WO2011153694A1 - 基于苝四羧酸二酰亚胺和苯并二噻吩的共轭聚合物及其制备方法和应用 - Google Patents

基于苝四羧酸二酰亚胺和苯并二噻吩的共轭聚合物及其制备方法和应用 Download PDF

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WO2011153694A1
WO2011153694A1 PCT/CN2010/073727 CN2010073727W WO2011153694A1 WO 2011153694 A1 WO2011153694 A1 WO 2011153694A1 CN 2010073727 W CN2010073727 W CN 2010073727W WO 2011153694 A1 WO2011153694 A1 WO 2011153694A1
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conjugated polymer
layer
organic
substrate
conductive layer
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French (fr)
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周明杰
黄杰
管榕
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海洋王照明科技股份有限公司
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Priority to EP10852687.2A priority Critical patent/EP2581399B1/en
Priority to PCT/CN2010/073727 priority patent/WO2011153694A1/zh
Priority to CN201080066879.XA priority patent/CN103025787B/zh
Priority to US13/702,141 priority patent/US20130085249A1/en
Priority to JP2013513512A priority patent/JP5628418B2/ja
Publication of WO2011153694A1 publication Critical patent/WO2011153694A1/zh

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    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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Definitions

  • the invention belongs to the field of optoelectronics, and in particular relates to a conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene and a preparation method thereof.
  • Polymer solar cells are attracting attention because of their low raw material price, light weight, flexibility, simple production process, large-area preparation by coating, printing, etc., if their energy conversion efficiency can be improved to close to commercial silicon solar cells. At the level, its market prospects will be very large. Since NS Sariciftci et al. in 1992 (N. S Sariciftci, L. Smilowitz, AJ Heeger, et al. Science, 1992, 258, 1474) reported light-induced electron transfer between a conjugated polymer and C60, People have invested a lot of research in polymer solar cells and have achieved rapid development.
  • Polymer solar cells are mainly focused on donor and acceptor blends.
  • the energy conversion efficiency of blends of PTB7 and PC71BM has reached 7.4% (Y. Liang et al., Adv. Mater.; DOI: 10.1002/ Adma.200903528 ), but still much lower conversion efficiency than inorganic solar cells.
  • the main limiting factors for limiting performance improvement are: relatively low carrier mobility of organic semiconductor devices, spectral response of the device does not match solar radiation spectrum, red light region of high photon flux is not effectively utilized, and carrier Electrode collection efficiency is low. In order to make polymer solar cells practical applications, it is still the primary task in this research field to develop new materials and greatly improve their energy conversion efficiency.
  • a conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene having the general formula:
  • n is a positive integer less than 101;
  • R 2 , R 3 are hydrogen, CH ⁇ o alkyl, ( ⁇ 0 20 alkoxybenzene or phenyl;
  • R 4 , R 5 is CH ⁇ Q alkyl .
  • a method for preparing a conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene comprises the following steps:
  • step S12 in an anaerobic environment, adding a catalyst to step S11, and performing Stille coupling reaction at 50 to 120 ° C for 24 to 72 hours to obtain the conjugated polymer solution, and the reaction equation is as follows:
  • the organic solvent is one or more selected from the group consisting of tetrahydrofuran, dinonylamide, dioxane, ethylene glycol dioxime ether, benzene and toluene; in step S12, the catalyst is added.
  • the catalyst is organic palladium or a mixture of organopalladium and an organophosphine ligand; the organic palladium is selected from the group consisting of Pd 2 (dba) 3 , Pd(PPh 3 ) 4 and Pd (PPh 3 ) One or more of 2 Cl 2 ; the organophosphine ligand is P(o-Tol) 3 ; the molar ratio of the mixture of the organic palladium and the organophosphine ligand is 1: 2 to 1:20.
  • the preparation method of the conjugated polymer further comprises a purification process after the conjugated polymer solution is obtained, and the specific steps are as follows:
  • the conjugated polymer solution is added dropwise to decyl alcohol, subjected to sedimentation treatment, and then suction-filtered, washed with decyl alcohol, and dried to obtain a colloid containing a conjugated polymer;
  • S14 a colloid containing a conjugated polymer Dissolved in toluene, and added the toluene solution to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 80 to 100 ° C, and then separated by crystallization of alumina to separate the conjugated polymer.
  • step S13 is repeated at least once, and the conjugated polymer separated in step S14 is subjected to Soxhlet extraction with acetone to obtain a conjugated polymer solid.
  • a solar cell device prepared by using the above conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene, comprising the following structures arranged in sequence: substrate, conductive layer, poly 3, 4-ethylene II Oxythiophene: a polystyrenesulfonic acid layer, an active conjugated polymer layer, and an aluminum metal layer.
  • a method of manufacturing the above solar cell device comprising the steps of:
  • An aluminum metal layer is disposed on the conjugated polymer layer to obtain the solar cell device.
  • An organic electroluminescent device prepared by using the above conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene, comprising the following structures arranged in sequence: a substrate, a conductive layer, and a conjugate having luminescent properties A polymer layer, a LiF buffer layer, and an aluminum metal layer.
  • a method for preparing the above organic electroluminescent device comprising the steps of:
  • An aluminum metal layer is disposed on the LiF buffer layer to obtain the organic electroluminescent device.
  • An organic field effect transistor prepared by using the above conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene, comprising the following structures arranged in sequence: doped silicon substrate, Si0 2 insulating layer, eighteen An alkyltrichlorosilane layer, a conjugated polymer organic semiconductor layer, a source electrode of a metal material, and a drain electrode.
  • ⁇ Sixiang S-diimide and its derivatives have a large co-benzene ring planar structure and two imine ring structures, which have strong absorption in the visible region and high light, heat and environmental stability.
  • Has a higher electron affinity (lower LUMO energy level) and because of its ⁇ - ⁇ stacking between the conjugated large ⁇ bonds, it has a high electron mobility in the stacking direction, so it is in an organic solar cell.
  • Various fields have shown broad application prospects.
  • the conjugated polymer by introducing a substituent at the "bay" position of the perylenetetracarboxylic diimide, and by copolymerizing the perylenetetracarboxylic diimide monomer with other monomers, increases the perylenetetracarboxylic acid The solubility of the imide.
  • the benzodithiophene unit is a unit having an excellent planar structure containing two five-membered rings and one six-membered ring skeleton, and its mobility is 4 ⁇ high due to its good flatness and conjugate degree, and benzene And dithia.
  • the 4th and 5th positions on the subunit can introduce a modification such as an alkyl group to improve the solubility and improve the solubility processability. Therefore, it is copolymerized with perylenetetracarboxylic acid diimide to form an electron donor-acceptor structure to adjust the band gap of the polymer and push the absorption band edge toward the infrared and near-infrared regions. Photoelectric conversion efficiency.
  • FIG. 1 is a schematic structural view of an embodiment of a solar cell device
  • FIG. 2 is a schematic structural view of an embodiment of an organic electroluminescent device
  • FIG. 3 is a schematic structural view of an embodiment of an organic field effect transistor.
  • the object of the present invention is to provide a conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene, which has good solubility, light absorption wave-latent width, and high photoelectric conversion. effectiveness.
  • the present invention also provides a process for preparing the conjugated polymer, and also indicates the use of the conjugated polymer in the field of optoelectronics.
  • a conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene having the general formula:
  • n is a positive integer less than 101;
  • R 2 , R 3 are hydrogen, CH ⁇ o alkyl, ( ⁇ 0 20 alkoxybenzene or phenyl;
  • R 4 , R 5 is CH ⁇ Q alkyl .
  • a method for preparing a conjugated polymer based on perylenetetracarboxylic acid diimide and benzodithiophene comprises the following steps:
  • the organic solvent is one or more selected from the group consisting of tetrahydrofuran, dinonylamide, dioxane, ethylene glycol dioxime ether, benzene and toluene; in step S12, an anaerobic environment It is composed of nitrogen or an inert gas; the amount of the catalyst added is 0.01% to 5% of the total moles of the substance; the catalyst is organic palladium or has a mixture of palladium and an organophosphine ligand; the organic palladium is one or more selected from the group consisting of Pd 2 (dba) 3 , Pd ( PPh 3 ) 4 and Pd(PPh 3 ) 2 Cl 2 ; P(o-Tol) 3 ; the molar ratio of the mixture of the organic palladium and the organophosphine ligand is 1: 2 ⁇ 1: 20.
  • the preparation method of the conjugated polymer further comprises a purification process after the conjugated polymer solution is obtained, and the specific steps are as follows:
  • the conjugated polymer solution is added dropwise to decyl alcohol, subjected to sedimentation treatment, and then suction-filtered, washed with decyl alcohol, and dried to obtain a colloid containing a conjugated polymer;
  • S14 a colloid containing a conjugated polymer Dissolved in toluene, and added the toluene solution to an aqueous solution of sodium diethyldithioaminopurine S, heated and stirred at 80 to 100 ° C, and then separated by alumina column chromatography to separate the conjugated polymer.
  • step S13 is repeated at least once, and the conjugated polymer separated in step S14 is subjected to Soxhlet extraction with acetone to obtain a conjugated polymer solid.
  • the preparation method of the conjugated polymer is simple and feasible, has low equipment requirements and is highly practical.
  • the conjugated polymer has broad application prospects in the field of optoelectronics, such as solar cell devices, organic electroluminescent devices, and organic field effect transistors.
  • a solar cell device as shown in FIG. 1 includes the following structures arranged in sequence: a substrate 110, a conductive layer 120, a poly(3-ethylenedioxythiophene): a polystyrene-t-butyl acid layer 130, having an activity
  • the conjugated polymer layer 140 and the aluminum metal layer 150 prepared using the aforementioned conjugated polymer are used.
  • the above method for manufacturing a solar cell device includes the following steps:
  • An aluminum metal layer is disposed on the conjugated polymer layer to obtain the solar cell device.
  • the substrate substrate is made of ITO glass (indium tin oxide glass), glass is used as the substrate, and indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ is used as the conductive layer.
  • the surface treatment process in step S22. Treatment with oxygen-Plasma (plasma), the conjugated polymer was applied to the poly(3-ethylenedioxythiophene) polyphenylene sulfite layer by spin coating techniques.
  • An organic electroluminescent device as shown in FIG. 2 includes the following structures: a substrate 210, a conductive layer 220, a conjugated polymer layer 230 prepared by using the conjugated polymer having luminescent properties, and a LiF buffer.
  • the layer 240 and the aluminum metal layer 250 is disposed on the conjugated polymer layer to obtain the solar cell device.
  • the substrate substrate is made of ITO glass (indium tin oxide glass), glass is used as the
  • the method for preparing the above organic electroluminescent device comprises the following steps:
  • the substrate substrate is made of ITO glass (indium tin oxide glass), glass is used as the substrate, and indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ is used as the conductive layer.
  • An organic field effect transistor as shown in FIG. 3 includes the following structures arranged in order from bottom to top: a doped silicon substrate 310, a SiO 2 insulating layer 320, and an octadecyltrichlorosilane layer 330, using the foregoing
  • the conjugated polymer organic semiconductor layer 340 prepared by the conjugate polymer, the source electrode 350 of the metal material, and the drain electrode 360.
  • the doped silicon substrate is a highly doped silicon wafer
  • the SiO 2 insulating layer has a thickness of 500 nm
  • the conjugated polymer is applied to the octadecyltrichlorosilane layer by spin coating.
  • the source electrode and the drain electrode are made of gold.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 90 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the separated conjugated polymer was added to methanol to precipitate, and then suction-filtered, washed with methanol, dried, and then subjected to Soxhlet extraction of the conjugated polymer to obtain a conjugated polymer solid.
  • conjugated polymer solution was added dropwise to methanol to carry out sedimentation treatment, followed by suction filtration and drying to obtain a colloid containing a conjugated polymer.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 90 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • conjugated polymer solution was added dropwise to methanol to carry out sedimentation treatment, followed by suction filtration and drying to obtain a colloid containing a conjugated polymer.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 80 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • conjugated polymer solution was added dropwise to methanol to carry out sedimentation treatment, followed by suction filtration and drying to obtain a colloid containing a conjugated polymer.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 80 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the conjugated polymer solution was added dropwise to methanol to carry out sedimentation treatment, followed by suction filtration and drying to obtain a colloid containing a conjugated polymer.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 80 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the conjugated polymer solution was added dropwise to methanol to carry out sedimentation treatment, followed by suction filtration and drying to obtain a colloid containing a conjugated polymer.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 90 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the separated conjugated polymer was added to methanol to precipitate, and then suction-filtered, washed with methanol, dried, and then subjected to Soxhlet extraction of the conjugated polymer to obtain a conjugated polymer solid.

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Description

基于茈四羧酸二酰亚胺和苯并二噻喻的共轭聚合物及其制备方法和应用
【技术领域】
本发明属于光电领域， 尤其涉及一种基于茈四羧酸二酰亚胺和苯并二噻吩 的共轭聚合物及其制备方法。
【背景技术】
利用廉价材料制备低成本、 高效能的太阳能电池一直是光伏领域的研究热 点和难点。 传统的用于地面的硅太阳能电池由于生产工艺复杂、 成本高， 使其 应用受到限制。 为了降低成本， 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。
聚合物太阳能电池因为原料价格低廉、 质量轻、 柔性、 生产工艺简单、 可 用涂布、 印刷等方式大面积制备等优点而备受关注， 如果能够将其能量转化效 率提高到接近商品硅太阳能电池的水平， 其市场前景将是非常巨大的。 自 1992 年 N. S. Sariciftci等在 SCIENCE ( N. S Sariciftci, L. Smilowitz, A. J. Heeger, et al. Science, 1992, 258, 1474 )上报道共轭聚合物与 C60之间的光诱导电子转移现象 后， 人们在聚合物太阳能电池方面投入了大量研究， 并取得了飞速的发展。
聚合物太阳能电池的研究主要集中于给体、 受体共混体系， 采用 PTB7 与 PC71BM共混体系的能量转化效率已经达到 7.4% ( Y. Liang et al., Adv. Mater.; DOI: 10.1002/adma.200903528 ), 但是仍比无机太阳能电池的转换效率低得多。 限制性能提高的主要制约因素有： 有机半导体器件相对较低的载流子迁移率， 器件的光谱响应与太阳辐射光谱不匹配， 高光子通量的红光区没有被有效利用 以及载流子的电极收集效率低等。 为了使聚合物太阳能电池得到实际的应用， 开发新型的材料， 大幅度提高其能量转换效率仍是这一研究领域的首要任务。
【发明内容】
基于此， 有必要提供一种光电转换效率高的基于茈四羧酸二酰亚胺和苯并 二噻吩的共轭聚合物。
此外， 还有必要提供一种该光电转换效率高的基于茈四羧酸二酰亚胺和苯 并二噻吩的共轭聚合物的制备方法。
一种基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚合物， 通式如下：
Figure imgf000004_0001
其中， n为小于 101 的正整数； R2、 R3为氢、 CH^o的烷基、 （^〜020 烷氧基苯或苯基； R4、 R5为 CH^Q的烷基。
一种基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚合物的制备方法， 包括 如下步骤：
S11、 将茈四羧酸二酰亚胺二溴代物或其衍生物和含苯并二噻。分单元的有机 锡化合物按摩尔比 1 : 1-1.5: 1混合溶解在有机溶剂中；
S12、 无氧环境下， 往步骤 S11 中加入催化剂， 并在 50〜120°C下进行 Stille 偶合反应 24〜72小时， 得到所述共轭聚合物溶液， 反应方程式如下：
Figure imgf000005_0001
优选的， 步骤 Sll中， 有机溶剂为选自四氢呋喃、 二曱基酰胺、 二氧六环、 乙二醇二曱醚、 苯和曱苯中的一种或几种； 步骤 S12 中， 催化剂加入量为总物 质摩尔数的 0.01%〜5%； 催化剂为有机钯或有机钯和有机膦配体的混合物； 有机 钯为选自 Pd2(dba)3、 Pd(PPh3)4和 Pd(PPh3)2Cl2中的一种或几种； 有机膦配体为 P(o-Tol)3; 有机钯和有机膦配体的混合物中两者摩尔比为 1 : 2〜1： 20。
优选的， 所述共轭聚合物的制备方法还包括得到所述共轭聚合物溶液后的 纯化过程， 具体步骤如下：
S13、 将所述共轭聚合物溶液滴加到曱醇中， 进行沉降处理， 然后抽滤， 曱 醇洗涤， 干燥， 得到含共轭聚合物的胶体； S14、 将含共轭聚合物的胶体溶解于 曱苯中， 并将该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中， 80 ~ 100°C加热搅拌后通过氧化铝柱层析， 分离出共轭聚合物， 氯苯淋洗后减压除去 有机溶剂； S15、 重复步骤 S13至少一次， 并用丙酮索氏提取步骤 S14中分离出 来的共轭聚合物， 得到共轭聚合物固体。
一种采用上述基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚合物制备的太 阳能电池器件， 包括依次排列的如下结构： 衬底、 导电层、 聚 3 , 4-亚乙二氧基 噻吩： 聚苯乙烯磺酸层、 具有活性作用的共轭聚合物层和铝金属层。
一种上述太阳能电池器件的制造方法， 包括如下步骤：
521、 清洗衬底， 并在衬底的一个表面沉积一层导电层；
522、 对所述导电层进行表面处理后， 在所述导电层上涂覆聚 3 , 4-亚乙二 氧基噻吩： 聚苯乙烯磺酸， 形成聚 3 , 4-亚乙二氧基噻吩： 聚苯乙烯磺酸层； 523、 在所述聚 3 , 4-亚乙二氧基噻吩： 聚苯乙烯磺酸层上涂覆所述共轭聚 合物， 形成具有活性作用的共轭聚合物层；
524、 在所述共轭聚合物层上设置铝金属层， 得到所述太阳能电池器件。 一种采用上述基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚合物制备的有 机电致发光器件， 包括依次排列的如下结构： 衬底、 导电层、 具有发光性能的 共轭聚合物层、 LiF緩冲层和铝金属层。
一种上述有机电致发光器件的制备方法， 包括如下步骤：
531、 清洗衬底， 并在衬底的一个表面沉积一层导电层；
532、对所述导电层进行表面处理后，在所述导电层上涂覆所述共轭聚合物， 形成具有发光作用的共轭聚合物层；
533、 在所述共轭聚合物层上蒸镀 LiF, 形成 LiF緩冲层；
534、 在所述 LiF緩冲层上设置铝金属层， 得到所述有机电致发光器件。 一种采用上述基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚合物制备的有 机场效应晶体管， 包括依次排列的如下结构： 掺杂硅衬底、 Si02绝缘层、 十八 烷基三氯硅烷层、 共轭聚合物有机半导体层、 金属材质的源电极和漏电极。
一种上述有机场效应晶体管的制备方法， 包括如下步骤：
541、 清洗掺杂硅衬底， 沉积具有绝缘作用的 Si02绝缘层；
542、在所述 Si02绝缘层上涂覆十八烷基三氯硅烷，形成十八烷基三氯硅烷 层；
543、 在所述十八烷基三氯硅烷层上涂覆所述共轭聚合物， 形成共轭聚合物 有机半导体层；
544、 在所述共轭聚合物有机半导体层上设置金属材质的源电极和漏电极， 得到所述有机场效应晶体管。
茈四象 S史二酰亚胺及其衍生物具有大的共苯环平面结构和两个亚胺环结 构， 在可见光区域有很强的吸收， 具有较高的光、 热和环境稳定性， 具有较高 电子亲和能 (较低的 LUMO 能级)， 并且由于其共轭大 π键之间的 π-π堆叠使沿 堆叠方向具有很高的电子迁移率， 因此， 它在有机太阳电池等多种领域都显现 出广阔的应用前景。 所述共轭聚合物， 通过在茈四羧酸二酰亚胺 "bay" 位置引入取代基， 及通 过茈四羧酸二酰亚胺单体与其他单体共聚， 增加了茈四羧酸二酰亚胺的溶解性。 另外， 苯并二噻吩单元是同时含有两个五元环和一个六元环骨架的具有优良的 平面结构的单元， 由于其良好的平面度和共轭度， 其迁移率 4艮高， 并且苯并二 噻。分单元上的 4, 5位可以引入烷基等修饰来提高其溶解性， 并改善其可溶性加 工性能。 因此， 将其与茈四羧酸二酰亚胺共聚， 形成电子给体 -受体结构， 来调 节聚合物的带隙， 并将其吸收带边推向红外及近红外区， 具有较高的光电转换 效率。
该共轭聚合物的制备方法简便可行， 设备要求低， 实用性强。 【附图说明】
图 1为太阳能电池器件一实施例的结构示意图；
图 2为有机电致发光器件一实施例的结构示意图；
图 3为有机场效应晶体管一实施例的结构示意图。
【具体实施方式】
本发明的目的在于提供一种基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚 合物， 该共轭聚合物溶解性好， 光吸收波-潜宽， 具有较高的光电转换效率。 本 发明还提供一种该共轭聚合物的制备方法， 同时指出该共轭聚合物在光电领域 的应用。
一种基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚合物， 通式如下：
Figure imgf000008_0001
其中， n为小于 101 的正整数； R2、 R3为氢、 CH^o的烷基、 （^〜020 烷氧基苯或苯基； R4、 R5为 CH^Q的烷基。
一种基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚合物的制备方法， 包括 如下步骤：
S11、 将茈四羧酸二酰亚胺二溴代物或其衍生物和含苯并二噻。分单元的有机 锡化合物按摩尔比 1 : 1-1.5: 1混合溶解在有机溶剂中；
S12、在无氧环境下，往步骤 S11中加入催化剂，并在 50〜120 下进行8 ^ 偶合反应 24〜72小时， 得到所述共轭聚合物溶液， 反应方程式如下：
Figure imgf000008_0002
优选的， 步骤 Sll中， 有机溶剂为选自四氢呋喃、 二曱基酰胺、 二氧六环、 乙二醇二曱醚、 苯和曱苯中的一种或几种； 步骤 S12 中， 无氧环境为氮气或惰 性气体组成； 催化剂加入量为总物质摩尔数的 0.01%〜5%； 催化剂为有机钯或有 机钯和有机膦配体的混合物； 有机钯为选自 Pd2(dba)3、 Pd(PPh3)4和 Pd(PPh3)2Cl2 中的一种或几种； 有机膦配体为 P(o-Tol)3; 有机钯和有机膦配体的混合物中两 者摩尔比为 1 : 2〜1： 20。
优选的， 所述共轭聚合物的制备方法还包括得到所述共轭聚合物溶液后的 纯化过程， 具体步骤如下：
S13、 将所述共轭聚合物溶液滴加到曱醇中， 进行沉降处理， 然后抽滤， 曱 醇洗涤， 干燥， 得含共轭聚合物的胶体； S14、 将含共轭聚合物的胶体溶解于曱 苯中， 并将该曱苯溶液加入到二乙基二硫代氨基曱 S史钠的水溶液中， 80 ~ 100°C 加热搅拌后过氧化铝柱层析， 分离出共轭聚合物， 氯苯淋洗后减压除去有机溶 剂； S15、 重复步骤 S13至少一次， 并用丙酮索氏提取步骤 S14中分离出来的共 轭聚合物， 得到共轭聚合物固体。
该共轭聚合物的制备方法简便可行， 设备要求低， 实用性强。
该共轭聚合物在光电领域有着广泛的应用前景， 例如用于太阳能电池器件、 有机电致发光器件以及有机场效应晶体管等。
如图 1所示的一种太阳能电池器件， 包括依次排列的如下结构： 衬底 110、 导电层 120、 聚 3 , 4-亚乙二氧基噻吩： 聚苯乙婦横酸层 130、 具有活性作用的 采用前述共轭聚合物制备的共轭聚合物层 140和铝金属层 150。
上述太阳能电池器件的制造方法， 包括如下步骤：
521、 清洗衬底， 并在衬底的一个表面沉积一层导电层；
522、 对所述导电层进行表面处理后， 在所述导电层上涂覆聚 3 , 4-亚乙二 氧基噻吩： 聚苯乙烯磺酸形成聚 3 , 4-亚乙二氧基噻吩： 聚苯乙烯磺酸层；
523、 在所述聚 3 , 4-亚乙二氧基噻吩： 聚苯乙烯磺酸层上涂覆所述共轭聚 合物， 形成具有活性作用的共轭聚合物层；
524、 在所述共轭聚合物层上设置铝金属层， 得到所述太阳能电池器件。 在优选的实施例中， 衬底基材采用 ITO玻璃（铟锡氧化物玻璃）， 玻璃作为 衬底， 方块电阻为 10-20Ω/口的铟锡氧化物作为导电层， 步骤 S22中表面处理过 程采用氧 -Plasma (等离子）处理， 所述共轭聚合物采用旋涂技术涂覆于聚 3 , 4-亚乙二氧基噻吩： 聚苯乙婦横酸层上。 如图 2所示的一种有机电致发光器件，包括依次排列的如下结构：衬底 210、 导电层 220、具有发光性能的采用前述共轭聚合物制备的共轭聚合物层 230、 LiF 緩冲层 240和铝金属层 250。
上述有机电致发光器件的制备方法， 包括如下步骤：
531、 清洗衬底， 并在衬底的一个表面沉积一层导电层；
532、对所述导电层进行表面处理后，在所述导电层上涂覆所述共轭聚合物， 形成具有发光作用的共轭聚合物层；
533、 在所述共轭聚合物层上蒸镀 LiF, 形成 LiF緩冲层；
534、 在所述 LiF緩冲层上设置金属铝层， 得到所述有机电致发光器件。 在优选的实施例中， 衬底基材采用 ITO玻璃（铟锡氧化物玻璃）， 玻璃作为 衬底， 方块电阻为 10-20Ω/口的铟锡氧化物作为导电层， 步骤 S22中表面处理过 程采用氧 -Plasma (等离子）处理， 所述共轭聚合物采用旋涂技术涂覆于聚 3 , 4-亚乙二氧基噻吩： 聚苯乙婦横酸层上。
如图 3所示的一种有机场效应晶体管， 包括自下而上依次排列的如下结构： 掺杂硅衬底 310、 Si02绝缘层 320、 十八烷基三氯硅烷层 330、 采用前述共轭聚 合物制备的共轭聚合物有机半导体层 340、金属材质的源电极 350和漏电极 360。
上述有机场效应晶体管的制备方法， 包括如下步骤：
541、 清洗掺杂硅衬底， 沉积具有绝缘作用的 Si02绝缘层；
542、在所述 Si02绝缘层上涂覆十八烷基三氯硅烷，形成十八烷基三氯硅烷 层；
543、 在所述十八烷基三氯硅烷层上涂覆所述共轭聚合物， 形成共轭聚合物 有机半导体层；
544、 在所述共轭聚合物有机半导体层上设置金属材质的源电极和漏电极， 得到所述有机场效应晶体管。
在优选的实施例中， 掺杂硅衬底采用高掺杂的硅片， Si02绝缘层厚度为 500nm, 所述共轭聚合物采用旋涂技术涂覆于十八烷基三氯硅烷层上， 所述源电 极和漏电极采用金制作。 下面主要结合具体实施例对本发明的共轭聚合物及其制备方法作进一步的 说明。
实施例 1
聚 N, Ν'-二 -(3, 4, 5-三-曱基苯) -3, 4, 9, 10-茈二酰亚胺- ( 4, 5-二己基）苯并 [2,l-b:3,4-b，
Figure imgf000011_0001
在氮气保护下，往含有 0.5mmol N, Ν'-二 -(3, 4, 5-三-曱基苯) -1, 7-二溴 -3, 4, 9, 10-茈二酰亚胺和 0.5mmol 2, 7-双三丁基锡- ( 4, 5-二-己基）苯并 [2,l-b:3,4-b，]二 噻吩的 DMF ( 18mL )溶液中鼓泡 0.5h 除去氧气， 然后加入 Pd2(dba)3 ( 0.14 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ), 鼓泡 0.5h除去残留的氧气， 加热到 80。C反应 48小时， 得到共轭聚合物溶液。 将所述共轭聚合物溶液滴加 到曱醇中， 进行沉降处理， 然后抽滤， 干燥， 得到含共轭聚合物的胶体。 将含 共轭聚合物的胶体溶解于曱苯中， 并将该曱苯溶液加入到二乙基二硫代氨基曱 酸钠的水溶液中， 90°C加热搅拌后过氧化铝柱层析， 分离出共轭聚合物， 氯苯 淋洗后减压除去有机溶剂。 将分离出的共轭聚合物加入到曱醇中进行沉降， 然 后抽滤， 曱醇洗涤， 干燥后用丙酮索氏提取共轭聚合物， 得到共轭聚合物固体。 Molecular weight ( GPC, THF, R. I): Mn = 24,300, MJMn = 2.66。 实施例 2
聚 N, N，-二 -(3, 4, 5-三-曱烷氧基苯) -3, 4, 9, 10-茈二酰亚胺- ( 4 -己基 -5-癸基 ) 苯并 [2,l-b:3,4-b，]二噻吩的制备
Figure imgf000012_0001
在氮气保护下，往含有 0.5mmol Ν, Ν'-二 -(3, 4, 5-三-曱烷氧基苯) -1, 7-二溴 -3, 4, 9, 10-茈二酰亚胺和 0.5mmol 2, 7-双三丁基锡- ( 4-己基 -5-癸基） 苯并 [2,l-b:3,4-b，]二噻吩的二氧六环 （15mL )溶液中鼓泡 0.5h 除去氧气， 然后加入 Pd(PPh3)2Cl2 10mg, 鼓泡 0.5h除去残留的氧气, 加热到 85。C反应 36小时， 得 到共轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱醇中， 进行沉降处理， 然 后抽滤， 干燥， 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯 中， 并将该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中， 90°C加热搅 拌后过氧化铝柱层析， 分离出共轭聚合物， 氯苯淋洗后减压除去有机溶剂。 将 分离出的共轭聚合物加入到曱醇中进行沉降， 然后抽滤， 曱醇洗涤， 干燥后用 丙酮索氏提取共轭聚合物 ,得到共轭聚合物固体。 Molecular weight ( GPC, THF, R. I): Mn = 24,200, MJMn = 2.57; ) 实施例 3
聚 N, Ν'-二 -(3, 4, 5-三-辛氧基苯 )-3, 4, 9, 10-茈二酰亚胺- ( 4, 5-二-二十烷基 ) 苯并 [2,l-b:3,4-b，]二噻吩的制备
Figure imgf000013_0001
在氮气保护下，往含有 0.5mmol Ν, Ν'-二 -(3, 4, 5-三-辛氧基苯 )-1, 7-二溴 -3, 4, 9, 10-茈二酰亚胺和 0.5mmol 2, 7-双三丁基锡- ( 4, 5-二 -二十烷基） 苯并 [2,l-b:3,4-b，]二噻吩的曱苯 /THF ( 30mL )溶液中鼓泡 0.5h 除去氧气， 然后加入 Pd(PPh3)48mg, 鼓泡 0.5h除去残留的氧气,， 加热到 80。C反应 72小时， 得到共 轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱醇中， 进行沉降处理， 然后抽 滤， 干燥， 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中， 并将该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中， 80°C加热搅拌后 过氧化铝柱层析， 分离出共轭聚合物， 氯苯淋洗后减压除去有机溶剂。 将分离 出的共轭聚合物加入到曱醇中进行沉降， 然后抽滤， 曱醇洗涤， 干燥后用丙酮 索氏提取共轭聚合物，得到共轭聚合物固体。 Molecular weight ( GPC, THF, R. I): Mn = 22,000, M Mn = 2.65。 实施例 4
聚 Ν, Ν'-二 -(3, 5-二 -二十烷氧基 -4-曱基苯 )-3, 4, 9, 10-茈二酰亚胺- ( 4, 5-二- 十二烷氧基 )苯并 [2,l-b:3,4-b，]二噻吩的制备
Figure imgf000014_0001
在氮气保护下， 往含有 0.52mmol N, N，-二 -(3, 5-二 -二十烷氧基 -4-曱基苯 )-1, 7-二溴 -3, 4, 9, 10-茈二酰亚胺和 0.5mmol 2, 7-双三丁基锡- ( 4, 5-二 -十二烷氧基 ) 苯并 [2,l-b:3,4-b，]二噻吩的苯（20mL )溶液中鼓泡 0.5h 除去的氧气， 然后加入 Pd(PPh3)2Cl2 5mg, 鼓泡 0.5h除去残留的氧气,加热到 100。C反应 56小时， 得到 共轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱醇中， 进行沉降处理， 然后 抽滤， 干燥， 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中， 并将该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中， 80 °C加热搅拌后 过氧化铝柱层析， 分离出共轭聚合物， 氯苯淋洗后减压除去有机溶剂。 将分离 出的共轭聚合物加入到曱醇中进行沉降， 然后抽滤， 曱醇洗涤， 干燥后用丙酮 索氏提取共轭聚合物 ,得到共轭聚合物固体。 Molecular weight ( GPC, THF, R. I): Mn = 25,600, M Mn = 3.76。 实施例 5
聚 N, Ν'-二 -(3, 5-二-二十基苯 )-3, 4, 9, 10-茈二酰亚胺- ( 4-曱基 -5-曱氧基 )苯 并 [2,l-b:3,4-b，]二噻吩
Figure imgf000015_0001
在氮气保护下，往含有 0.51mmol N, N'-二 -(3, 5-二-二十基苯 )-1, 7-二溴 -3, 4, 9, 10-茈二酰亚胺和 0.5mmol 2, 7-双三丁基锡- ( 4-曱基 -5-曱氧基） 苯并 [2,l-b:3,4-b，]二噻吩的曱苯 /DMF ( 25mL ) 溶液中鼓泡 0.5h 除去氧气， 加入 Pd(PPh3)4 10mg, 鼓泡 0.5h除去残留的氧气， 加热到 70。C反应 40小时， 得到共 轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱醇中， 进行沉降处理， 然后抽 滤， 干燥， 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中， 并将该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中， 80°C加热搅拌后 过氧化铝柱层析， 分离出共轭聚合物， 氯苯淋洗后减压除去有机溶剂。 将分离 出的共轭聚合物加入到曱醇中进行沉降， 然后抽滤， 曱醇洗涤， 干燥后用丙酮 索氏提取共轭聚合物 ,得到共轭聚合物固体。 Molecular weight ( GPC, THF, R. I): Mn = 23,300, M Mn = 2.44。 实施例 6
聚 N, Ν'-二 -(3, 4, 5-三-苯基苯) -3, 4, 9, 10-茈二酰亚胺- ( 4,4-二 -二十烷氧基 ) 苯并 [2,l-b:3,4-b，]二噻吩的制备
Figure imgf000016_0001
在氩气保护下，往含有 0.75mmo N, Ν'-二 -(3, 4, 5-三-苯基苯) -1, 7-二溴 -3, 4, 9 10-茈二酰亚胺 1 和 0.5mmol 2, 7-双三丁基锡- ( 4, 5-二-二十烷氧基） 苯并 [2,l-b:3,4-b，]二噻吩的二氧六环 /THF ( 18mL )溶液中鼓泡 0.5h 除去氧气， 加入 Pd(PPh3)2Cl2 8mg, 鼓泡 0.5h除去残留的氧气， 加热到 65。C反应 72小时， 得到 共轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱醇中， 进行沉降处理， 然后 抽滤， 干燥， 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中， 并将该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中， 90 °C加热搅拌后 过氧化铝柱层析， 分离出共轭聚合物， 氯苯淋洗后减压除去有机溶剂。 将分离 出的共轭聚合物加入到曱醇中进行沉降， 然后抽滤， 曱醇洗涤， 干燥后用丙酮 索氏提取共轭聚合物 , 得到共轭聚合物固体。 Molecular weight (GPC, THF, R. I): Mn = 28,900, MJMn = 2.37。
但并不能因此而理解为对本发明专利范围的限制。 应当指出的是， 对于本领域 的普通技术人员来说， 在不脱离本发明构思的前提下， 还可以做出若干变形和 改进， 这些都属于本发明的保护范围。 因此， 本发明专利的保护范围应以所附 权利要求为准。

Claims

权利要求书
1、 一种基于茈四羧酸二酰亚胺和苯并二噻。分的共轭聚合物， 通式如下:
Figure imgf000017_0001
其中， n为小于 101的正整数；
Ri、 R2、 R3为氢、 C^C^Q的烷基、 C^Q烷氧基苯或苯基；
R4、 R5为 C^C 的烷基。
2、 一种基于茈四羧酸二酰亚胺和苯并二噻吩的共轭聚合物的制备方法， 其 特征在于， 包括如下步骤：
S11、 将茈四羧酸二酰亚胺二溴代物或其衍生物和含苯并二噻。分单元的有机 锡化合物按摩尔比 1 : 1-1.5: 1混合溶解在有机溶剂中；
S12、 无氧环境下， 往步骤 S11 中加入催化剂， 并在 50〜120°C下进行 Stille 偶合反应 ， 得到所述共轭聚合物溶液， 反应方程式如下：
Figure imgf000017_0002
3、如权利要求 2所述的共轭聚合物的制备方法， 其特征在于， 步骤 S11中， 所述有机溶剂为选自四氢呋喃、 二曱基酰胺、 二氧六环、 乙二醇二曱醚、 苯和 曱苯中的一种或几种。
4、如权利要求 2所述的共轭聚合物的制备方法，其特征在于， 步骤 S12中， 所述催化剂加入量为总物质摩尔数的 0.01%〜5%；
所述催化剂为有机钯或有机钯和有机膦配体的混合物；
所述有机钯为选自 Pd2(dba)3、 Pd(PPh3)4和 Pd(PPh3)2Cl2中的一种或几种； 所述有机膦配体为 P(o-Tol)3;
所述有机钯和有机膦配体的混合物中， 有机钯与有机膦配体的摩尔比为 1 : 2〜1： 20。
5、 如权利要求 2所述的共轭聚合物的制备方法， 其特征在于， 还包括得到 所述共轭聚合物溶液后的纯化过程， 具体步骤如下：
513、 将所述共轭聚合物溶液滴加到曱醇中， 进行沉降处理， 然后抽滤， 曱 醇洗涤， 干燥， 得到含共轭聚合物的胶体；
514、 将含共轭聚合物的胶体溶解于曱苯中， 并将该曱苯溶液加入到二乙基 二硫代氨基曱酸钠的水溶液中， 80 ~ 100°C加热搅拌后过氧化铝柱层析， 分离出 共轭聚合物， 氯苯淋洗后减压除去有机溶剂；
515、 重复步骤 S13至少一次， 并用丙酮索氏提取步骤 S14中分离出来的共 轭聚合物， 得到共轭聚合物固体。
6、 一种采用权利要求 1所述共轭聚合物制备的太阳能电池器件， 其特征在 于， 包括依次排列的如下结构： 衬底、 导电层、 聚 3 , 4-亚乙二氧基噻吩： 聚苯 乙婦横酸层、 具有活性作用的共轭聚合物层和铝金属层。
7、 一种权利要求 6所述太阳能电池器件的制造方法， 其特征在于， 包括如 下步骤：
521、 清洗衬底， 并在衬底的一个表面沉积一层导电层；
522、 对所述导电层进行表面处理后， 在所述导电层上涂覆聚 3 , 4-亚乙二 氧基噻吩： 聚苯乙烯磺酸， 形成聚 3 , 4-亚乙二氧基噻吩： 聚苯乙烯磺酸层；
523、 在所述聚 3 , 4-亚乙二氧基噻吩： 聚苯乙烯磺酸层上涂覆所述共轭聚 合物， 形成具有活性作用的共轭聚合物层；
S24、 在所述共轭聚合物层上设置铝金属层， 得到所述太阳能电池器件。
8、 一种采用权利要求 1所述共轭聚合物制备的有机电致发光器件， 其特征 在于， 包括依次排列的如下结构： 衬底、 导电层、 具有发光性能的共轭聚合物 层、 LiF緩冲层和铝金属层。
9、 一种权利要求 8所述有机电致发光器件的制备方法， 其特征在于， 包括 如下步骤：
531、 清洗衬底， 并在衬底的一个表面沉积一层导电层；
532、对所述导电层进行表面处理后，在所述导电层上涂覆所述共轭聚合物， 形成具有发光作用的共轭聚合物层；
533、 在所述共轭聚合物层上蒸镀 LiF, 形成 LiF緩冲层；
534、 在所述 LiF緩冲层上设置铝金属层， 得到所述有机电致发光器件。
10、 一种采用权利要求 1 所述共轭聚合物制备的有机场效应晶体管， 其特 征在于， 包括依次排列的如下结构： 掺杂硅衬底、 Si02绝缘层、 十八烷基三氯 硅烷层、 共轭聚合物有机半导体层、 金属材质的源电极和漏电极。
11、 一种权利要求 10所述有机场效应晶体管的制备方法， 其特征在于， 包 括如下步骤：
541、 清洗掺杂硅衬底， 沉积具有绝缘作用的 Si02绝缘层；
542、在所述 Si02绝缘层上涂覆十八烷基三氯硅烷，形成十八烷基三氯硅烷 层；
543、 在所述十八烷基三氯硅烷层上涂覆所述共轭聚合物， 形成共轭聚合物 有机半导体层；
544、 在所述共轭聚合物有机半导体层上设置金属材质的源电极和漏电极， 得到所述有机场效应晶体管。
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