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WO2011091608A1 - 醌型噻吩有机光电材料、其制备方法和应用 - Google Patents

醌型噻吩有机光电材料、其制备方法和应用 Download PDF

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WO2011091608A1
WO2011091608A1 PCT/CN2010/070436 CN2010070436W WO2011091608A1 WO 2011091608 A1 WO2011091608 A1 WO 2011091608A1 CN 2010070436 W CN2010070436 W CN 2010070436W WO 2011091608 A1 WO2011091608 A1 WO 2011091608A1
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organic
organic photoelectric
photoelectric material
thiophene
reaction
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周明杰
黄杰
刘辉
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Oceans King Lighting Science and Technology Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
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Priority to EP10844386.2A priority Critical patent/EP2530132B1/en
Priority to CN201080048104XA priority patent/CN102575157A/zh
Priority to US13/575,648 priority patent/US8710094B2/en
Priority to JP2012550293A priority patent/JP5480403B2/ja
Priority to PCT/CN2010/070436 priority patent/WO2011091608A1/zh
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    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/50—Photovoltaic [PV] energy
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Definitions

  • the present invention relates to the field of organic material technology, and in particular to a quinone type thiophene.
  • the organic photoelectric material its manufacturing method and application.
  • Organic solar cells are a new type of solar cells. Compared with inorganic semiconductor materials, which are limited in source, expensive, toxic, complicated in preparation process and high in cost, they have some advantages that inorganic solar cells cannot match, such as a wide range of materials. Structure diversity and controllability, low cost, safety and environmental protection, simple production process, light weight, large area flexible preparation, etc., can be widely used in various fields such as construction, lighting and power generation, with important development and application. prospect. Therefore, many research institutions and enterprises at home and abroad have given considerable attention and input. However, so far, the photoelectric conversion efficiency of organic solar cells is still much lower than that of inorganic solar cells. Therefore, the development of new organic optoelectronic materials is important for improving the efficiency of organic solar cells and other semiconductor devices. To be meaningful. Summary of the invention
  • a thiophene thiophene having a wide response and stable stability is provided. It is divided into organic photoelectric materials, and a simple and low-cost synthetic thiophene. A method of manufacturing an organic photoelectric material.
  • the embodiments of the present invention also provide the above-mentioned quinone thiophene.
  • a quinone type thiophene A quinone type thiophene.
  • An organic photoelectric material comprising a compound represented by the following structural formula (1):
  • R 2 , R 3 , R 4 , R 5 and R 6 are the same or different alkyl or alkoxy group represented by 11 or dC ⁇ , and m and n are the same or different between 1 and 20 Integer.
  • a quinone type thiophene comprising the steps of:
  • the compound, B, and C are subjected to Stille coupling reaction under the conditions of a catalyst and a solvent; the Stille coupling reaction product is subjected to a bromination substitution reaction to form a brominated product; The bromination product is subjected to a condensation reaction with malononitrile under the conditions of a catalyst, a condensing agent and a solvent to obtain a compound represented by the following structural formula (1):
  • the above quinone type thiophene Among the organic photoelectric materials, it has a plurality of quinone thiophene ring structures, because the thiophene ring is a five-membered ring structure, conforms to the shock rule, has a moderate band gap, a wide optical response, and good thermal stability. And environmental stability. Moreover, the above quinone type thiophene.
  • the absorption range for example, can push the absorption band edge of the material toward the red light and the near-infrared region, thereby improving the photoelectric performance and photoelectric conversion efficiency of the material.
  • quinone type thiophene In the above quinone type thiophene. In the method of manufacturing organic optoelectronic materials, a simpler synthesis route and a Stille coupling reaction are used, which simplifies the process and reduces the manufacturing cost. The above-mentioned thiophene.
  • organic photoelectric materials are used in solar cell devices, organic field effect transistors, organic electroluminescent devices, organic optical storage devices, organic nonlinear materials or organic laser devices, their photoelectric or semiconductor-related properties can be improved, and devices can be lightened. The quality is easy to prepare in large quantities.
  • Figure 1 is a bismuth thiophene of an embodiment of the present invention a schematic diagram of a structural formula (1) of an organic photoelectric material compound
  • FIG. 2 is a bismuth thiophene of an embodiment of the present invention.
  • Fig. 3 is a bismuth thiophene according to an embodiment of the present invention.
  • Figure 4 is a bismuth thiophene employing an embodiment of the present invention. Schematic diagram of the structure of an organic electroluminescent device divided into organic photoelectric materials.
  • Figure 5 is a bismuth thiophene employing an embodiment of the present invention. Schematic diagram of the structure of an organic field effect transistor with organic photoelectric materials. detailed description
  • R 2 , R 3 , R 4 , R 5 , R 6 are the same or different alkyl or alkoxy group represented by 11 or d-Cso, and m and n are the same or different 1-20 An integer between.
  • the quinone form has a symmetrical molecular structure.
  • the molecular weight of the organic photoelectric material is small, and the quality of the produced product is light.
  • R 6 is the same 11, C r C 3 .
  • Alkyl or alkoxy, R 2 , R 5 are the same 11, d-Cso alkyl or alkoxy.
  • R 3 and R 4 are the same 11, dC ⁇ alkyl or alkoxy group.
  • R 2 , R 3 , R 4 , R 5 and R 6 are all H.
  • the above quinone type thiophene In the above quinone type thiophene. In the organic photoelectric material, it has a plurality of quinone thiophene ring structures, because the thiophene ring is a five-membered ring structure, conforms to the shock rule, has a moderate band gap, and has a wide optical response, wave The segment is approximately 300-700 nm and covers the visible light band. In addition, it also has good thermal stability and environmental stability, and exhibits good photoelectric properties. Moreover, the above quinone type thiophene.
  • the absorption range for example, can push the absorption band edge of the material toward the red light and the near-infrared region, thereby improving the photoelectric performance and photoelectric conversion efficiency of the material.
  • the method for manufacturing an organic photoelectric material includes the following steps:
  • R 3 , , R 5 , and R 6 are the same or different alkyl or alkoxy groups represented by H or dC ⁇ , and m and n are the same or different integers between 1 and 20, ! ! a pit base of ⁇ - ⁇ ;
  • S02 Stille coupling reaction of the compound, B, and C under the conditions of a catalyst and a solvent
  • S03 performing a bromination substitution reaction of the Stille coupling reaction product to form a bromination product
  • step S01 the compounds A, B, C and malononitrile are commercially available or can be prepared by existing synthetic methods and will not be described in detail herein.
  • the structures in the compounds A, B, and C are the above-mentioned quinone thiophenes.
  • the description of the organic photoelectric materials is basically the same and will not be described in detail herein.
  • An may be an alkyl group having a fluorenyl group, an n-butyl group or a tert-butyl group as d-C4.
  • the catalyst used in the Stille coupling reaction is an organic palladium catalyst, such as Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 , etc., preferably Is Pd 2 (dba) 3 /P(o-Tol) 3 .
  • the solvent may be tetrahydrofuran, dichlorodecane, ethylene glycol dioxime ether, benzene or toluene, etc., preferably tetrahydrofuran.
  • the compound A, B, and C may be added in an amount of from 1% to 20% by weight based on the chemical reaction, or the compounds A and B are not limited thereto.
  • the reaction is as follows:
  • step S02 The specific implementation process of step S02 is as follows: Under the protection of nitrogen, anhydrous THF is added to the pressure tube, and the compounds A and B and the compound C are quickly added, and after bubbling for several tens of minutes, the organic palladium catalyst is added, capped, and heated. At 80 ° C, reflux for 24 hours.
  • the purification step is as follows: Add KF (such as 1.00 M) aqueous solution to the reaction product, stir for several tens of minutes, add saturated aqueous sodium chloride solution, extract with ethyl acetate, dry over anhydrous magnesium sulfate, Chromatographic separation gave the product.
  • KF such as 1.00 M
  • the solvent may be dimercaptophthalamide (DMF), tetrahydrofuran, carbon tetrachloride chloroform, dichlorodecane or acetonitrile, and the like, and N-bromosuccinimide (NBS), Br 2 is used.
  • HBr or PBr 3 or the like is preferably NBS.
  • the catalyst is an organic palladium catalyst such as Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 or the like, preferably Pd 2 (dba) 3 /P(o-Tol) 3
  • the solvent used may be ethylene glycol diterpene ether, ethanol, decyl alcohol, dichlorodecane, trichlorodecane, tetrahydrofuran, ethyl acetate, DMF, toluene or acetone It is preferably ethylene glycol dioxime ether.
  • the condensing agent may be sodium hydride or sodium alkoxide, and the sodium alkoxide may be, for example, sodium decoxide or sodium t-butoxide. The reaction is as follows:
  • step S03 The specific implementation process is as follows: Add malononitrile to a suspension of sodium hydride (60% in oil) and ethylene glycol dioxime (DME) under ice bath, return to room temperature, stir for 30 minutes, and add to step S03.
  • the obtained brominated product and the organic palladium catalyst were heated to reflux for 12 hours, cooled to 0 ° C, added to a saturated aqueous solution of Br 2 /H 2 0, water was added, suction filtered, washed with water, dried and then purified by column chromatography.
  • the synthesis routes of the three monomers of the compounds A, B and C are relatively simple and mature, thereby reducing the process flow and reducing the manufacturing cost.
  • the Stille coupling reaction is a mature polymerization reaction with high yield, mild conditions, easy control, and easy introduction of an alkyl group or an alkoxy group to improve the solubility of the product, which is advantageous for expanding the processing property of the material.
  • the quinone type thiophene of this embodiment The organic optoelectronic material can be applied to various optoelectronic or semiconductor devices, for example, for solar cell devices, organic field effect transistors, organic electroluminescent devices, organic optical memory devices, organic nonlinear materials, and organic laser devices.
  • a solar cell device, an organic field effect transistor, and an organic electroluminescence device will be described as an example.
  • Others such as organic optical memory devices, organic nonlinear materials and organic laser devices are similar to the following, all of which are ruthenium-type thiophenes of this embodiment.
  • the organic photoelectron material is classified as an optical storage material, a nonlinear material, a laser material or a semiconductor material.
  • a solar cell device comprising an organic photoelectric material, comprising a glass substrate 11, a transparent anode 12, an intermediate auxiliary layer 13, an active layer 14, and a cathode 15 which are sequentially laminated, and the intermediate auxiliary layer 13 is made of polyethylene dioxythiophene: polystyrene-
  • the cross-acid composite material abbreviated as PEDOT:PSS
  • the active layer 14 includes an electron donor material and an electron acceptor material
  • the electron donor material adopts the above-mentioned quinone type thiophene.
  • the electron acceptor material may be [6,6]phenyl-C 61 -butyric acid acrylate (abbreviated as PCBM).
  • the transparent anode 12 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ /.
  • the cathode 15 can be an aluminum electrode.
  • the glass base layer 11 can be used as a bottom layer. When fabricated, an ITO electrode is first deposited on the glass base layer 11, and an intermediate-assisted layer 13 is formed on the ITO electrode by an oxygen-plasma treatment process, and the ruthenium is formed. Type thiophene.
  • the organic photoelectric material and the electron acceptor material are deposited on the intermediate auxiliary layer 13 by a vacuum evaporation technique to form the active layer 14, and then the cathode 15 is deposited on the active layer 14 by a vacuum evaporation technique to obtain the above solar cell device.
  • the organic optoelectronic material absorbs light energy and generates excitons, which then migrate to the interface of the electron donor/acceptor material, and transfer the electrons to an electron acceptor material, such as PCBM, to separate the charge, thereby forming Free carriers, ie free electrons and holes.
  • the organic photoelectric material can more fully utilize the light energy due to its wide optical response range, thereby obtaining higher photoelectric conversion efficiency and increasing the power generation capability of the solar cell device. Moreover, the organic material can also reduce the quality of the solar cell device, and can be fabricated by techniques such as vacuum evaporation, which is convenient for mass production.
  • An organic electroluminescent device of an organic photoelectric material comprising a glass base layer 21, a transparent anode 22, a light-emitting layer 23, a buffer layer 24, and a cathode 25 which are laminated in this order.
  • the transparent anode 22 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a square resistance of 10-20 ⁇ /.
  • the light-emitting layer 23 contains the quinone type thiophene in the above embodiment. Divided into organic photovoltaic materials.
  • the buffer layer 24 may be LiF or the like, but is not limited thereto.
  • the cathode 25 may be, but not limited to, metal A1 or Ba or the like, but is not limited thereto.
  • the organic electroluminescent device structure is represented by: ITO/ ⁇ -type thiophene. Divided into organic optoelectronic material /LiF/Al. Each layer can be formed by an existing method, and a thiophene type. The organic optoelectronic material can be formed on ITO by vacuum evaporation.
  • An organic field-effect transistor having an organic photoelectric material includes a substrate 31, an insulating layer 32, a modifying layer 33, an organic semiconductor layer 34, and a source electrode 35 and a drain electrode 36 provided on the organic semiconductor layer 34.
  • the substrate 31 may be, but not limited to, a highly doped silicon wafer (Si), and the insulating layer 32 may be, but not limited to, a micro-nano (eg, 450 nm) thick SiO 2 .
  • the organic semiconductor layer 34 employs the quinone type thiophene described above. Divided into organic photoelectric materials.
  • Both the source electrode 35 and the drain electrode 36 may be, but not limited to, gold.
  • the modifying layer 33 can be, but is not limited to, octadecyltrichlorosilane.
  • the substrate 31, the insulating layer 32, the modifying layer 33, and the source electrode 35 and the drain electrode 36 can be formed by a conventional method.
  • the organic semiconductor layer 34 may be at a vacuum degree close to 1 (T 4 Pa, which will be as described above) Indole type thiophene in the examples.
  • the organic photoelectric material is vapor-deposited on the insulating layer 32 modified by the modification layer 33.
  • the quinone type thiophene is exemplified below by way of specific examples. The preparation method of the organic photoelectric material and its performance and the like.
  • the raw materials used in the following examples can be prepared by an existing synthesis method, for example, the following raw material dithiophene [3, 2-b: 2,, 3, -d] and thiophene is passed from 2,3-dibromothiophene.
  • the literature for detailed preparation “Tetrahedron Express” (73 ⁇ 4ra zei ra” e era ) 2002, 43, 1553 ; 2, 2,-dithiophene from the raw material 2-bromothiophene through two steps After the preparation process, please refer to the literature: J. Am. Chem. Soc. 1997, 1 19, 12568.
  • the quinone type thiophene of this Example 1 The structure of the organic photoelectric material is as follows:
  • the indole type thiophene of the first embodiment is known.
  • the organic photoelectric material has relatively good light absorption performance and photoelectric performance, and the molecular weight is small, and the quality of the produced product is light.
  • the specific preparation steps are as follows: 39.16 g of NBS is added in portions to a reaction flask containing 19.60 g of dithiophene [3,2-b,3'-d] and thiophene and 200 mL of DMF in an ice bath and protected from light. The mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction solution was poured into ice water and quenched, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and evaporated. The product was isolated by silica gel column chromatography.
  • the compounds A and B in this step have the same structure, so that only one step 2) is required to prepare the compounds A and B, which simplifies the preparation process and reduces the cost. Conversely, if it is a thiophene.
  • the organic photoelectric material is not a symmetrical structure, and if the structures of the compounds A and B are different, it is necessary to carry out the steps 2) for the different raw materials.
  • the specific preparation steps are as follows: 8.4 g of thiophene is added to the reaction vessel. The mixture was dissolved in 100.0 mL of THF and 34.5 mL of n-butyllithium solution (2.9 M n-hexane solution) was added dropwise at -25 °C. After stirring for 1 hour, 32.5 mL of tributyltin chloride was added dropwise, and stirring was continued for 4 hours. After completion of the reaction, the reaction solution was returned to room temperature, and then a saturated aqueous solution of ammonium chloride was added, and the mixture was evaporated. After this step is completed, you do not need to purify and proceed directly to the next step.
  • this step i.e., the aforementioned step S02
  • the source of the raw material can be simplified in one aspect, thereby simplifying the preparation process and reducing the cost.
  • this step has a higher yield relative to the use of different compounds A and B.
  • the specific preparation process was as follows: Under the protection of nitrogen, 40 mL of anhydrous THF was added to the pressure-resistant tube, and 3.54 g of 2,6-dibromo-dithiane was quickly added. [3, 2-b, 3'-d] and thiophene and 8.21 g of tributyl-(thiophen-2-yl)tin, after bubbling for 30 minutes, 0.18 g of Pd 2 (dba) 3 and 0.12 g of P ( o-Tol) 3 , cover, warm to 80 ° C, reflux for 24 hours. At the end of the reaction, add 10.0 mL of KF (1.00 ⁇ ) aqueous solution, stir for 30 minutes, add The mixture was poured into a saturated aqueous solution of sodium chloride and ethyl acetate.
  • test results are: MALDI-TOF-MS (m/z): 518.4 (M + ).
  • the specific preparation process is as follows: 0.17 g of malononitrile is added to a suspension of 0.22 g of sodium hydride (60% in oil) and 20 mL of ethylene glycol dioxime in an ice bath, returned to room temperature, stirred for 30 minutes, and added. 0.56 g of 2,6-bis(5-bromo-thiazol-2-yl)-dithiophene [3,2-b,3'-d] thiophene and 0.074 g of PdCl 2 (PPh 3 ) 2o heated to reflux After 12 hours, cool to 0 ° C and add 20 mL of saturated Br 2 /H 2 0 solution. Water was added, suction filtration, washing with water, and dried.
  • the quinone type thiophene of the second embodiment is as follows:
  • the organic photoelectric material has relatively good light absorption performance and photoelectric performance.
  • the quinone type thiophene of this embodiment is as follows:
  • the compounds A and B in this step have the same structure, so that only one step 2) can be carried out to prepare the compounds A and B, which simplifies the preparation process and reduces the cost.
  • ⁇ type thiophene if ⁇ type thiophene.
  • the organic photoelectric material is not a symmetrical structure, and if the structures of the compounds A and B are different, it is necessary to carry out the steps 2) for the different raw materials.
  • the specific preparation process is as follows: Under the protection of nitrogen, 80 mL of anhydrous THF is added to the pressure resistant tube, and 7.08 g of 2,6-dibromo-dithiophene [3, 2-b, 3'-d] thiophene and 20.05 g of 5,5,-bis-tributyltin chloride-2, 2,-bi-dithio. After 40 minutes of bubbling, 0.40 g of Pd 2 (dba) 3 and 0.26 g of P(o-Tol) 3 were added , and the mixture was capped, heated to 80 ° C, and refluxed for 24 hours. After the reaction was completed, 20.0 mL of a KF (1.00 M) solution was added, and the mixture was stirred for 40 minutes, and then aq.
  • the specific preparation process is as follows: 3.92 g of NBS is added in portions to 5.25 g of 2,6-bis(2,2'-bidithiophen-5-yl)-dithiophene [3] in an ice bath and protected from light. , 2-b, 3'-d] and thiophene and 40 mL DMF in a reaction flask, stirred at room temperature for 10 hours. At the end of the reaction, the reaction solution was poured into ice water, extracted with trichloromethane, anhydrous The mixture was dried over magnesium sulfate, and then evaporated to silica.
  • the specific preparation process is as follows: 0.37 g of malononitrile is added to a suspension of 0.48 g of sodium hydride (60% in oil) and 30 mL of ethylene glycol dioxime in an ice bath, returned to room temperature, stirred for 30 minutes, and added. 1.47 g 2,6-bis(5,-bromo-2, 2,-bidithiophen-5-yl)-dithiophene [3,2-b,3'-d] thiophene and 0.16 g PdCl 2 (PPh 3 ) 2 . After heating to reflux for 12 hours, it was cooled to 0 ° C and a saturated Br 2 /H 2 0 solution was added. Water was added, suction filtration, water washing, and dried, and then purified by silica gel column chromatography.
  • the above-mentioned quinone type thiophene is known.
  • the organic photoelectric materials it has a plurality of quinone thiophene ring structures, because the thiophene ring is a five-membered ring structure, conforms to the shock rule, has a moderate band gap, a wide optical response, and good thermal stability. And environmental stability.
  • the above quinone type thiophene is known.
  • the absorption range of the language for example, can push the absorption band edge of the material toward the red light and the near-infrared region, thereby improving the photoelectric performance and photoelectric conversion efficiency of the material.
  • quinone type thiophene In the above quinone type thiophene.
  • a simpler synthesis route and a Stille coupling reaction are used, which simplifies the process and reduces the manufacturing cost.
  • organic photoelectric materials are used in solar cell devices, organic field effect transistors, organic electroluminescent devices, organic optical storage devices, organic nonlinear materials or organic laser devices, their photoelectric or semiconductor-related properties can be improved, and devices can be lightened.
  • the quality is easy to prepare in large quantities.

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Description

醌型噻吩有机光电材料、 其制造方法和应用
技术领域 本发明属于有机材料技术领域， 具体涉及一种醌型噻。分有机光电材料、 其 制造方法和应用。
说 背景技术
当今世界经济主要是建立在以化石能源， 如煤炭、 石油和天然气等基石出之 上的经济。然而，这些不可再生的化石能源都在书不断的枯竭。进入 21世纪以来， 全球性的能源问题以及随之而来的环境污染和气候变暖等问题日益凸现和逐渐 加剧。 由于太阳能具有分布普遍和广阔， 资源数量多， 无污染， 清洁， 安全以 及获取方便等突出优点， 被认为是最有希望的可再生能源之一。 太阳能电池直 接把太阳光能转化成电能， 是利用太阳能切实可行的有效方法。 然而， 目前商 品化的太阳能电池还局限于硅基等无机太阳能电池， 但它们的价格过于昂贵， 超出了目前人们普遍可以接受的程度， 这大大限制了它们的使用范围。 为了降 低电池成本， 拓展应用范围， 长期以来， 人们一直在寻找新型的太阳能电池材 料。
有机太阳能电池是一种新型的太阳能电池， 相对于无机半导体材料来源有 限、 价格昂贵、 有毒、 制备工艺复杂、 成本太高等而言， 它具有无机太阳能电 池无法比拟的一些优点， 如材料来源广泛、 结构多样性和可调控性、 成本低廉、 安全环保、 制作工艺简单、 产品重量轻、 可大面积柔性制备等等， 可以广泛应 用在建筑、 照明和发电等多种领域， 具有重要的发展和应用前景。 因此， 国内 外众多的研究机构和企业等都给予了相当的关注和投入。 然而， 到目前为止， 有机太阳能电池的光电转换效率比无机太阳能电池还是要低 4艮多。 因此， 开发 新型的有机光电材料对于提高有机太阳能电池及其它半导体器件的效率具有重 要意义。 发明内容
有鉴于此， 提供一种光语响应宽、 稳定性好的醌型噻。分有机光电材料， 以 及一种合成路线简单、 成本低的醌型噻。分有机光电材料制造方法。
本发明实施例还提供上述醌型噻。分有机光电材料在制造太阳能电池器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线性材料或 有机激光器件中的应用。
一种醌型噻。分有机光电材料， 其包含如下结构式（1 )表示的化合物：
Figure imgf000004_0001
式中： R2、 R3、 R4、 R5、 R6是相同或不同的表示为 11或 d-C^的烷基 或烷氧基， m、 n是相同或不同的 1-20之间的整数。
一种醌型噻。分有机光电材料制造方法， 其包括如下步骤：
分别提供如下结构式表示的化合物 A、 B、 C以及丙二腈，
Figure imgf000004_0002
或不同的表示为 H或 d-C^的烷基或烷氧基， m、 n是相同或不同的 1-20之间 的整数， ！！为 ^-^的坑基；
在催化剂和溶剂的条件下， 将化合物 、 B、 C进行 Stille耦合反应； 将 Stille耦合反应产物进行溴化取代反应， 生成溴化产物； 在催化剂、 缩合剂和溶剂的条件下， 将溴化产物与丙二腈进行缩合反应, 获得如下结构式 ( 1 )表示的化合物：
Figure imgf000005_0001
以及， 上述醌型噻。分有机光电材料在制造太阳能电池器件、 有机场效应晶 体管、 有机电致发光器件、 有机光存储器件、 有机非线性材料或有机激光器件 中的应用。
在上述醌型噻。分有机光电材料中， 其具有多个醌型噻吩环结构， 由于噻吩 环是五元环结构， 符合休克儿规则， 具有适中的能带隙， 较宽的光语响应， 较 好的热稳定性和环境稳定性。 而且， 上述醌型噻。分有机光电材料在分子链两端 引入强吸电子基团二氰基乙烯基（ = C(CN)2 ),成为含二噻吩并噻吩单元的醌型 噻吩结构， 进一步加宽材料对太阳光语的吸收范围， 例如可将材料的吸收带边 沿推向红光及近红外区， 从而提高材料的光电性能和光电转换效率。 在上述醌 型噻。分有机光电材料制造方法中， 采用较简单的合成路线和 Stille耦合反应， 可简化工艺和降低制造成本。 上述醌型噻。分有机光电材料应用于太阳能电池器 件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线性材 料或有机激光器件中时， 可提高其光电或半导体相关性能， 并能减轻器件的质 量， 且便于大批量的制备。 附图说明
下面将结合附图及实施例对本发明作进一步说明， 附图中：
图 1是本发明实施例的醌型噻。分有机光电材料化合物的结构式（ 1 )的示意 图；
图 2是本发明实施例的醌型噻。分有机光电材料制造方法流程图； 图 3是采用本发明实施例的醌型噻。分有机光电材料的太阳能电池器件结构 示意图。
图 4是采用本发明实施例的醌型噻。分有机光电材料的有机电致发光器件的 结构示意图。
图 5是采用本发明实施例的醌型噻。分有机光电材料的有机场效应晶体管的 结构示意图。 具体实施方式
为了使本发明的目的、 技术方案及优点更加清楚明白， 以下结合附图及实 施例， 对本发明进行进一步详细说明。 应当理解， 此处所描述的具体实施例仅 仅用以解释本发明， 并不用于限定本发明。
请参阅图 1 , 显示本发明实施例的醌型噻。分有机光电材料化合物的结构式 ( 1 ) , 即包含如下结构式（ 1 )表示的化合物：
Figure imgf000006_0001
式中： 、 R2、 R3、 R4、 R5、 R6是相同或不同的表示为 11或 d-Cso的烷基 或烷氧基， m、 n是相同或不同的 1-20之间的整数。
在本发明的一个实施例中， 醌型噻。分有机光电材料具有对称的分子结构。 例如， m、 n是相同的表示为 1-20之间的整数， 即 m=n。 在一个优选的实施例 中， m=n=l或 2, 此时， 该醌型噻。分有机光电材料分子量较小， 制成的产品质 量较轻。 在本发明一个实施例中， R6为相同的 11、 CrC3。烷基或烷氧基， R2、 R5为相同的 11、 d-Cso烷基或烷氧基。 R3、 R4为相同的 11、 d-C^烷基或 烷氧基。 这样的结构可以简化制备工艺， 降低生产成本。 在本发明一个优选的 实施例中， R2、 R3、 R4、 R5、 R6均为 H。
在上述醌型噻。分有机光电材料中， 其具有多个醌型噻吩环结构， 由于噻吩 环是五元环结构， 符合休克儿规则， 具有适中的能带隙， 较宽的光语响应， 波 段大约在 300-700 nm, 基本涵盖可见光波段。 另外， 还具有较好的热稳定性和 环境稳定性， 表现出较好的光电性能。 而且， 上述醌型噻。分有机光电材料在分 子链两端引入强吸电子基团二氛基乙烯基（ = C(CN)2 ),成为含二噻吩并噻吩单 元的醌型噻吩结构， 进一步加宽材料对太阳光谱的吸收范围， 例如可将材料的 吸收带边沿推向红光及近红外区， 从而提高材料的光电性能和光电转换效率。
请参阅图 2, 上述醌型噻。分有机光电材料的制造方法包括如下步骤：
S01 : 分别提供如下结构式表示的化合物 A、 B、 C以及丙二腈，
Figure imgf000007_0001
3、 、 R5、 R6是相同 或不同的表示为 H或 d-C^的烷基或烷氧基， m、 n是相同或不同的 1-20之间 的整数， ！！为 ^-^的坑基；
S02: 在催化剂和溶剂的条件下， 将化合物 、 B、 C进行 Stille耦合反应； S03: 将 Stille耦合反应产物进行溴化取代反应， 生成溴化产物；
S04: 在催化剂、 缩合剂和溶剂的条件下， 将溴化产物与丙二腈进行缩合反 应， 获得如下结构式 (1)表示的化合物：
Figure imgf000007_0002
在步骤 S01 中， 化合物 A、 B、 C以及丙二腈可直接从市场上购得或者通 过现有的合成方法制备， 在此不再详述。 其中， 化合物 A、 B、 C中的结构与上 述醌型噻。分有机光电材料的描述基本一致， 在此不再详述。 其中， 需要说明的 是， An可以是曱基、 正丁基或叔丁基为 d-C4的烷基。 在步骤 S02 中， Stille 耦合反应采用的催化剂为有机钯催化剂， 例如 Pd2(dba)3/P(o-Tol)3, Pd(PPh3)4或 Pd(PPh3)2Cl2等， 优选为 Pd2(dba)3/P(o-Tol)3。 溶剂可以是四氢呋喃、 二氯曱烷、 乙二醇二曱醚、 苯或曱苯等， 优选为四氢呋 喃。 化合物 A、 B、 C的加入量可以是按照化学反应计量， 或者是化合物 A、 B 采用过量 1%-20%的摩尔量， 并不限于此。 其反应如下式所示：
Figure imgf000008_0001
步骤 S02的具体实施过程如下： 在氮气保护下， 将无水 THF加入至耐压管 中，快速加入化合物 A和 B 以及和化合物 C,鼓泡数十分钟后加入有机钯催化 剂， 封盖， 升温至 80°C , 回流 24小时。 反应结束， 再进行提纯步骤如下： 往 反应产物中加入 KF (如 1.00 M) 水溶液， 搅拌数十分钟， 加入饱和氯化钠水溶 液， 乙酸乙酯萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得到产物。
Stille耦合反应时， 当 m≠n时， 理论上化合物 A和 B 自身会与化合物 C 发生 Stille耦合反应， 分别形成具有 （2m+2 )和（ 2n+2 )个噻吩环的化合物。 此时， 得到上述反应式中的目的产物的产率较低， 可通过上述提纯步骤来获得 纯的结构式中的产物。 可以理解的是， 此时， （2m+2 )和（2n+2 )个噻吩环的 化合物同样可提纯出， 作为醌型噻。分有机光电材料， 属于本发明构思的保护结 构之列。 当 m=n时， 化合物 A和 B相同， 目的产物的产率较高。
在步骤 S03中， 溶剂可采用二曱基曱酰胺（DMF ) 、 四氢呋喃、 四氯化碳 氯仿、 二氯曱烷或乙腈等， 并采用 N-溴代丁二酰亚胺（NBS ) 、 Br2、 HBr或 PBr3等， 优选为 NBS。 其反应如下式所示：
Figure imgf000009_0001
具体实施过程如下： 在冰浴、 避光条件下， 将 NBS分批加入至盛有 2, 6- 双 (噻。分 -2-基)-二噻吩 [3,2-b,3'-d]并噻吩和 DMF的反应器中， 室温搅拌 12小时。 反应结束， 将反应液倒入冰水中淬灭， 三氯曱烷萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得到产物。
在步骤 S04中，催化剂为有机钯催化剂，例如 Pd2(dba)3/P(o-Tol)3、 Pd(PPh3)4 或 Pd(PPh3)2Cl2等， 优选为 Pd2(dba)3/P(o-Tol)3, 采用的溶剂可以为乙二醇二曱 醚、 乙醇、 曱醇、 二氯曱烷、 三氯曱烷、 四氢呋喃、 乙酸乙酯、 DMF、 曱苯或 丙酮， 优选为乙二醇二曱醚。 缩合剂可以是氢化钠或醇钠， 醇钠可以是例如曱 醇钠或叔丁醇钠等。 其反应如下式所示：
Figure imgf000009_0002
具体实施过程如下： 冰浴下将丙二腈加入至氢化钠 （ 60%在油中）和乙二 醇二曱醚 (简称 DME)的悬浮液中， 恢复至室温， 搅拌 30分钟， 加入步骤 S03 获得的溴化产物和有机钯催化剂， 加热至回流 12小时后， 冷却至 0°C , 加入饱 和 Br2/H20溶液， 加入水， 抽滤， 水洗， 干燥， 柱层析分离得到产物。
在上述醌型噻。分有机光电材料的制备方法中， 化合物 A、 B、 C三种单体的 合成路线比较简单且成熟， 从而减少工艺流程， 降低制造成本。 而且 Stille耦 合反应是一种成熟的聚合反应， 产率高、 条件温和， 易于控制， 且易通过引入 烷基或烷氧基， 提高产物的溶解性， 有利于扩大材料的加工性能。
本实施例的醌型噻。分有机光电材料可应用于各种光电或半导体器件中， 例 如， 可用于太阳能电池器件、 有机场效应晶体管、 有机电致发光器件、 有机光 存储器件、 有机非线性材料和有机激光器件等。 下面以太阳能电池器件、 有机 场效应晶体管， 有机电致发光器件为例进行说明。 其它如有机光存储器件， 有 机非线性材料和有机激光器件与下面类似， 都是以本实施例的醌型噻。分有机光 电材料作为其的光存储材料、 非线性材料、 激光材料或半导体材料等。
请参阅图 3 , 显示采用上述实施例中醌型噻。分有机光电材料的太阳能电池 器件， 其包括依次层叠的玻璃基层 11、 透明阳极 12、 中间辅助层 13、 活性层 14、 阴极 15, 中间辅助层 13采用聚乙烯二氧基噻吩： 聚苯乙烯-横酸复合材料 (简称为 PEDOT:PSS ), 活性层 14包括电子给体材料和电子受体材料， 电子给 体材料采用上述醌型噻。分有机光电材料， 电子受体材料可以是 [6,6]苯基 -C61 -丁 酸曱酯 (简称为 PCBM )。 透明阳极 12可采用氧化铟锡 (简称为 ITO ) , 优选 为方块电阻为 10-20 Ω/ 的氧化铟锡。 阴极 15可采用铝电极。 其中， 玻璃基层 11可作为底层， 制作时， 先将 ITO电极沉积于玻璃基层 11 , 再用氧-等离子喷 涂（氧 -Plasma )处理工艺， 将中间辅助层 13形成于 ITO电极上， 以及将醌型 噻。分有机光电材料和电子受体材料通过真空蒸镀技术沉积于中间辅助层 13上， 形成活性层 14, 然后再通过真空蒸镀技术在活性层 14上沉积阴极 15, 获得上 述太阳能电池器件。 如图所示， 在光照下， 光透过玻璃基层 11和 ITO电极 12, 活性层 14中的 醌型噻。分有机光电材料吸收光能， 并产生激子， 这些激子再迁移到电子给体 / 受体材料的界面处， 并将电子转移给电子受体材料， 如 PCBM, 实现电荷的分 离， 从而形成自由的载流子， 即自由的电子和空穴。 这些自由的电子沿电子受 体材料向金属阴极传递并被阴极所收集， 自由的空穴沿电子给体材料向 ITO阳 极传递并被阳极所收集， 从而形成光电流和光电压， 实现光电转换， 外接负载 16时， 可对其进行供电。 在此过程中， 醌型噻。分有机光电材料由于其具有艮宽 的光语响应范围， 能够更充分地利用光能， 以获得更高的光电转换效率， 增加 太阳能电池器件的产电能力。 而且这种有机材料还能减轻太阳能电池器件的质 量， 并通过真空蒸镀等技术即可制作， 便于大批量的制备。
请参阅图 4, 显示采用上述实施例中的醌型噻。分有机光电材料的有机电致 发光器件， 其包括依次层叠设置的玻璃基层 21、 透明阳极 22、 发光层 23、 緩 冲层 24、 阴极 25。 透明阳极 22可采用氧化铟锡（简称为 ITO ) , 优选为方块 电阻为 10-20 Ω/ 的氧化铟锡。 发光层 23包含上述实施例中的醌型噻。分有机光 电材料。 緩冲层 24可采用 LiF等， 但不限于此。 阴极 25可以是但不限于金属 A1或 Ba等， 但不限于此。 因而， 在一个具体实施例中， 有机电致发光器件结 构表示为： ITO/醌型噻。分有机光电材料 /LiF/Al。 各层可采用现有方法形成， 而 醌型噻。分有机光电材料可通过真空蒸镀技术形成于 ITO上。
请参阅图 5 , 显示采用上述实施例中的醌型噻。分有机光电材料的有机场效 应晶体管， 其包括依次层叠设置的衬底 31、 绝缘层 32、 修饰层 33、 有机半导 体层 34以及设于有机半导体层 34上的源电极 35和漏电极 36。 其中， 衬底 31 可以是但不限于高掺杂的硅片 （Si ) , 绝缘层 32 可以是但不限于微纳米（如 450 nm )厚的 Si02。 有机半导体层 34采用上述描述的醌型噻。分有机光电材料。 源电极 35和漏电极 36均可采用但不限于金。修饰层 33可以是但不限于十八烷 基三氯硅烷。 衬底 31、 绝缘层 32、 修饰层 33以及源电极 35和漏电极 36都可 采用现有的方法形成。有机半导体层 34可以是在真空度接近 l(T4Pa下，将上述 实施例中的醌型噻。分有机光电材料蒸镀于由修饰层 33修饰的绝缘层 32上。 以下通过具体实施例来举例说明醌型噻。分有机光电材料制备方法以及其性 能等方面。 以下各实施例用到的原料可采用现有的合成方法制备， 例如， 下面 的原料二噻吩 [3, 2-b: 2，， 3，-d]并噻吩由 2, 3-二溴噻吩经过两步反应后制得，详细 制备过程请参考文献： 《四面体快报》（7¾ra zei ra" e era ) 2002, 43, 1553 ; 2, 2，-联二噻吩由原料 2-溴噻吩经过两步后制得，详细制备过程请参考文献：《美国 化学会志》 ( J. Am. Chem. Soc. ) 1997, 1 19, 12568。
实施例 1
本实施例 1的醌型噻。分有机光电材料结构如下所示：
Figure imgf000012_0001
由该结构式可知， 本实施例 1的醌型噻。分有机光电材料具有对称的结构， 具有四个醌型噻。分环以及两对氛基， 、 R2、 R3、 R4、 R5、 R6均为 H, m=n=l, 氛基作为吸电子基团， 通过此种均匀对称的结构， 使得醌型噻。分有机光电材料 相对具有较好的吸光性能和光电性能等， 而且分子量小，制成的产品质量较轻。
本实施例 1的醌型噻。分有机光电材料的制备方法具体过程如下：
1) 制备 2, 6-二溴-二噻吩 [3, 2-b, 3'-d]并噻吩， 即本实施例的化合物 C, 其 结构式如下所示：
Figure imgf000012_0002
其具体制备步骤为： 在冰浴、 避光条件下， 将 39.16 g NBS分批加入至盛有 19.60 g二噻吩 [3,2-b,3'-d]并噻吩和 200 mL DMF的反应瓶中， 室温搅拌 12小时。 反应结束， 将反应液倒入冰水中淬灭， 二氯曱烷萃取， 无水硫酸镁干燥， 旋蒸， 用硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 354.1 (M+)。
2) 制备三丁基- (噻。分 -2-基)锡， 作为本实施例的化合物 A和 B, 其结构式 如下所示：
Figure imgf000013_0001
在此步骤中的化合物 A和 B结构相同， 由此只需要进行一次步骤 2 ) 即可 制备出化合物 A和 B, 简化了制备工艺和降低成本。 相反， 如果醌型噻。分有机 光电材料不是对称的结构， 那么化合物 A和 B结构不同， 则需要对不同的原料 分别进行步骤 2 )。
其具体制备步骤为： 在反应容器中加入 8.4 g噻。分和无水 100.0 mL THF溶 液， 在 -25 °C下逐滴加入 34.5 mL正丁基锂溶液（2.9 M正己烷溶液） 。 搅拌 1 小时后， 逐滴加入 32.5 mL三丁基氯化锡， 继续搅拌 4小时。 反应完毕， 将反 应液恢复到至室温， 加入饱和氯化铵水溶液， 二氯曱烷萃取， 无水硫酸镁干燥， 旋蒸。 此步骤结束后可不需要提纯， 直接做下一步。
3) 制备 2, 6-双 (噻吩 -2-基)-二噻吩 [3, 2-b, 3'-d]并噻吩， 其结构式如下所示：
Figure imgf000013_0002
在此步骤中， 即前述的步骤 S02, 由于化合物 A和 B结构相同， 因此， 一 方面可简化原料来源， 由此也简化了制备工艺和降低成本。 另一方面， 本步骤 相对于采用不同化合物 A和 B时具有更高的产率。
具体制备过程为： 在氮气保护下， 将 40mL无水 THF加入至耐压管中， 快 速加入 3.54 g 2, 6-二溴-二噻。分 [3, 2-b, 3'-d]并噻吩和 8.21 g三丁基- (噻吩 -2-基) 锡，鼓泡 30分钟后加入 0.18 g Pd2(dba)3和 0.12 g P(o-Tol)3,封盖，升温至 80°C , 回流 24小时。 反应结束， 加入 10.0 mL KF ( 1.00 Μ) 水溶液， 搅拌 30分钟， 加 入饱和氯化钠水溶液， 乙酸乙酯萃取， 无水硫酸镁干燥， 旋蒸， 用硅胶柱层析 分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 360.6 (M+).
4) 制备 2, 6-双(5-溴-噻吩-2-基)-二噻吩[3,2 ,3'-(1]并噻吩， 其结构式如下所
Figure imgf000014_0001
具体制备过程为： 在冰浴、 避光条件下， 将 1.80 g NBS分批加入至盛有 1.80 g 2, 6-双 (噻吩 -2-基)-二噻吩 [3,2-b,3'-d]并噻吩和 30 mL DMF的反应瓶中， 室温搅 拌 12小时。 反应结束， 将反应液倒入冰水中淬灭， 三氯曱烷萃取， 无水硫酸镁 干燥， 旋蒸， 用硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 518.4 (M+).
5) 最终产物的制备， 其结构式如上所示。
具体制备过程为： 冰浴下将 0.17 g 丙二腈加入至 0.22 g 氢化钠 （60%在油 中）和 20 mL 乙二醇二曱醚的悬浮液中， 恢复至室温，搅拌 30分钟，加入 0.56 g 2, 6-双 (5-溴-噻。分 -2-基)-二噻吩 [3,2-b,3'-d]并噻吩和 0.074 g PdCl2(PPh3)2o 加热 至回流 12小时后， 冷却至 0°C , 加入 20 mL饱和 Br2/H20溶液。加入水，抽滤， 水洗， 干燥， 用硅胶柱层析分离得到产物， 产率为 65%。
测试结果为： MALDI-TOF-MS (m/z): 488.7 (M+)。
实施例 2
本实施例 2的醌型噻。分有机光电材料结构如下所示：
Figure imgf000015_0001
结构式与实施例 1的结构类似， 同样具有对称的结构， R2、 R3、 R4、 R5、 R6均为 H, 不同在于具有六个醌型噻吩环， m=n=2, 氛基作为吸电子基团， 通过此种均勾对称的结构， 使得醌型噻。分有机光电材料相对具有较好的吸光性 能和光电性能等。
本实施例的醌型噻。分有机光电材料的制备方法具体过程如下：
1) 制备 2, 6-二溴-二噻。分 [3, 2-b, 3'-d]并噻吩， 其与实施例 1的化合物 C相 同， 具体制备过程也与实施例 1中的步骤 1 )相同， 在此不再详述。
2) 制备 5-三丁基氯化锡 -2, 2，-联二噻吩， 作为本实施例的化合物 A和 B, 其结构式如下所示：
Figure imgf000015_0002
同实施例 1 , 在此步骤中的化合物 A和 B结构相同， 由此只需要进行一次 步骤 2 ) 即可制备出化合物 A和 B, 简化了制备工艺和降低成本。 相反， 如果 醌型噻。分有机光电材料不是对称的结构， 那么化合物 A和 B结构不同， 则需要 对不同的原料分别进行步骤 2 )。
其具体制备步骤为： 在反应容器中加入 16.60 g 2, 2，-联二噻吩和无水 120.0 mL THF溶液，在 -25 °C下逐滴加入 34.0 mL正丁基锂溶液（ 2.9 M正己烷溶液）。 搅拌 1小时后， 逐滴加入 33.0 mL三丁基氯化锡， 继续搅拌 6小时。 反应完毕， 将反应液恢复到至室温， 加入饱和氯化铵水溶液， 二氯曱烷萃取， 无水硫酸镁 干燥， 旋蒸。 此步骤结束后可不需要提纯， 直接做下一步。 3) 制备 2, 6-双 (2, 2'-联二噻吩 -5-基)-二噻吩 [3, 2-b, 3'-d]并噻吩， 其结构式 如下所示：
Figure imgf000016_0001
同实施例 1 , 由于化合物 A和 B结构相同， 因此，一方面可简化原料来源 , 由此也简化了制备工艺和降低成本。 另一方面， 本步骤相对于采用不同化合物 A和 B时具有更高的产率。
具体制备过程为： 在氮气保护下， 将 80mL无水 THF加入至耐压管中， 快 速加入 7.08 g 2, 6-二溴-二噻吩 [3, 2-b, 3'-d]并噻吩和 20.05 g 5, 5，-双 -三丁基氯化 锡 -2, 2，-联二噻。分， 鼓泡 40分钟后加入 0.40 g Pd2(dba)3和 0.26 g P(o-Tol)3, 封 盖， 升温至 80°C , 回流 24小时。 反应结束， 加入 20.0 mL KF ( 1.00 M) 溶液， 搅拌 40分钟，加入饱和氯化钠水溶液， 乙酸乙酯萃取，无水硫酸镁干燥，旋蒸， 用硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 524.8 (M+)。
4) 制备 2, 6-双 (5'-溴 -2, 2'-联二噻吩 -5-基) -二噻吩 [3, 2-b, 3'-d]并噻吩， 其结 构式如下所示：
Figure imgf000016_0002
具体制备过程为： 在冰浴、 避光条件下， 将 3.92 g NBS分批加入至盛有 5.25 g 2, 6-双 (2, 2'-联二噻吩 -5-基)-二噻吩 [3, 2-b, 3'-d]并噻吩和 40 mL DMF的反应瓶 中， 室温搅拌 10小时。 反应结束， 将反应液倒入冰水中， 三氯曱烷萃取， 无水 硫酸镁干燥， 旋蒸， 用硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 682.7 (M+)。
5) 最终产物的制备， 其结构式如上所示。
具体制备过程为： 冰浴下将 0.37 g 丙二腈加入至 0.48 g 氢化钠 （ 60%在油 中）和 30 mL 乙二醇二曱醚的悬浮液中， 恢复至室温，搅拌 30分钟，加入 1.47 g 2, 6-双（5，-溴 -2, 2，-联二噻吩 -5-基）-二噻吩 [3,2-b,3'-d]并噻吩和 0.16 g PdCl2(PPh3)2。 加热至回流 12小时后， 冷却至 0°C , 加入饱和 Br2/H20溶液。 加 入水， 抽滤， 水洗， 干燥， 用硅胶柱层析分离得到产物， 产率为 62%。
测试结果为： MALDI-TOF-MS (m/z): 650.9 (M+)。
由上可知， 上述醌型噻。分有机光电材料中， 其具有多个醌型噻吩环结构， 由于噻吩环是五元环结构， 符合休克儿规则， 具有适中的能带隙， 较宽的光语 响应， 较好的热稳定性和环境稳定性。 而且， 上述醌型噻。分有机光电材料在分 子链两端引入强吸电子基团二氛基乙烯基（ = C(CN)2 ),成为含二噻吩并噻吩单 元的醌型聚噻吩结构， 进一步加宽材料对太阳光语的吸收范围， 例如可将材料 的吸收带边沿推向红光及近红外区，从而提高材料的光电性能和光电转换效率。 在上述醌型噻。分有机光电材料制造方法中， 采用较简单的合成路线和 Stille耦 合反应， 可简化工艺和降低制造成本。 上述醌型噻。分有机光电材料应用于太阳 能电池器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、 有机 非线性材料或有机激光器件中时， 可提高其光电或半导体相关性能， 并能减轻 器件的质量， 且便于大批量的制备。
以上所述仅为本发明的较佳实施例而已， 并不用以限制本发明， 凡在本发 明的精神和原则之内所作的任何修改、 等同替换和改进等， 均应包含在本发明 的保护范围之内。

Claims

权 利 要 求 书
1、 一种醌型噻。分有机光电材料， 其包含如下结构式（1 )表示的化合物:
Figure imgf000018_0001
式中： R2、 R3、 R4、 R5、 R6是相同或不同的表示为 11或 d-C^的烷基 或烷氧基， m、 n是相同或不同的 1-20之间的整数。
2、 如权利要求 1所述的醌型噻。分有机光电材料， 其特征在于， 所述 、 R6为相同的 H或 -C3。烷基或烷氧基， 所述 R2、 R5为相同的 H或 CrC3。烷基 或烷氧基。
3、 如权利要求 1所述的醌型噻。分有机光电材料， 其特征在于， 所述 m、 n 是相同的 1-20之间的整数。
4、 如权利要求 1所述的醌型噻。分有机光电材料， 其特征在于， 所述 m、 n 均为 1或 2。
5、 一种醌型噻。分有机光电材料制造方法， 其包括如下步骤：
分别提供如下结构式表示的化合物 A、 B、 C以及丙二腈，
Figure imgf000018_0002
R3、 、 R5、 R6是相同 或不同的表示为 H或 CrC3()的烷基， m、 n是相同或不同的 1-20之间的整数, An为 d-C4的烷基；
在催化剂和溶剂的条件下， 将化合物 、 B、 C进行 Stille耦合反应； 将 Stille耦合反应产物进行溴化取代反应， 生成溴化产物；
在催化剂、 缩合剂和溶剂的条件下， 将溴化产物与丙二腈进行缩合反应, 获得如下结构式 ( 1 )表示的化合物：
Figure imgf000019_0001
6、 如权利要求 5所述的醌型噻。分有机光电材料制造方法， 其特征在于， 在 进行 Stille耦合反应、 溴化取代反应和缩合反应后， 分别进一步用硅胶柱层析 分离提纯， 得到对应的耦合反应产物、 溴化产物和结构式 (1)表示的化合物。
7、 如权利要求 5所述的醌型噻。分有机光电材料制造方法， 其特征在于， 所 述溴化取代反应是在二曱基曱酰胺、 四氢呋喃、 四氯化碳、 氯仿、 二氯曱烷或 乙腈作为溶剂的条件下，将 Stille耦合反应产物与 N-溴代丁二酰亚胺、 Br2、 HBr 或 PBr3进行的取代反应。
8、 如权利要求 5所述的醌型噻。分有机光电材料制造方法， 其特征在于， 所 述缩合反应采用的催化剂为有机钯催化剂，采用的溶剂为乙二醇二曱醚、 乙醇、 曱醇、 二氯曱烷、 三氯曱烷、 四氢呋喃、 乙酸乙酯、 DMF、 曱苯或丙酮。
9、 如权利要求 5所述的醌型噻。分有机光电材料制造方法， 其特征在于， 所 述 Stille耦合反应采用的催化剂为有机钯催化剂， 溶剂为四氢呋喃、 二氯曱烷、 乙二醇二曱醚、 苯或曱苯， 缩合剂为氢化钠或醇钠。
10、 如权利要求 1-4任一项所述的醌型噻。分有机光电材料在制造太阳能电 池器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线 性材料或有机激光器件中的应用。
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