and the organic semiconductor layer, the desired p-type organic semiconductor material (PEDOT) is coated on the positive electrode by a spin coating method, a rod coating method, a casting method by a doctor blade, or the like. After the), the solution is removed by vacuum oven or hot plate. The agent forms a hole transport layer. In the case of using a low molecular organic material such as an anthraquinone derivative or a purple derivative, a vacuum vapor deposition method using a vacuum vapor deposition machine is also possible.
在有機半導體層與負極之間設置電子輸送層之情形下，利用旋轉塗布法、桿塗布法、藉刮刀所進行的澆鑄法、噴霧法等，在有機半導體層上塗布所要之n型有機半導體材料(富勒烯衍生物等)、n型無機半導體材料(氧化鈦凝膠等)後，利用真空恆溫槽或熱板等而去除溶劑，形成電子輸送層。於使用啡啉衍生物或C60等之低分子有機材料之情形下，採取利用真空蒸鍍機之真空蒸鍍法也為可能。 When an electron transport layer is provided between the organic semiconductor layer and the negative electrode, the desired n-type organic semiconductor material is coated on the organic semiconductor layer by a spin coating method, a rod coating method, a casting method by a doctor blade, a spray method, or the like. After the (fullerene derivative or the like) or the n-type inorganic semiconductor material (such as a titanium oxide gel), the solvent is removed by a vacuum oven or a hot plate to form an electron transport layer. In the case of using a phenanthroline derivative or a low molecular organic material such as C 60 , it is also possible to employ a vacuum evaporation method using a vacuum vapor deposition machine.
本發明之光伏元件能夠應用於利用光電轉換功能、光整流功能等之各種光電轉換元件。例如，有用於光電池(太陽能電池等)、電子元件(光感測器、光切換器、光電晶體等)、光記錄材(光記憶體等)等。 The photovoltaic element of the present invention can be applied to various photoelectric conversion elements using a photoelectric conversion function, an optical rectification function, and the like. For example, it can be used for a photovoltaic cell (such as a solar cell), an electronic component (photosensor, an optical switch, a photoelectric crystal, etc.), an optical recording material (optical memory, etc.), or the like.
以下，根據實施例而進一步具體說明本發明。還有，本發明並不受下列實施例所限定。又，在實施例等所用之化合物中，針對使用縮寫者，顯示如下。 Hereinafter, the present invention will be further specifically described based on examples. Also, the present invention is not limited by the following examples. Further, among the compounds used in the examples and the like, the following is shown for the use of the abbreviations.
ITO：銦錫氧化物 ITO: indium tin oxide
PEDOT：聚伸乙二氧基噻吩 PEDOT: Poly(ethylenedioxythiophene)
PSS：聚苯乙烯磺酸酯 PSS: polystyrene sulfonate
PC70BM：苯基C71丁酸甲酯 PC 70 BM: phenyl C71 butyrate
Eg：能帶間隙 Eg: can have gap
HOMO：最高佔據分子軌域 HOMO: the highest occupied molecular orbital
ISC：短路電流密度 I SC : short circuit current density
VOC：釋放電壓 V OC : release voltage
FF：填充因子 FF: fill factor
η：光電轉換效率 η: photoelectric conversion efficiency
還有，於1H-NMR測定中，利用FT-NMR裝置(日本電子股份有限公司製JEOL JNM-EX270)。 Further, in the 1 H-NMR measurement, an FT-NMR apparatus (JEOL JNM-EX270 manufactured by JEOL Ltd.) was used.
又，平均分子量(數量平均分子量、重量平均分子量)係利用GPC裝置(輸送氯仿之TOSOH公司製、高速GPC裝置HLC-8320GPC)，依照使用聚苯乙烯標準試料之絕對檢量線法而算出。聚合度n係以下式所算出。 In addition, the average molecular weight (amount of the average molecular weight, the weight average molecular weight) was calculated by an absolute calibration line method using a polystyrene standard sample by a GPC apparatus (a high-speed GPC apparatus HLC-8320GPC manufactured by TOSOH Co., Ltd.). The degree of polymerization n is calculated by the following formula.
聚合度n=[(重量平均分子量)/(重複單元之分子量(計算值))] Degree of polymerization n = [(weight average molecular weight) / (molecular weight of the repeating unit (calculated value))]
又，能帶間隙(Eg)係依照下式而從光吸收端波長所算出。還有，光吸收端波長係針對將氯仿用於溶劑，利用旋轉塗布法，在玻璃上形成約60nm厚之薄膜，從利用日立製作所製股份有限公司製之U-3010型分光光度計所測出的薄膜之紫外線可見光吸收光譜(測定波長範圍：300至900nm)所獲得。 Further, the band gap (Eg) is calculated from the wavelength of the light absorption end in accordance with the following formula. In addition, the light absorption end wavelength is a film of about 60 nm thick formed on the glass by a spin coating method, and the wavelength of the light absorption end is measured by a U-3010 spectrophotometer manufactured by Hitachi, Ltd. The ultraviolet visible light absorption spectrum of the film (measuring wavelength range: 300 to 900 nm) was obtained.
Eg(eV)=1240/薄膜之光吸收端波長(nm) Eg(eV)=1240/length of light absorption end of film (nm)
還有，電子供給性有機材料或電子接受性有機材料(p型半導體特性或n型半導體特性)係藉由FET測定或能量準位測定上述薄膜而能夠特定。 Further, the electron-donating organic material or the electron-accepting organic material (p-type semiconductor property or n-type semiconductor property) can be specified by measuring the film by FET measurement or energy level.
合成例1 Synthesis Example 1
利用顯示於式1之方法而合成化合物A-1。還有，式1記載之化合物(1-g)係參考Advanced Functional Materials、2011年、21卷、718-728頁所記載的方法而合成。 Compound A-1 was synthesized by the method shown in Formula 1. Further, the compound (1-g) described in Formula 1 is referred to Advanced Functional. Synthesized by the methods described in Materials, 2011, Vol. 21, pp. 718-728.
於噻吩二羧酸(Frontier Scientific公司製)4.5g(26.1mmol)之乙酸溶液50ml中，慢慢地添加溴25g(156mmol)，在室溫下攪拌1小時、在60℃下攪拌6小時。於攪拌結束後，直到反應液顏色消失為止，將飽和硫代硫酸鈉水溶液慢慢地添加於反應液中，在0℃下放置12小時。過濾所析出的固體後，藉由以丙酮/水進行再結晶而獲得白色固體之化合物(1-b)5.7g(產率66%)。以下，顯示化合物(1-b)之13C-NMR的測定結果。 To 50 ml of a 4.5 g (26.1 mmol) acetic acid solution of thiophene dicarboxylic acid (manufactured by Frontier Scientific Co., Ltd.), 25 g (156 mmol) of bromine was gradually added thereto, and the mixture was stirred at room temperature for 1 hour and at 60 ° C for 6 hours. After the completion of the stirring, the saturated aqueous sodium thiosulfate solution was gradually added to the reaction liquid until the color of the reaction liquid disappeared, and the mixture was allowed to stand at 0 ° C for 12 hours. After the precipitated solid was filtered, 5.7 g (yield: 66%) of Compound (1-b) of white solid was obtained by recrystallization from acetone/water. The measurement results of 13 C-NMR of the compound (1-b) are shown below.
13C-NMR(67.5MHz、DMSO-d6)：162.46,135.11,114.39ppm。 13 C-NMR (67.5 MHz, DMSO-d 6 ): 162.46, 135.11, 114.39.
將乙酸酐(和光純藥工業股份有限公司製)80ml添加於上述化合物(1-b)4.9g(14.9mmol)中，加熱回流6小時。藉由減壓蒸餾反應液後，利用己烷洗淨所析出的固體、使其乾燥而獲得白色固體之化合物(1-c)3.4g(產率74%)。以下，顯示化合物(1-c)之13C-NMR的測定結果。 80 ml of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 4.9 g (14.9 mmol) of the above compound (1-b), and the mixture was heated under reflux for 6 hours. After the reaction liquid was distilled under reduced pressure, the precipitated solid was washed with hexane and dried to give 3.4 g (yield: 74%) of Compound (1-c) as a white solid. The measurement results of 13 C-NMR of the compound (1-c) are shown below.
13C-NMR(67.5MHz、CDCl3)：153.78,133.66,116.99ppm。 13 C-NMR (67.5 MHz, CDCl 3 ): 153.78, 133.66, 116.99.
在室溫下，於鄰甲苯胺(東京化成工業股份有限公司製)343mg(3.2mmol)之二甲基甲醯胺溶液(15ml)中添加上述化合物(1-c)936mg(3.0mmol)，在70℃下攪拌3小時。於反應結束後，減壓蒸餾溶劑而獲得白色固體之化合物(1-e)1.3g(粗精製物)。化合物(1-e)係直接用於下列反應。以下，顯示化合物(1-e)之1H-NMR的測定結果。 The above compound (1-c) 936 mg (3.0 mmol) was added to a solution of 343 mg (3.2 mmol) of dimethylformamide (15 ml) of o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature. Stir at 70 ° C for 3 hours. After the completion of the reaction, the solvent was evaporated under reduced pressure to give Compound (1-e) (yield: 1.3 g). The compound (1-e) was used directly in the following reaction. The measurement results of 1 H-NMR of the compound (1-e) are shown below.
1H-NMR(270MHz、DMSO-d6)：9.96(s,1H),7.40(d,J=8.4Hz,1H),7.25-7.11(m,3H),2.28(s,3H)ppm。 1 H-NMR (270 MHz, DMSO-d 6 ): 9.96 (s, 1 H), 7.40 (d, J = 8.4 Hz, 1H), 7.25-7.11 (m, 3H), 2.28 (s, 3H) ppm.
於80℃下，將乙酸鈉(和光純藥工業股份有限公司製)800mg添加於上述化合物(1-e)1.3g之乙酸酐溶液(20ml)中，攪拌5小時。將反應液慢慢地注入甲醇(200ml)中，暫時在室溫下攪拌後，減壓蒸餾溶劑。藉由利用矽膠管柱層析儀(氯仿洗提液)精製而獲得白色固體之化合物(1-f)960mg(產率80%)。以下，顯示化合物(1-f)之1H-NMR及13C-NMR的測定結果。 800 mg of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 1.3 g of the above-mentioned compound (1-e) in an acetic anhydride solution (20 ml) at 80 ° C, and the mixture was stirred for 5 hours. The reaction solution was slowly poured into methanol (200 ml), and the mixture was stirred at room temperature for a while, and then the solvent was evaporated under reduced pressure. The compound (1-f) 960 mg (yield 80%) obtained as a white solid was purified by using a silica gel column chromatography (chloroform elution). The measurement results of 1 H-NMR and 13 C-NMR of the compound (1-f) are shown below.
1H-NMR(270MHz、CDCl3)：7.4-7.3(m,3H),7.14(d,J=7.6Hz,1H),2.21(s,3H)ppm。 1 H-NMR (270 MHz, CDCl 3 ): 7.4-7.3 (m, 3H), 7.14 (d, J = 7.6 Hz, 1H), 2.21. (s, 3H) ppm.
13C-NMR(67.5MHz、CDCl3)：159.09,136.65,134.32,131.1,130.33,129.5,128.2,126.8,113.95,18.01ppm。 13 C-NMR (67.5 MHz, CDCl 3 ): 159.09, 136.65, 134.32, 131.1, 130.33, 129.5, 128.2, 126.8, 113.95, 18.01 ppm.
使上述化合物60mg(0.15mmol)及化合物(1-g)115mg(0.15mmol)溶解於甲苯(和光純藥工業股份有限公司製)10ml中之後，再添加三(二亞苄基丙酮)二鈀(東京化成工業股份有限公司製)4mg、三(2-甲基苯基)膦(東京化成工業股份有限公司製)7mg，於氮氣環境中，在100℃下攪拌12小時。接著，添加溴苯(東京化成工業股份有限公司製)10mg，在100℃下攪拌1小時。接著，添加三丁基(2-噻吩基)錫(東京化成工業股份有限公司製)40mg，在100℃下進一步攪拌1小時。於攪拌結束後，將反應混合物冷卻至室溫，注入甲醇100ml中。過濾所析出的固體，依照甲醇、水、丙酮之順序洗淨。接著，利用索氏(Soxhlet)萃取器，依照丙酮、己烷之順序洗淨。接著，使所獲得的固體溶解於氯仿中，通入矽藻土(Nakarai Tesc股份有限公司製)，接著於通入矽膠管柱(洗提液：氯仿)後，減壓蒸餾溶劑。使所得之固體再度溶解於氯仿中之後，於甲醇中再沉澱而獲得化合物A-1(84mg)。重量平均分子量為29,800、數量平均分子量為14,200、聚合度n為43。又，光吸收端波長為680nm、能帶間隙(Eg)為1.82eV、最高佔據分子軌域(HOMO)準位為-5.34eV。 60 mg (0.15 mmol) of the above compound and 115 mg (0.15 mmol) of the compound (1-g) were dissolved in 10 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), followed by the addition of tris(dibenzylideneacetone)dipalladium ( 7 mg of 3 mg of tris(2-methylphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 100 ° C for 12 hours in a nitrogen atmosphere. Then, 10 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C for 1 hour. Then, 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 the completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was filtered and washed in the order of methanol, water and acetone. Next, it was washed in the order of acetone and hexane by a Soxhlet extractor. Then, the obtained solid was dissolved in chloroform, passed through diatomaceous earth (manufactured by Nakarai Tesc Co., Ltd.), and then passed through a gel column (eluent: chloroform), and then the solvent was distilled under reduced pressure. The obtained solid was dissolved again in chloroform, and then reprecipitated in methanol to give Compound A-1 (84 mg). The weight average molecular weight was 29,800, the number average molecular weight was 14,200, and the degree of polymerization n was 43. Further, the light absorption end wavelength was 680 nm, the energy band gap (Eg) was 1.82 eV, and the highest occupied molecular orbital (HOMO) level was -5.34 eV.
合成例2 Synthesis Example 2
利用顯示於式2之方法而合成化合物A-2。 Compound A-2 was synthesized by the method shown in Formula 2.
在室溫下，將上述化合物(1-c)936mg(3.0mmol)加入4-氟-2-甲基苯胺(Aldrich公司製)400mg(3.2mmol)之二甲基甲醯胺溶液(15ml)中，在70℃下攪拌3小時。於反應結束後，減壓蒸餾溶劑而獲得白色固體之化合物(2-b)1.3g(粗精製物)。化合物(2-b)係直接用於下列反應。以下，顯示化合物(2-b)之1H-NMR的測定結果。 936 mg (3.0 mmol) of the above compound (1-c) was added to a solution of 400 mg (3.2 mmol) of dimethylformamide (15 ml) of 4-fluoro-2-methylaniline (manufactured by Aldrich) at room temperature. Stir at 70 ° C for 3 hours. After the completion of the reaction, the solvent was evaporated under reduced pressure to give Compound (2-b) (yel. The compound (2-b) was used directly in the following reaction. The measurement results of 1 H-NMR of the compound (2-b) are shown below.
1H-NMR(270MHz、DMSO-d6)：7.28(m,2H),6.95(dd,J=8.6Hz,2.7Hz,1H),2.25(s,3H)ppm。 1 H-NMR (270 MHz, DMSO-d 6 ): 7.28 (m, 2H), 6.95 (dd, J = 8.6 Hz, 2.7 Hz, 1H), 2.25 (s, 3H) ppm.
於80℃下，將乙酸鈉(和光純藥工業股份有限公司製)800mg添加於上述化合物(2-b)1.3g之乙酸酐溶液(20ml)中，攪拌5小時。將反應液慢慢地注入甲醇(200ml)中，暫時在室溫下攪拌後，減壓蒸餾溶劑。藉由利用矽膠管柱層析儀(氯仿洗提液)精製而獲得白色固體之化合物(2-c)875mg(產率70%)。以下，顯示化合物(2-c)之1H-NMR的測定結果。 800 mg of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 1.3 g of the above-mentioned compound (2-b) in an acetic anhydride solution (20 ml) at 80 ° C, and the mixture was stirred for 5 hours. The reaction solution was slowly poured into methanol (200 ml), and the mixture was stirred at room temperature for a while, and then the solvent was evaporated under reduced pressure. The compound (2-c) 875 mg (yield 70%) obtained as a white solid was purified by using a silica gel column chromatography (chloroform elution). The measurement results of 1 H-NMR of the compound (2-c) are shown below.
1H-NMR(270MHz、CDCl3)：7.31(m,1H),7.10(m,1H),6.90(d,J=8.6Hz,1H),2.17(s,3H)ppm。 1 H-NMR (270 MHz, CDCl 3 ): 7.31 (m, 1H), 7.10 (m, 1H), 6.90 (d, J = 8.6 Hz, 1H), 2.17 (s, 3H) ppm.
使上述化合物(2-c)63mg(0.15mmol)及化合物(1-g)115mg(0.15mmol)溶解於甲苯(和光純藥工業股份有限公司製)10ml中之後，再添加三(二亞苄基丙酮)二鈀(東京化成工業股份有限公司製)4mg、三(2-甲基苯基)膦(東京化成工業股份有限公司製)7mg，於氮氣環境中，在100℃下攪拌12小時。接著，添加溴苯(東京化成工業股份有限公司製)10mg，在100℃下攪拌1小時。接著，添加三丁基(2-并二噻吩)錫(東京化成工業股份有限公司製)40mg，在100℃下進一步攪拌1小時。於攪拌結束後，將反應混合物冷卻至室溫，注入甲醇100ml中。過濾所析出的固體，依照甲醇、水、丙酮之順序洗淨。接著，利用索氏萃取器，依照丙酮、己烷之順序洗淨。接著，使所獲得的固體溶解於氯仿中，通入矽藻土(Nakarai Tesc股份有限公司製)，接著於通入矽膠管柱(洗提液：氯仿)後，減壓蒸餾溶劑。使所得之固體再度溶解於氯仿中之後，於甲醇中再沉澱而獲得化合物A-2(79mg)。重量平均分子量為42,800、數量平均分子量為21,200、聚合度n為61。又，光吸收端波長為680nm、能帶間隙(Eg)為1.82eV、最高佔據分子軌域(HOMO)準位為-5.41eV。 After dissolving 63 mg (0.15 mmol) of the above compound (2-c) and 115 mg (0.15 mmol) of the compound (1-g) in 10 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), tris(dibenzylidene) was further added. Acetone) 2 mg of palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7 mg of tris(2-methylphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C for 12 hours under a nitrogen atmosphere. Then, 10 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C for 1 hour. Then, 40 mg of tributyl(2-dithiophene) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C for 1 hour. After the completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was filtered and washed in the order of methanol, water and acetone. Then, it was washed in the order of acetone and hexane by a Soxhlet extractor. Then, the obtained solid was dissolved in chloroform, passed through diatomaceous earth (manufactured by Nakarai Tesc Co., Ltd.), and then passed through a gel column (eluent: chloroform), and then the solvent was distilled under reduced pressure. The obtained solid was dissolved again in chloroform, and then reprecipitated in methanol to give Compound A-2 (79 mg). The weight average molecular weight was 42,800, the number average molecular weight was 21,200, and the degree of polymerization n was 61. Further, the light absorption end wavelength was 680 nm, the energy band gap (Eg) was 1.82 eV, and the highest occupied molecular orbital (HOMO) level was -5.41 eV.
合成例3 Synthesis Example 3
利用顯示於式3之方法而合成化合物A-3。 Compound A-3 was synthesized by the method shown in Formula 3.
在室溫下，將上述化合物(1-c)624mg(2.0mmol)加入2-胺三氟甲苯(東京化成工業股份有限公司製)338mg(2.1mmol)之二甲基甲醯胺溶液(10ml)中，在70℃下攪拌3小時。於反應結束後，減壓蒸餾溶劑而獲得白色固體之化合物(3-b)950mg(粗精製物)。化合物(3-b)係直接用於下列反應。 624 mg (2.0 mmol) of the above-mentioned compound (1-c) was added to 238 mg (2.1 mmol) of dimethylformamide solution (10 ml) of 2-amine benzotrifluoride (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature. The mixture was stirred at 70 ° C for 3 hours. After the completion of the reaction, the solvent was evaporated under reduced pressure to give Compound (3-b) 950 (yield of crude product) as a white solid. The compound (3-b) was used directly in the following reaction.
於80℃下，將乙酸鈉(和光純藥工業股份有限公司製)500mg添加於上述化合物(3-b)950mg之乙酸酐溶液(10ml)中，攪拌5小時。將反應液慢慢地注入甲醇(100ml)中，暫時在室溫下攪拌後，減壓蒸餾溶劑。藉由利用矽膠管柱層析儀(氯仿洗提液)精製而獲得白色固體之化合物(3-c)592mg(產率65%)。以下，顯示化合物(3-c)之1H-NMR的測定結果。 500 mg of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 950 mg of the above compound (3-b) in an acetic anhydride solution (10 ml) at 80 ° C, and the mixture was stirred for 5 hours. The reaction solution was slowly poured into methanol (100 ml), and the mixture was stirred at room temperature for a while, and then the solvent was evaporated under reduced pressure. The compound (3-c) 592 mg (yield 65%) was obtained as a white solid by purification using a silica gel column chromatography (chloroform elution). The measurement results of 1 H-NMR of the compound (3-c) are shown below.
1H-NMR(270MHz、CDCl3)：7.83(d,J=7.6Hz,1H),7.68(m,2H),7.31(d,J=7.6Hz,1H)ppm。 1 H-NMR (270 MHz, CDCl 3 ): 7.83 (d, J = 7.6 Hz, 1H), 7.68 (m, 2H), 7.31 (d, J = 7.6 Hz, 1H) ppm.
使上述化合物(3-c)68mg(0.15mmol)及化合物(1-g)115mg(0.15mmol)溶解於甲苯(和光純藥工業股份有限公司製)10ml中之後，再添加三(二亞苄基丙酮)二鈀(東京化成工業股份有限公司製)4mg、三(2-甲基苯基)膦(東京化成工業股份有限公司製)7mg，於氮氣環境中，在100℃下攪拌12小時。接著，添加溴苯(東京化成工業股份有限公司製)10mg，在100℃下攪拌1小時。接著，添加三丁基(2-并二噻吩)錫(東京化成工業股份有限公司製)40mg，在100℃下進一步攪拌1小時。於攪拌結束後，將反應混合物冷卻至室溫，注入甲醇100ml中。過濾所析出的固體，依照甲醇、水、丙酮之順序洗淨。接著，利用索氏萃取器，依照丙酮、己烷之順序洗淨。接著，使所獲得的固體溶解於氯仿中，通入矽藻土(Nakarai Tesc股份有限公司製)，接著於通入矽膠管柱(洗提液：氯仿)後，減壓蒸餾溶劑。使所得之固體再度溶解於氯仿中之後，於甲醇中再沉澱而獲得化合物A-3(80mg)。重量平均分子量為34,100、數量平均分子量為12,200、聚合度n為46。又，光吸收端波長為672nm、能帶間隙(Eg)為1.85eV、最高佔據分子軌域(HOMO)準位為-5.46eV。 After dissolving 68 mg (0.15 mmol) of the above compound (3-c) and 115 mg (0.15 mmol) of the compound (1-g) in 10 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), tris(dibenzylidene) was further added. Acetone) 2 mg of palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7 mg of tris(2-methylphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C for 12 hours under a nitrogen atmosphere. Then, 10 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C for 1 hour. Then, 40 mg of tributyl(2-dithiophene) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C for 1 hour. After the completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was filtered and washed in the order of methanol, water and acetone. Then, it was washed in the order of acetone and hexane by a Soxhlet extractor. Then, the obtained solid was dissolved in chloroform, passed through diatomaceous earth (manufactured by Nakarai Tesc Co., Ltd.), and then passed through a gel column (eluent: chloroform), and then the solvent was distilled under reduced pressure. The obtained solid was dissolved again in chloroform, and then reprecipitated in methanol to give Compound A-3 (80 mg). The weight average molecular weight was 34,100, the number average molecular weight was 12,200, and the degree of polymerization n was 46. Further, the light absorption end wavelength was 672 nm, the energy band gap (Eg) was 1.85 eV, and the highest occupied molecular orbital (HOMO) level was -5.66 eV.
合成例4 Synthesis Example 4
利用顯示於式4之方法而合成化合物A-4。還有，式4記載之化合物(4-d)係參考Macromolecules、2007年、40卷、1981-1986頁所記載的方法而合成。 Compound A-4 was synthesized by the method shown in Formula 4. Further, the compound (4-d) described in Formula 4 is synthesized by the method described in Macromolecules, 2007, Vol. 40, pp. 1981-1986.
在室溫下，將上述化合物(1-c)624mg(2.0mmol)加入4-氟苯胺(東京化成工業股份有限公司製)233mg(2.1mmol)之二甲基甲醯胺溶液(10ml)中，在70℃下攪拌3小時。於反應結束後，減壓蒸餾溶劑而獲得白色固體之化合物(4-b)850mg(粗精製物)。化合物(4-b)係直接用於下列反應。 624 mg (2.0 mmol) of the above compound (1-c) was added to a solution of 233 mg (2.1 mmol) of dimethylformamide (10 ml) of 4-fluoroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature. Stir at 70 ° C for 3 hours. After the completion of the reaction, the solvent was evaporated under reduced pressure to give Compound (4-b) 850 (yield of crude material) as white solid. The compound (4-b) was used directly in the following reaction.
於80℃下，將乙酸鈉(和光純藥工業股份有限公司製)400mg添加於上述化合物(4-b)850mg之乙酸酐溶液(10ml)中，攪拌5小時。將反應液慢慢地注入甲醇(100ml)中，暫時在室溫下攪拌後，減壓蒸餾溶劑。藉由利用矽膠管柱層析儀(氯仿洗提液)精製而獲得白色固體之化合物(4-c)570mg(產率70%)。以下，顯示化合物(4-c)之1H-NMR的測定結果。 400 mg of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 850 mg of the above compound (4-b) in an acetic anhydride solution (10 ml) at 80 ° C, and the mixture was stirred for 5 hours. The reaction solution was slowly poured into methanol (100 ml), and the mixture was stirred at room temperature for a while, and then the solvent was evaporated under reduced pressure. The compound (4-c) 570 mg (yield 70%) was obtained as a white solid (yield: EtOAc). The measurement results of 1 H-NMR of the compound (4-c) are shown below.
1H-NMR(270MHz、CDCl3)：7.35(m,1H),7.18(m,1H),1.55(s,3H)ppm。 1 H-NMR (270 MHz, CDCl 3 ): 7.35 (m, 1H), 7.18 (m, 1H), 1.55 (s, 3H) ppm.
使上述化合物(4-c)61mg(0.15mmol)及化合物(4-d)109mg(0.15mmol)溶解於甲苯(和光純藥工業股份有限公司製)5ml中之後，再添加三(二亞苄基丙酮)二鈀(東京化成工業股份有限公司製)4mg、三(2-甲基苯基)膦(東京化成工業股份有限公司製)7mg，於氮氣環境中，在100℃下攪拌12小時。接著，添加溴苯(東京化成工業股份有限公司製)10mg，在100℃下攪拌1小時。接著，添加三丁基(2-并二噻吩)錫(東京化成工業股份有限公司製)40mg，在100℃下進一步攪拌1小時。於攪拌結束後，將反應混合物冷卻至室溫，注入甲醇100ml中。過濾所析出的固體，依照甲醇、水、丙酮之順序洗淨。接著，利用索氏萃取器，依照丙酮、己烷之順序洗淨。接著，使所獲得的固體溶解於氯仿中，通入矽藻土(Nakarai Tesc股份有限公司製)，接著於通入矽膠管柱(洗提液：氯仿)後，減壓蒸餾溶劑。使所得之固體再度溶解於氯仿中之後，於甲醇中再沉澱而獲得化合物A-4(68mg)。重量平均分子量為32,000、數量平均分子量為12,200、聚合度n為50。又，光吸收端波長為739nm、能帶間隙(Eg)為1.68eV、最高佔據分子軌域(HOMO)準位為-5.49eV。 After dissolving 61 mg (0.15 mmol) of the compound (4-c) and 109 mg (0.15 mmol) of the compound (4-d) in 5 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), tris(dibenzylidene) was further added. Acetone) 2 mg of palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7 mg of tris(2-methylphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C for 12 hours under a nitrogen atmosphere. Then, 10 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C for 1 hour. Then, 40 mg of tributyl(2-dithiophene) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C for 1 hour. After the completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was filtered and washed in the order of methanol, water and acetone. Then, it was washed in the order of acetone and hexane by a Soxhlet extractor. Then, the obtained solid was dissolved in chloroform, passed through diatomaceous earth (manufactured by Nakarai Tesc Co., Ltd.), and then passed through a gel column (eluent: chloroform), and then the solvent was distilled under reduced pressure. The obtained solid was dissolved again in chloroform, and then reprecipitated in methanol to give Compound A-4 (68 mg). The weight average molecular weight was 32,000, the number average molecular weight was 12,200, and the degree of polymerization n was 50. Further, the light absorption end wavelength was 739 nm, the energy band gap (Eg) was 1.68 eV, and the highest occupied molecular orbital (HOMO) level was -5.49 eV.
合成例5 Synthesis Example 5
利用顯示於式5之方法而合成化合物B-1。還有，式5記載之化合物(5-a)係參考Advanced Functional Materials、2011年、21卷、71-728頁所記載的方法而合成。 Compound B-1 was synthesized by the method shown in Formula 5. Further, the compound (5-a) described in Formula 5 is synthesized by referring to the methods described in Advanced Functional Materials, 2011, Vol. 21, and 71-728.
使上述化合物(5-a)63mg(0.15mmol)及化合物(1-g)116mg(0.15mmol)溶解於甲苯(和光純藥工業股份有限公司製)10ml中之後，再添加三(二亞苄基丙酮)二鈀(東京化成工業股份有限公司製)4mg、三(2-甲基苯基)膦(東京化成工業股份有限公司製)7mg，於氮氣環境中，在100℃下攪拌12小時。接著，添加溴苯(東京化成工業股份有限公司製)10mg，在100℃下攪拌1小時。接著，添加三丁基(2-并二噻吩)錫(東京化成工業股份有限公司製)40mg，在100℃下進一步攪拌1小時。於攪拌結束後，將反應混合物冷卻至室溫，注入甲醇100ml中。過濾所析出的固體，依照甲醇、水、丙酮之順序洗淨。接著，利用索氏萃取器，依照丙酮、己烷之順序洗淨。接著，使所獲得的固體溶解於氯仿中，通入矽藻土(Nakarai Tesc股份有限公司製)，接著於通入矽膠管柱(洗提液：氯仿)後，減壓蒸餾溶劑。使所得之固體再度溶解於氯仿中之後，於甲醇中再沉澱而獲得化合物B-1(79mg)。重量平均分子量為65,000、數量平均分子量為26,100、聚合度n為91。又，光吸收端波長為670nm、 能帶間隙(Eg)為1.85eV、最高佔據分子軌域(HOMO)準位為-5.23eV。 After dissolving 63 mg (0.15 mmol) of the compound (5-a) and 116 mg (0.15 mmol) of the compound (1-g) in 10 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), tris(dibenzylidene) was further added. Acetone) 2 mg of palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7 mg of tris(2-methylphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C for 12 hours under a nitrogen atmosphere. Then, 10 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C for 1 hour. Then, 40 mg of tributyl(2-dithiophene) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C for 1 hour. After the completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was filtered and washed in the order of methanol, water and acetone. Then, it was washed in the order of acetone and hexane by a Soxhlet extractor. Then, the obtained solid was dissolved in chloroform, passed through diatomaceous earth (manufactured by Nakarai Tesc Co., Ltd.), and then passed through a gel column (eluent: chloroform), and then the solvent was distilled under reduced pressure. The obtained solid was dissolved again in chloroform, and then reprecipitated in methanol to give Compound B-1 (79 mg). The weight average molecular weight was 65,000, the number average molecular weight was 26,100, and the degree of polymerization n was 91. Moreover, the wavelength of the light absorption end is 670 nm, The band gap (Eg) is 1.85 eV and the highest occupied molecular orbital (HOMO) level is -5.23 eV.
合成例6 Synthesis Example 6
利用顯示於式6之方法而合成化合物B-2。還有，式6記載之化合物(6-a)係參考Advanced Functional Materials、2011年、21卷、71-728頁所記載的方法而合成。 Compound B-2 was synthesized by the method shown in Formula 6. Further, the compound (6-a) described in Formula 6 is synthesized by referring to the methods described in Advanced Functional Materials, 2011, Vol. 21, and 71-728.
將二氯雙(三苯基膦)鈀觸媒(東京化成工業股份有限公司製)100mg加入上述化合物(6-a)1.18g(2.0mmol)及三丁基(2-并二噻吩)錫(東京化成工業股份有限公司製)2.2g(6.0mmol)之甲苯/二甲基甲醯胺溶液(50ml/10ml)中，在氮氣中回流8小時。將反應液冷卻至室溫後，添加水50ml，洗淨有機層係分別利用水洗淨2次、接著利用飽和食鹽水洗淨1次。利用無水硫酸鎂， 於使溶劑乾燥後，並過濾而減壓蒸餾溶劑。藉由利用矽膠管柱層析儀(洗提液、己烷：乙酸乙酯=20：1)精製而獲得黃色固體(900mg、產率75%)之化合物(6-b)。以下，顯示化合物(6-b)之1H-NMR的測定結果。 100 mg of dichlorobis(triphenylphosphine)palladium catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the above compound (6-a) 1.18 g (2.0 mmol) and tributyl(2-dithiophene) tin ( 2.2 g (6.0 mmol) of a toluene/dimethylformamide solution (50 ml/10 ml) of Tokyo Chemical Industry Co., Ltd. was refluxed for 8 hours under nitrogen. After cooling the reaction liquid to room temperature, 50 ml of water was added, and the organic layer was washed and washed twice with water, and then washed once with saturated brine. After the solvent was dried using anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The compound (6-b) was obtained as a yellow solid (900 mg, yield: 75%) by using a silica gel column chromatography (eluent, hexane: ethyl acetate = 20:1). The measurement results of 1 H-NMR of the compound (6-b) are shown below.
1H-NMR(270MHz、CDCl3)：8.02(d,J=3.4Hz,2H),7.43(d,J=3.4Hz,2H),7.12(t,J=7.3Hz,2H),3.55(d,J=7.3Hz,2H),1.89(brs,1H),1.4-1.2(m,34H),0.86(m,6H)ppm。 1 H-NMR (270MHz, CDCl 3 ): 8.02 (d, J = 3.4 Hz, 2H), 7.43 (d, J = 3.4 Hz, 2H), 7.12 (t, J = 7.3 Hz, 2H), 3.55 (d) , J = 7.3 Hz, 2H), 1.89 (brs, 1H), 1.4-1.2 (m, 34H), 0.86 (m, 6H) ppm.
將N-溴丁二醯亞胺(東京化成工業股份有限公司製)498mg(2.8mmol)加入上述化合物(6-b)837mg(1.4mmol)之氯仿溶液(50ml)，在室溫下攪拌6小時。於添加水50ml後，洗淨有機層係分別利用水洗淨2次、接著利用飽和食鹽水洗淨1次，利用無水硫酸鎂乾燥後，減壓蒸餾溶劑。藉由利用矽膠管柱層析儀(洗提液、己烷：氯仿=1：1)精製粗生成物而獲得黃色固體(820mg、產率78%)之化合物(6-c)。以下，顯示化合物(6-c)之1H-NMR的測定結果。 498 mg (2.8 mmol) of N-bromobutaneimine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the above compound (6-b) 837 mg (1.4 mmol) in chloroform solution (50 ml), and stirred at room temperature for 6 hours. . After adding 50 ml of water, the organic layer was washed twice with water, and then washed once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The crude product was purified by a silica gel column chromatography (eluent, hexane: chloroform = 1:1) to afford compound (6-c) as a yellow solid (820 mg, yield 78%). The measurement results of 1 H-NMR of the compound (6-c) are shown below.
1H-NMR(270MHz、CDCl3)：7.66(d,J=4.1Hz,2H),7.07(J=4.1Hz,2H),3.53(d,J=7.3Hz,2H),1.87(brs,1H),1.4-1.1(m,34H),0.86(m,6H)ppm。 1 H-NMR (270MHz, CDCl 3 ): 7.66 (d, J = 4.1 Hz, 2H), 7.07 (J = 4.1 Hz, 2H), 3.53 (d, J = 7.3 Hz, 2H), 1.87 (brs, 1H) ), 1.4-1.1 (m, 34H), 0.86 (m, 6H) ppm.
使上述化合物(6-c)113mg(0.15mmol)及化合物(1-g)116mg(0.15mmol)溶解於甲苯(和光純藥工業股份有限公司製)10ml中之後，再添加三(二亞苄基丙酮)二鈀(東京化成工業股份有限公司製)4mg、三(2-甲基苯基)膦(東京化成工業股份有限公司製)7mg，於氮氣環境 中，在100℃下攪拌12小時。接著，添加溴苯(東京化成工業股份有限公司製)10mg，在100℃下攪拌1小時。接著，添加三丁基(2-并二噻吩)錫(東京化成工業股份有限公司製)40mg，在100℃下進一步攪拌1小時。於攪拌結束後，將反應混合物冷卻至室溫，注入甲醇100ml中。過濾所析出的固體，依照甲醇、水、丙酮之順序洗淨。接著，利用索氏萃取器，依照丙酮、己烷之順序洗淨。接著，使所獲得的固體溶解於氯仿中，通入矽藻土(Nakarai Tesc股份有限公司製)，接著於通入矽膠管柱(洗提液：氯仿)後，減壓蒸餾溶劑。使所得之固體再度溶解於氯仿中之後，於甲醇中再沉澱而獲得化合物B-2(72mg)。重量平均分子量為45,300、數量平均分子量為22,000、聚合度n為44。又，光吸收端波長為658nm、能帶間隙(Eg)為1.88eV、最高佔據分子軌域(HOMO)準位為-5.35eV。 After dissolving 113 mg (0.15 mmol) of the compound (6-c) and 116 mg (0.15 mmol) of the compound (1-g) in 10 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), tris(dibenzylidene) was further added. Acetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 4 mg, tris(2-methylphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), 7 mg, in a nitrogen atmosphere The mixture was stirred at 100 ° C for 12 hours. Then, 10 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C for 1 hour. Then, 40 mg of tributyl(2-dithiophene) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C for 1 hour. After the completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was filtered and washed in the order of methanol, water and acetone. Then, it was washed in the order of acetone and hexane by a Soxhlet extractor. Then, the obtained solid was dissolved in chloroform, passed through diatomaceous earth (manufactured by Nakarai Tesc Co., Ltd.), and then passed through a gel column (eluent: chloroform), and then the solvent was distilled under reduced pressure. The obtained solid was dissolved again in chloroform, and then reprecipitated in methanol to give Compound B-2 (72 mg). The weight average molecular weight was 45,300, the number average molecular weight was 22,000, and the degree of polymerization n was 44. Further, the light absorption end wavelength was 658 nm, the energy band gap (Eg) was 1.88 eV, and the highest occupied molecular orbital (HOMO) level was -5.35 eV.
合成例7 Synthesis Example 7
利用顯示於式7之方法而合成化合物B-3。 Compound B-3 was synthesized by the method shown in Formula 7.
使上述化合物(5-a)63mg(0.15mmol)及化合物(4-d)109mg(0.15mmol)溶解於甲苯(和光純藥工業股份有限公司製)5ml中之後，再添加三(二亞苄基丙酮)二鈀(東京化成工業股份有限公司製)4mg、三(2-甲基苯基)膦(東京化成工業股份有限公司製)7mg，於氮氣環境中，在100℃下攪拌12小時。接著，添加溴苯(東京化成工業股份有限公司製)10mg，在100℃下攪拌1小時。接著，添加三丁基(2-并二噻吩)錫(東京化成工業股份有限公司製)40mg，在100℃下進一步攪拌1小時。於攪拌結束後，將反應混合物冷卻至室溫，注入甲醇100ml中。過濾所析出的固體，依照甲醇、水、丙酮之順序洗淨。接著，利用索氏萃取器，依照丙酮、己烷之順序洗淨。接著，使所獲得的固體溶解於氯仿中，通入矽藻土(Nakarai Tesc股份有限公司製)，接著於通入矽膠管柱(洗提液：氯仿)後，減壓蒸餾溶劑。使所得之固體再度溶解於氯仿中之後，於甲醇中再沉澱而獲得化合物B-3(50mg)。重量平均分子量為19,400、數量平均分子量為11,000、聚合度n為29。又，光吸收端波長為752nm、能帶間隙(Eg)為1.65eV、最高佔據分子軌域(HOMO)準位為-5.28eV。 After dissolving 63 mg (0.15 mmol) of the compound (5-a) and 109 mg (0.15 mmol) of the compound (4-d) in 5 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), tris(dibenzylidene) was further added. Acetone) 2 mg of palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7 mg of tris(2-methylphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C for 12 hours under a nitrogen atmosphere. Then, 10 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C for 1 hour. Then, 40 mg of tributyl(2-dithiophene) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C for 1 hour. After the completion of the stirring, the reaction mixture was cooled to room temperature and poured into 100 ml of methanol. The precipitated solid was filtered and washed in the order of methanol, water and acetone. Then, it was washed in the order of acetone and hexane by a Soxhlet extractor. Then, the obtained solid was dissolved in chloroform, passed through diatomaceous earth (manufactured by Nakarai Tesc Co., Ltd.), and then passed through a gel column (eluent: chloroform), and then the solvent was distilled under reduced pressure. The obtained solid was dissolved again in chloroform, and then reprecipitated in methanol to give Compound B-3 (50 mg). The weight average molecular weight was 19,400, the number average molecular weight was 11,000, and the degree of polymerization n was 29. Further, the light absorption end wavelength was 752 nm, the energy band gap (Eg) was 1.65 eV, and the highest occupied molecular orbital (HOMO) level was -5.28 eV.
實施例1 Example 1
藉由將上述A-1(1mg)與PC70BM(4mg、Solenne公司製)加入已裝有氯苯0.25ml之試樣瓶中，在超音波洗淨機(井內盛榮堂股份有限公司製US-2(商品名)、輸出功率120W)中超音波照射30分鐘而獲得溶液A。 The above-mentioned A-1 (1 mg) and PC 70 BM (4 mg, manufactured by Solenne Co., Ltd.) were added to a sample bottle containing 0.25 ml of chlorobenzene, and the ultrasonic cleaning machine was used in the US. -2 (trade name), output power 120 W) The ultrasonic wave was irradiated for 30 minutes to obtain a solution A.
將利用濺鍍法堆積有120nm之成為正極之ITO透明導電層的玻璃基板切斷成38mm×46mm後，利用光刻法而將ITO圖案化成38mm×13mm之長方形。利用鹼洗淨液(Furuuchi化學股份有限公司製、”Semico Clean”EL56(商品名))超音波洗淨10分鐘後，利用超純水洗淨。 The glass substrate on which the 120 nm-thick ITO transparent conductive layer was deposited by sputtering was cut into 38 mm × 46 mm, and then ITO was patterned into a rectangle of 38 mm × 13 mm by photolithography. After washing with an alkali washing solution ("Semico Clean" EL56 (trade name), manufactured by Furuu Chemical Co., Ltd.) for 10 minutes, it was washed with ultrapure water.
於UV/臭氧處理該基板30分鐘後，利用旋轉塗布法，使成為電洞輸送層之PEDOT：PSS水溶液(PEDOT 0.8重量%、PPS 0.5重量%)在基板上長膜成60nm之厚度。藉由熱板而在200℃下加熱乾燥5分鐘後，將上述溶液A滴於PEDOT：PSS層上，利用旋轉塗布法，形成膜厚100nm之有機半導體層。之後，將已形成有機半導體層之基板與陰極用遮罩設置於真空蒸鍍裝置內，直到使裝置內之真空度成為1×10-3Pa以下後再度排氣，利用電阻加熱法，使得成為負極之鋁層成為80nm之厚度、與帶狀之ITO層交叉的部分之面積成為5mm×5mm的方式來蒸鍍。進行如上方式，作成發電層面積為5mm×5mm的光伏元件。如上所述，製得帶狀之ITO層與鋁層交叉的部分之面積為5mm×5mm的光伏元件。 After the substrate was treated with UV/ozone for 30 minutes, a PEDOT:PSS aqueous solution (PEDOT 0.8 wt%, PPS 0.5 wt%) serving as a hole transport layer was grown to a thickness of 60 nm on the substrate by a spin coating method. After heating and drying at 200 ° C for 5 minutes by a hot plate, the solution A was dropped on the PEDOT:PSS layer, and an organic semiconductor layer having a thickness of 100 nm was formed by a spin coating method. After that, the substrate and the cathode mask in which the organic semiconductor layer has been formed are placed in a vacuum vapor deposition apparatus, and the degree of vacuum in the apparatus is set to 1 × 10 -3 Pa or less, and then exhausted again, and the resistance heating method is used. The aluminum layer of the negative electrode was vapor-deposited so as to have a thickness of 80 nm and an area of a portion intersecting the strip-shaped ITO layer of 5 mm × 5 mm. In the above manner, a photovoltaic element having a power generation layer area of 5 mm × 5 mm was produced. As described above, a photovoltaic element having an area of a portion where the strip-shaped ITO layer and the aluminum layer intersect was 5 mm × 5 mm.
將進行如此方式所製得的光伏元件之正極與負極連接至Hewlett Packard公司製Pico-Amp Meter/Voltage Source 4140B，在空氣中，從ITO層側照射模擬陽光(山下電裝股份有限公司製之簡易型陽光模擬器YSS-E40、光譜形狀：AM1.5、強度：100mW/cm2)，測定使外加電壓從-1V變化至+2V時之電流值。此時之 短路電流密度(外加電壓為0V時之電流密度值)為6.45A/cm2、釋放電壓(使電流密度成為0時之外加電壓值)為0.97V、填充因子(FF)為0.60，從該等數值所算出的光電轉換效率為3.75%。還有，填充因子與光電轉換效率係由下式所算出。 The positive electrode and the negative electrode of the photovoltaic element obtained in this manner were connected to a Pico-Amp Meter/Voltage Source 4140B manufactured by Hewlett Packard Co., Ltd., and the simulated sunlight was irradiated from the ITO layer side in the air (simple by Yamashita Denso Co., Ltd.) The type of sunlight simulator YSS-E40, spectral shape: AM1.5, intensity: 100 mW/cm 2 ), and the current value when the applied voltage was changed from -1 V to +2 V was measured. The short-circuit current density at this time (the current density value when the applied voltage is 0 V) is 6.45 A/cm 2 , the release voltage (the voltage value when the current density becomes 0) is 0.97 V, and the fill factor (FF) is 0.60. The photoelectric conversion efficiency calculated from these values was 3.75%. Further, the fill factor and the photoelectric conversion efficiency were calculated by the following formula.
填充因子=IVmax(mA．V/cm2)/(短路電流密度(mA/cm2)×釋放電壓(V)) Fill factor=IVmax(mA.V/cm 2 )/(short circuit current density (mA/cm 2 )×release voltage (V))
(於此，IVmax係外加電壓從0V至釋放電壓值之間而使電流密度與外加電壓之乘積成為最大之時點的電流密度與外加電壓乘積之值)。 (In this case, IVmax is the value of the product of the current density and the applied voltage at the time when the product of the current density and the applied voltage is maximized from 0 V to the release voltage value).
光電轉換效率=[(短路電流密度(mA/cm2)×釋放電壓(V)×填充因子/模擬陽光強度(100mW/cm2)]×100(%) Photoelectric conversion efficiency = [(short circuit current density (mA/cm 2 ) × release voltage (V) × fill factor / simulated sunlight intensity (100 mW / cm 2 )] × 100 (%)
由上式也算出在下列實施例與比較例中之全部填充因子與光電轉換效率。 The filling factor and photoelectric conversion efficiency in the following examples and comparative examples were also calculated from the above formula.
實施例2 Example 2
除了使用上述A-2取代A-1之外，完全相同於實施例1進行而製作光伏元件，測定電流-電壓特性。此時之短路電流密度為7.83mA/cm2，釋放電壓為0.98V，填充因子(FF)為0.54，從該等數值所算出的光電轉換效率為4.14%。 A photovoltaic element was fabricated in the same manner as in Example 1 except that the above A-2 was used instead of A-1, and the current-voltage characteristics were measured. The short-circuit current density at this time was 7.83 mA/cm 2 , the discharge voltage was 0.98 V, and the fill factor (FF) was 0.54. The photoelectric conversion efficiency calculated from these values was 4.14%.
實施例3 Example 3
除了使用上述A-3取代A-1之外，完全相同於實施例1進行而製作光伏元件，測定電流-電壓特性。此時之短路電流密度為7.23mA/cm2，釋放電壓為0.98V，填充因子(FF)為0.50，從該等數值所算出的光電轉換效率為3.54%。 The photovoltaic element was fabricated in the same manner as in Example 1 except that the above A-3 was used instead of A-1, and the current-voltage characteristics were measured. The short-circuit current density at this time was 7.23 mA/cm 2 , the release voltage was 0.98 V, and the fill factor (FF) was 0.50. The photoelectric conversion efficiency calculated from these values was 3.54%.
實施例4 Example 4
除了使用上述A-4取代A-1之外，完全相同於實施例1進行而製作光伏元件，測定電流-電壓特性。此時之短路電流密度為7.68mA/cm2，釋放電壓為0.94V，填充因子(FF)為0.46，從該等數值所算出的光電轉換效率為3.32%。 A photovoltaic element was fabricated in the same manner as in Example 1 except that the above A-4 was used instead of A-1, and the current-voltage characteristics were measured. The short-circuit current density at this time was 7.68 mA/cm 2 , the release voltage was 0.94 V, and the fill factor (FF) was 0.46. The photoelectric conversion efficiency calculated from these values was 3.32%.
比較例1 Comparative example 1
除了使用上述B-1取代A-1之外，完全相同於實施例1進行而製作光伏元件，測定電流-電壓特性。此時之短路電流密度為6.10mA/cm2，釋放電壓為0.96V，填充因子(FF)為0.45，從該等數值所算出的光電轉換效率為2.64%。 A photovoltaic element was fabricated in the same manner as in Example 1 except that the above B-1 was used instead of A-1, and the current-voltage characteristics were measured. The short-circuit current density at this time was 6.10 mA/cm 2 , the release voltage was 0.96 V, and the fill factor (FF) was 0.45. The photoelectric conversion efficiency calculated from these values was 2.64%.
比較例2 Comparative example 2
除了使用上述B-2取代A-1之外，完全相同於實施例1進行而製作光伏元件，測定電流-電壓特性。此時之短路電流密度為2.45mA/cm2，釋放電壓為0.76V，填充因子(FF)為0.56，從該等數值所算出的光電轉換效率為1.04%。 A photovoltaic element was fabricated in the same manner as in Example 1 except that the above B-2 was used instead of A-1, and the current-voltage characteristics were measured. The short-circuit current density at this time was 2.45 mA/cm 2 , the release voltage was 0.76 V, and the fill factor (FF) was 0.56. The photoelectric conversion efficiency calculated from these values was 1.04%.
比較例3 Comparative example 3
除了使用上述B-3取代A-1之外，完全相同於實施例1進行而製作光伏元件，測定電流-電壓特性。此時之短路電流密度為5.43mA/cm2，釋放電壓為0.80V，填充因子(FF)為0.41，從該等數值所算出的光電轉換效率為1.78%。 A photovoltaic element was fabricated in the same manner as in Example 1 except that the above B-3 was used instead of A-1, and the current-voltage characteristics were measured. The short-circuit current density at this time was 5.43 mA/cm 2 , the discharge voltage was 0.80 V, and the fill factor (FF) was 0.41. The photoelectric conversion efficiency calculated from these values was 1.78%.
如表1可明確得知，與利用同樣條件所製作的其他光伏元件(比較例1至3)作一比較，使用具有通式(1)所表示的結構之電子供給性有機材料所製作的光伏元件(實施例1至4)係顯示較高的光電轉換效率。 As can be clearly seen from Table 1, the photovoltaics produced using the electron-donating organic material having the structure represented by the general formula (1) were compared with other photovoltaic elements (Comparative Examples 1 to 3) produced under the same conditions. The elements (Examples 1 to 4) showed high photoelectric conversion efficiency.
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