WO2011094950A1 - 含芴共轭聚合物、其制备方法和太阳能电池器件 - Google Patents

含芴共轭聚合物、其制备方法和太阳能电池器件 Download PDF

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WO2011094950A1
WO2011094950A1 PCT/CN2010/070551 CN2010070551W WO2011094950A1 WO 2011094950 A1 WO2011094950 A1 WO 2011094950A1 CN 2010070551 W CN2010070551 W CN 2010070551W WO 2011094950 A1 WO2011094950 A1 WO 2011094950A1
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conjugated polymer
ruthenium
containing conjugated
represented
polymer
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PCT/CN2010/070551
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French (fr)
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周明杰
黄杰
刘辉
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海洋王照明科技股份有限公司
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Priority to CN201080048107.3A priority Critical patent/CN102686636B/zh
Priority to US13/575,667 priority patent/US20120312374A1/en
Priority to EP10845035.4A priority patent/EP2532696A4/en
Priority to JP2012551464A priority patent/JP5599903B2/ja
Priority to PCT/CN2010/070551 priority patent/WO2011094950A1/zh
Publication of WO2011094950A1 publication Critical patent/WO2011094950A1/zh

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Definitions

  • the present invention relates to the field of organic materials, and in particular to a cerium-containing conjugated polymer, a method for preparing the same, and a solar cell device.
  • 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. However, to the eyes Until now, the photoelectric conversion efficiency of organic solar cells has been lower than that of inorganic solar cells. Therefore, the development of new organic materials is of great significance for improving the efficiency of organic solar cells and other semiconductor devices or optoelectronic devices. Summary of the invention
  • a ruthenium-containing conjugated polymer having a broad response to light and stability and a preparation method of a ruthenium-containing conjugated polymer having a simple synthesis route and low cost are provided.
  • Embodiments of the present invention also provide a solar cell device having the above ruthenium-containing conjugated polymer.
  • a ruthenium-containing conjugated polymer comprising the polymer represented by the following structural formula (1):
  • a method for preparing a ruthenium containing conjugated polymer comprising the steps of:
  • the compound A, B, and C are subjected to a Suzuki reaction in the presence of a catalyst, a solvent, and an alkaline solution to obtain a polymer represented by the following structural formula (1):
  • n in the structural formula (1) is a natural number between 1 and 1000.
  • a solar cell device comprising a glass substrate, a transparent anode, an intermediate auxiliary layer, an active layer and a cathode which are sequentially laminated, the active layer comprising an electron donor material and an electron acceptor material, wherein the electron donor material is The above ruthenium-containing conjugated polymer.
  • ruthenium-containing conjugated polymer ruthenium or a derivative thereof contained has excellent photostability and thermal stability, and thiophene is introduced into the polymer main chain. Subgroup, due to thiophene.
  • the fraction is a five-membered ring structure, conforming to the Hugh's rule, with a moderate energy band gap, a wide spectral response, good thermal stability and environmental stability, which helps to broaden the optical response range of the polymer.
  • the benzothiadiazole group is also introduced into the main chain of the polymer, and has a five-membered ring structure and a conjugated diene structure, which not only produces a similar action to the thiophene, but also functions as a conjugated diene.
  • the spectral response range of a wide polymer is also introduced into the main chain of the polymer, and has a five-membered ring structure and a conjugated diene structure, which not only produces a similar action to the thiophene, but also functions as a conjugated diene.
  • these introduced groups have a macrocyclic ring and/or a fused ring structure, which can increase the electron cloud density of the polymer skeleton, so that the absorption spectrum of the ruthenium-containing conjugated polymer can be adjusted over a wide range, which makes These materials can have a wider spectral response range, and when used as a photovoltaic material, they can better match the solar emission spectrum and make full use of solar energy.
  • a relatively simple synthesis route is adopted, which is basically a one-step synthesis, thereby reducing the process flow and reducing the manufacturing cost.
  • the above solar cell device can not only improve its photoelectric conversion efficiency but also reduce the quality of the solar cell device by using a ruthenium-containing conjugated polymer, thereby facilitating mass production.
  • FIG. 1 is a schematic view showing the structural formula of a ruthenium-containing conjugated polymer according to an embodiment of the present invention
  • FIG. 2 is a flow chart showing a preparation method of a ruthenium-containing conjugated polymer according to an embodiment of the present invention
  • FIG. 3 is a schematic view showing the structure of a solar cell device containing a ruthenium-containing conjugated polymer according to an embodiment of the present invention
  • a structural formula of a ruthenium-containing conjugated polymer of an embodiment of the present invention i.e., a polymer represented by the following structural formula (1):
  • ⁇ ⁇ is selected from at least one of the groups represented by the structural formula:
  • R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are the same or different alkyl groups represented by H or dC ⁇ , and R u , R 12 , R 13 , R 14 and R 15 are the same Or a different alkyl group represented by C C20 , m is a natural number between 1 and 20.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 1 () are the same or different alkyl groups represented by H or dC 6
  • R u , R 12 , R 13 , R 14 , R 15 is preferably the same or different alkyl group represented by C Qs
  • m is preferably a natural number between 2 and 10.
  • the group represented by the formula (c), R 7 and R 8 are preferably H, that is, the ⁇ ⁇ formula is represented by -C 6 H 2 S 2 -.
  • the preparation method of the above ruthenium-containing conjugated polymer comprises the following steps:
  • R 2 , R 3 , and R 4 are the same or different alkyl groups represented by H or dC ⁇ , and the molar fractions of the reaction amounts of the compounds B and C are X and y, respectively.
  • y l , x ⁇ 0, y ⁇ 0, the group containing a thiophene;
  • n in the structural formula (1) A natural number between 1 and 1000.
  • the compounds A, B, and C can be directly obtained from the market or prepared by an existing synthesis method.
  • x and y are both 50%.
  • 1 and may be the same linear alkyl group, preferably C 8 H 17 , that is, an isomer of n-octyl or octyl group, more preferably an n-octyl group.
  • R 3 and R 4 are each preferably hydrogen.
  • n is preferably from 30 to 800, more preferably from 50 to 500.
  • ⁇ ⁇ is selected from at least one of the groups represented by the above structural formulae (a) - (g), preferably, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same Or a different alkyl group represented by 11 or dC 6 , R u , R 12 , R 13 , R 14 , R 15 are preferably the same or different alkyl group represented by -C 6 , and m is preferably between 2 and 10 Natural number.
  • A is a group represented by the formula (c), and R 7 and R 8 are preferably H, that is, the formula A is represented by -C 6 H 2 S 2 -.
  • the catalyst may be an organic palladium catalyst in an amount of from 0.1 to 20% by mole based on the amount of the compound A.
  • the organic palladium catalyst may be, for example but not limited to, Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 .
  • the alkaline solution may be an inorganic alkali solution or an organic alkali solution, and the inorganic alkali solution may be an aqueous solution of an alkali metal hydroxide or an alkali metal carbonate, and may be, for example, but not limited to, a sodium hydroxide solution, a potassium hydroxide solution, or a sodium carbonate.
  • the solution, the potassium carbonate solution or the like is preferably a sodium carbonate solution
  • the organic alkali solution may be an aqueous solution of an alkyl ammonium hydroxide, such as, but not limited to, tetradecyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl hydroxide.
  • the above alkaline solution may be used in an amount of from 1 to 10 times the molar amount of the compound A.
  • the solvent is a weakly polar or polar aprotic organic solvent or a mixed solvent thereof, and may be, for example but not limited to, chloroform, dichlorodecane, dimercaptosulfoxide (DMSO), tetrahydrofuran (THF), toluene, diterpene Benzene or a similar compound thereof is preferably anthracene.
  • the solvent is used in an amount sufficient to dissolve the respective reactants and sufficiently react.
  • step S02 The reaction carried out in step S02 can be expressed by the following reaction equation (i):
  • step S02 is carried out under the protection of nitrogen. After adding each raw material and reagent, it is first replaced with nitrogen for 0.5-3 hours, then heated to reflux, reacted for 1-5 days, and then reacted with bromobenzene under reflux. After 24 hours, the reaction was continued for a further 6-24 hours by the addition of phenylboronic acid to give the product.
  • reaction product may be further subjected to the following purification step: the solvent is removed under reduced pressure, extracted with chloroform/water, washed, dried, and the chloroform is removed under reduced pressure, precipitated with decyl alcohol, suction filtered, and the precipitate is filtered off with chloroform.
  • the washing agent was separated by alumina column chromatography, rotary-scrayed, sedimented with methanol, and suction filtered.
  • the obtained solid was subjected to Soxhlet extraction with acetone for three days, sedimented with decyl alcohol, suction filtered, and the precipitate was filtered off under vacuum to obtain a solid. ⁇ Conjugated polymer.
  • the solvent is distilled off under reduced pressure, extracted with chloroform/water, washed with saturated brine, and dried over anhydrous sodium sulfate. Then, the dried product was evaporated to dryness under reduced pressure to a large amount of chloroform, which was precipitated with methanol and filtered. The precipitate was filtered off and separated by alumina column chromatography with chloroform as the eluent. The mixture was subjected to rotary distillation, and the mixture was filtered with decyl alcohol. The obtained solid was subjected to Soxhlet extraction with acetone for three days, and then decyl alcohol was precipitated, suction filtered, vacuum. The precipitate was filtered off to give a solid product in a yield of about 60-85%.
  • the synthesis routes of the three monomers of the compounds A, B and C are relatively simple and mature, and are basically one-step synthesis, thereby reducing the process flow and reducing the manufacturing cost.
  • the Suzuki reaction is a very mature polymerization reaction with high yield, mild conditions, easy control, and easy introduction of an alkyl group to increase the solubility and molecular weight of the product to achieve a spin-coatable polymer.
  • a solar cell device using the ruthenium-containing conjugated polymer in the above embodiment comprises a glass base layer 11 , a transparent anode 12 , an intermediate auxiliary layer 13 , an active layer 14 , and a cathode 15 which are sequentially laminated.
  • the intermediate auxiliary layer 13 is made of polyethylene dioxythiophene: polystyrene-cross-acid composite (referred to as PEDOT: PSS), the active layer 14 comprises an electron donor material and an electron acceptor material, the electron donor material adopts the above-mentioned ruthenium-containing conjugated polymer, and the electron acceptor material may be [6,6]phenyl-C 61 -butyrate Ester (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 may be an aluminum electrode or a bimetal electrode such as Ca/Al or Ba/Al.
  • the glass base layer 11 can be used as a bottom layer.
  • ITO glass is selected, and after ultrasonic cleaning, treated with oxygen-Plasma, the intermediate auxiliary layer 13 is coated on the ITO glass, and the ytterbium-containing conjugated polymer and electrons are subjected to
  • the bulk material is applied to the intermediate auxiliary layer 13 by blending 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 transparent anode 12, the intermediate auxiliary layer 13, the active layer 14, the bimetal layer Ca, and the A1 layer have thicknesses of 160 nm, 40 nm, 150 nm, 20 nm, and 70 nm, respectively.
  • the ytterbium-containing conjugated polymer in the active layer 14 absorbs light energy and generates excitons, which then migrate to the electron donor/ At the interface of the acceptor material, electrons are transferred to an electron acceptor material, such as PCBM, to separate the charge, thereby forming free carriers, ie free electrons and holes. These free electrons are transported along the electron acceptor material to the metal cathode and collected by the cathode. Free holes are transported along the electron donor material to the ITO anode and collected by the anode, thereby forming photocurrent and photovoltage for photoelectric conversion, external connection. When the load is 16, it can be powered.
  • the polymer Since the polymer has thiophene.
  • these introduced groups have a macrocyclic ring and/or a fused ring structure, which can increase the electron cloud density of the polymer skeleton, so that the absorption spectrum of the ruthenium-containing conjugated polymer can be adjusted within a wide range. So that these materials can have a wider spectral response range, used as In the case of optoelectronic materials, it can better match the solar emission language, make full use of solar energy, and increase the power generation capacity of solar cell devices.
  • the organic material can also reduce the quality of the solar cell device, and can be fabricated by techniques such as spin coating, which is convenient for mass production.
  • the ytterbium-containing conjugated polymer can be applied not only to solar cell devices but also to electroluminescent devices, organic field effect transistors, organic optical memory devices, organic nonlinear materials or organic laser devices.
  • the preparation of the ruthenium-containing conjugated polymer and its properties and the like are exemplified below by way of a preferred embodiment.
  • the eighth, B, and C in the following embodiments are directly prepared, and of course, they may be directly purchased from the market in other embodiments, and are not limited thereto.
  • Compound A is prepared, wherein Compound A is 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolanyl)-9, 9- Take Dixinji as an example, its structural formula is as follows:
  • the specific preparation process was as follows: 1.44 mL (4.20 mmol) of n-butyllithium solution was added to a solution containing 1.10 g (2.00 mmol) of 2,7-dibromo-9, 9- under a nitrogen atmosphere at -78 °C. The two-necked flask of dioctylhydrazine and 20 mL of tetrahydrofuran was stirred for 10 minutes, then warmed to 0 ° C and stirring was continued for 20 minutes.
  • test results were: MALDI-TOF-MS (m/z): 642.5 (M + ).
  • a compound B is prepared in which the compound B is 2, 5-dibromothiophene [3, 2-b] thiophene. Divided into examples, its structural formula is:
  • the specific preparation process was as follows: 2.15 g (12.10 mmol) of NBS and 10 mL of DMF were added to an ice bath and protected from light to contain 0.84 g (6.00 mmol) of thiophene [3, 2-b] thiophene and 20 mL of DMF. Stir in the two-necked flask for 4 hours. After the reaction was completed, the reaction solution was poured into ice water and quenched, extracted with dichloromethane, washed once with deionized water, dried over anhydrous magnesium sulfate, and the filtrate was collected and then evaporated, and then separated by a neutral alumina column. The product was obtained as a pale yellow solid with a yield of 81%.
  • compound C is prepared, wherein compound C is exemplified by 4,7-dibromo-2,1-3-benzothiadiazole, and its structural formula is:
  • the specific preparation process is as follows: 13.6 g (100.00 mmol) of benzothiadiazole is weighed, dissolved in 20 mL of 45% hydrobromic acid, stirred under heating to reflux, and 48 g (300.00 mmol) of bromine is added dropwise. After the addition was completed, 10 mL of hydrobromic acid was added and reflux was continued for 3 hours. The reaction mixture was filtered while hot, cooled, filtered, washed with water, dried, chloroform, and crystals.
  • the third step the formation of the ruthenium-containing conjugated polymer, the structural formula of the ruthenium-containing conjugated polymer of the present embodiment is:
  • the specific formation process is as follows: Under nitrogen protection, it contains 0.321 g (0.50 mmol) of 2,7-bis(4 4,5,5-tetradecyl-1,3,2-dioxaborolanyl)- 9, 9-dioctylhydrazine, 0.0745 g (0.25 mmol) 2, 5-dibromothiophene [3, 2-b] thiophene, 0.0735 g (0.25 mmol) 4, 7-dibromo-2, 1, 3-benzothiadiazole, 0.00416 g (0.0036 mmol) Pd ( To the reactor of PPh 3 ) 4 was added 10 mL of a Na 2 C0 3 ( 2 M ) aqueous solution and toluene (20 mL).
  • Alumina column chromatography was carried out using chloroform as a eluent, and the mixture was subjected to rotary distillation, decyl alcohol, and suction filtration, and the obtained solid was subjected to Soxhlet extraction with acetone for three days. The decyl alcohol was precipitated, suction filtered, and dried in vacuo to give a solid material.
  • ruthenium-containing conjugated polymer ruthenium or a derivative thereof contained has excellent photostability and thermal stability, and thiophene is introduced into the polymer main chain. Subgroup, due to thiophene.
  • the fraction is a five-membered ring structure, conforming to the Hugh's rule, with a moderate energy band gap, a wide spectral response, good thermal stability and environmental stability, which helps to broaden the optical response range of the polymer.
  • the benzothiadiazole group is also introduced into the main chain of the polymer, and has a five-membered ring structure and a conjugated diene structure, which not only produces a similar action to the thiophene, but also functions as a conjugated diene.
  • the spectral response range of a wide polymer is also introduced into the main chain of the polymer, and has a five-membered ring structure and a conjugated diene structure, which not only produces a similar action to the thiophene, but also functions as a conjugated diene.
  • these introduced groups have a macrocyclic ring and/or a fused ring structure, which can increase the electron cloud density of the polymer skeleton, so that the absorption spectrum of the ruthenium-containing conjugated polymer can be adjusted over a wide range, which makes These materials can have a wider spectral response range, and when used as a photovoltaic material, they can better match the solar emission spectrum and make full use of solar energy.
  • a relatively simple synthesis route is adopted, which is basically a one-step synthesis, thereby reducing the process flow and reducing the manufacturing cost.
  • the above solar cell device adopts a ruthenium-containing conjugated polymer, which not only can improve its photoelectric conversion efficiency, but also can reduce the quality of the solar cell device, and is convenient for mass production.

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Description

含芴共轭聚合物、 其制备方法和太阳能电池器件 技术领域 本发明属于有机材料技术领域， 具体涉及一种含芴共轭聚合物、 其制备方 法和太阳能电池器件。
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。
为充分利用太阳光照射的能量， 人们不断开发出能够吸收太阳光的新型材 料， 其中无机半导体材料获得较为广泛的发展和应用， 例如目前用于地面的硅 晶电池， 然而由于其生产工艺复杂、 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替代的半导体材料。
近年来，有机材料逐渐引起人们广泛的兴趣，例如，在 1992年 N. S. Sariciftci 等报道了共轭聚合物与 C6。之间的光诱导电子转移现象后， 人们在共轭聚合物 用作太阳能电池等方面投入了大量研究， 并取得了飞速的发展。 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。
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。 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 ^艮多。 因 此， 开发新型的有机材料对于提高有机太阳能电池及其它半导体器件或光电器 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、 稳定性好的含芴共轭聚合物， 以及一种 合成路线简单、 成本低的含芴共轭聚合物制备方法。
本发明实施例还提供一种具有上述含芴共轭聚合物的太阳能电池器件。 一种含芴共轭聚合物， 其包含如下结构式（1 )表示的聚合物：
Figure imgf000004_0001
式中： R2、 R3、 R4为相同或不同的表示为 11或 d-C^的烷基， x+y=l , x≠0, y≠0, n为 1-1000之间的自然数， Αι^为含噻吩的基团。
一种含芴共轭聚合物制备方法， 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,
Figure imgf000004_0002
C:
Figure imgf000004_0003
，其中： R2、 R3、 R4为相同或不同的表示为 H或 d-C2C 的烷基,化合物 B和 C的反应计量占两者总量的摩尔分数分别为 X和 y, x+y=l , x≠0, y≠0, A 为含噻吩的基团； 在催化剂、溶剂以及碱性溶液存在的条件下，将化合物 A、 B、 C进行 Suzuki 合反应， 获得如下结构式 (1)表示的聚合物：
Figure imgf000005_0001
结构式 (1)中的 n为 1-1000之间的自然数。
以及， 一种太阳能电池器件， 其包括依次层叠的玻璃基层、 透明阳极、 中 间辅助层、 活性层及阴极， 所述活性层包括电子给体材料和电子受体材料， 所 述电子给体材料采用上述含芴共轭聚合物。
在上述含芴共轭聚合物中， 所含的芴或其衍生物具有优异的光稳定性和热 稳定性， 而且该聚合物主链中引入噻。分基团， 由于噻。分是五元环结构， 符合休 克儿规则， 具有适中的能带隙， 较宽的光谱响应， 较好的热稳定性和环境稳定 性， 有助于加宽聚合物的光语响应范围。 同时该聚合物主链中还引入苯并噻二 唑基团， 具有五元环结构以及共轭双烯结构， 不仅能产生与噻吩类似的作用， 还能发挥共轭双烯的作用， 进一步加宽聚合物的光谱响应范围。 另外， 这些引 入的基团具有大环和 /或稠环结构， 能增大聚合物骨架的电子云密度， 使得含芴 共轭聚合物的吸收光谱可以在很大范围内进行调节， 这就使得这类材料可以具 有更宽的光谱响应范围， 用作光电材料时， 可更好的匹配太阳发射光谱， 充分 利用太阳能。 在上述含芴共轭聚合物制备方法中， 采用较简单的合成路线， 基 本上是一步合成， 从而减少工艺流程， 降低制造成本。 上述太阳能电池器件通 过采用含芴共轭聚合物， 不仅能提高其光电转换效率， 而且能减轻太阳能电池 器件的质量， 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是本发明实施例的含芴共轭聚合物的结构式的示意图；
图 2是本发明实施例的含芴共轭聚合物制备方法流程图；
图 3 是采用本发明实施例的含芴共轭聚合物的太阳能电池器件结构示意
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含芴共轭聚合物的结构式， 即包含如下 结构式（ 1 )表示的聚合物：
Figure imgf000006_0001
式中： R2、 R3、 R4为相同或不同的表示为 11或 d-C^的烷基， x+y=l , x≠0, y≠0, n为 1-1000之间的自然数， Αι^为含噻吩的基团。
在本发明的一些实施例中， X和 y的取值范围分别优选为： x=20%-80%, y=20%-80%。 在一个更优选的实施例中， X和 y的取值均为 50%。 1^和 可以 为相同的直链烷基， 优选为 C8H17, 即正辛基或辛基的同分异构体， 更优选为 正辛基。 R3和 R4均优选为氢。 n优选为 30-800, 更优选为 50-500。
在本发明的一些实施例中， ΑΓι选自如下结构式表示的基团中的至少一种：
Figure imgf000006_0002
Figure imgf000007_0001
其中： R5、 R6、 R7、 R8、 R9、 R10是相同或不同的表示为 H或 d-C^的烷 基， Ru、 R12、 R13 、 R14、 R15是相同或不同的表示为 C C20的烷基， m为 1-20 之间的自然数。 优选地， R5、 R6、 R7、 R8、 R9、 R1()是相同或不同的表示为 H 或 d-C6的烷基， Ru、 R12、 R13 、 R14、 R15优选为相同或不同的表示为 C Qs 的烷基， m优选为 2-10之间的自然数。 在本发明的一个较佳实施例中， 入 为 结构式（c )表示的基团， R7、 R8优选为 H, 即 ΑΓι分子式表示为 -C6H2S2-。
请参阅图 2, 上述含芴共轭聚合物的制备方法包括如下步骤：
S01 : 分别提供如下结构式表示的化合物 A、 B、 C,
A:
Figure imgf000007_0002
, 其中： 、 R2、 R3、 R4为相同或不同的表示为 H或 d-C^的烷基， 化合物 B和 C的 反应计量占两者总量的摩尔分数分别为 X和 y, x+y=l , x≠0, y≠0, 入 为含 噻吩的基团；
S02: 在催化剂、 溶剂以及碱性溶液存在的条件下， 将化合物 、 B、 C进 行 Suzuki聚合反应， 获得如下结构式 1)表示的聚合物：
Figure imgf000007_0003
(1),结构式 (1)中的 n 为 1-1000之间的自然数。
在步骤 S01 中， 化合物 A、 B、 C可直接从市场上购得或者通过现有的合 成方法制备。 其中， 与上述含芴共轭聚合物的描述基本相同， X和 y的取值范 围分别优选为： x=20%-80%, y=20%-80%。 在一个更优选的实施例中， x和 y 的取值均为 50%。 1^和 可以为相同的直链烷基， 优选为 C8H17, 即正辛基或 辛基的同分异构体， 更优选为正辛基。 R3和 R4均优选为氢。 n优选为 30-800, 更优选为 50-500。
与上面描述相同， ΑΓι选自上述结构式（a ) - ( g )表示的基团中的至少一 种， 优选地， R5、 R6、 R7、 R8、 R9、 R10是相同或不同的表示为 11或 d-C6的烷 基， Ru、 R12、 R13 、 R14、 R15优选为相同或不同的表示为 -C6的烷基， m优 选为 2-10之间的自然数。在一个较佳实施例中， A 为结构式（c )表示的基团， R7、 R8优选为 H, 即 A 分子式表示为 -C6H2S2-。
在步骤 S02中， 催化剂可以为有机钯催化剂， 其用量为化合物 A的摩尔用 量的 0.1-20%。有机钯催化剂例如可以是但不限于 Pd2(dba)3/P(o-Tol)3、 Pd(PPh3)4 或 Pd(PPh3)2Cl2。碱性溶液可以是无机碱溶液或有机碱溶液，无机碱溶液可以是 碱金属氢氧化物或碱金属碳酸盐的水溶液，例如可以是但不限于氢氧化钠溶液、 氢氧化钾溶液、 碳酸钠溶液、 碳酸钾溶液等， 优选为碳酸钠溶液， 有机碱溶液 可以是烷基氢氧化铵水溶液， 例如可以是但不限于四曱基氢氧化铵、 四乙基氢 氧化铵、 四丙基氢氧化铵、 四丁基氢氧化铵等水溶液。 上述碱性溶液的用量可 以为化合物 A的摩尔用量的 1-10倍。溶剂为弱极性或极性非质子性有机溶剂或 其混合溶剂， 例如可以是但不限于氯仿、 二氯曱烷、 二曱基亚砜（DMSO ) 、 四氢呋喃 （THF ) 、 曱苯、 二曱苯或其类似化合物， 优选为曱苯。 溶剂的用量 足量， 以使各反应物溶解并充分反应。
步骤 S02进行的反应可用如下反应方程式（i )表示：
Figure imgf000009_0001
上述 Suzuki反应温度为 30- 150 °C , 优选为 80-140°C , 更优选为 130°C ; 反 应时间为 1-7天， 优选为 2-5天， 更优选为 3天。 优选地， 步骤 S02是在氮气 保护下进行， 加入各原料及试剂后， 先用氮气置换 0.5-3小时后， 加热至回流， 反应 1-5天， 然后在回流状态下加入溴苯反应 6-24小时后， 再加入苯硼酸继续 反应 6-24小时， 得到产物。
另外， 还可进一步对反应产物进行如下提纯步骤： 减压去除溶剂， 用氯仿 / 水萃取， 洗涤， 干燥， 减压除去氯仿， 用曱醇沉降， 抽滤， 取滤出沉降物以氯 仿为淋洗剂进行氧化铝柱层析分离， 旋蒸， 用曱醇沉降， 抽滤， 所得固体用丙 酮索氏提取三天， 用曱醇沉降， 抽滤， 真空干燥滤出沉降物， 得到固态的含芴 共轭聚合物。 具体可以为如下步骤： 减压蒸去溶剂， 用氯仿 /水萃取、 饱和食盐 水洗涤、 无水石克 S史钠干燥。 然后将干燥的产物通过减压蒸去大量氯仿， 用曱醇 沉降， 抽滤。 取滤出沉降物并以氯仿为淋洗剂进行氧化铝柱层析分离， 旋蒸， 用曱醇沉降， 抽滤， 所得固体用丙酮索氏提取三天， 再曱醇沉降， 抽滤， 真空 干燥滤出沉降物， 得到固体产物， 产率大约为 60-85%。
在上述方法中， 化合物 A、 B、 C三种单体的合成路线比较简单且成熟， 基 本上是一步合成， 从而减少工艺流程， 降低制造成本。 而且 Suzuki反应是一种 非常成熟的聚合反应， 产率高、 条件温和， 易于控制， 且易通过引入烷基提高 产物的溶解性和分子量， 以实现可旋涂的聚合物。
请参阅图 3 , 显示采用上述实施例中含芴共轭聚合物的太阳能电池器件， 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 采用上述含芴共轭聚合物， 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可采用铝电极或者双金属层电极， 例如 Ca/Al 或 Ba/Al等。 其中， 玻璃基层 11可作为底层， 制作时， 选取 ITO玻璃， 并经超 声波清洗后， 用氧 -Plasma处理， 在 ITO玻璃上涂覆中间辅助层 13 , 再将含芴 共轭聚合物和电子受体材料通过共混后涂覆于中间辅助层 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。 在一个优选的实施例中， 透明阳极 12、 中间辅助层 13、 活性层 14、 双金属层 Ca和 A1层的厚度分别为 160 nm、 40 nm、 150 nm、 20 nm、 70 nm。
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 含芴共轭聚合物吸收光能， 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。
由于聚合物具有噻。分基团和芴基， 两者都是非常优异的给体材料， 苯并噻 二唑基是一种非常优异的受体材料， 因此， 本实施例的含芴共轭聚合物能够形 成一种 ^[艮强的电子给体 -受体结构， 一方面有利于提高材料的稳定性， 另一方面 由于电子给体-受体之间的相关作用， 有利于降低材料的能带隙， 从而扩大太阳 光吸收范围， 提高光电转化效率。 另外， 这些引入的基团具有大环和 /或稠环结 构， 能增大聚合物骨架的电子云密度， 使得含芴共轭聚合物的吸收光谱可以在 ^[艮大范围内进行调节， 这就使得这类材料可以具有更宽的光谱响应范围， 用作 光电材料时， 可更好的匹配太阳发射光语， 充分利用太阳能， 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 旋涂等技术即可制作， 便于大批量的制备。
另外， 含芴共轭聚合物不仅可应用于太阳能电池器件中， 还可以应用于有 机电致发光器件、 有机场效应晶体管、 有机光存储器件、 有机非线性材料或有 机激光器件等
以下通过一个较佳的实施例来举例说明含芴共轭聚合物制备方法以及其性 能等方面。 下面实施例中的八、 B、 C分别直接制备而得， 当然， 在其它实施例 中也可以直接从市场上购得， 并不限于此。
第一步， 制备化合物 A, 其中， 化合物 A以 2, 7-双（4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷基） - 9, 9-二辛基芴为例， 其结构式如下：
Figure imgf000011_0001
具体制备过程如下：在 -78°C、氮气条件下，用注射器将 1.44 mL( 4.20 mmol ) 正丁基锂溶液加入至盛有 1.10 g ( 2.00 mmol ) 2, 7-二溴 -9, 9-二辛基芴和 20 mL 四氢呋喃的两口烧瓶中， 搅拌 10分钟后升温至 0°C , 继续搅拌 20分钟。 降温至 -78 °C , 用注射器慢慢滴加 1.00 mL ( 4.80 mmol ) 2-异丙氧基 -4, 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷， 恢复至室温， 继续搅拌 24小时。 反应结束， 将反应液倒入 水中， 乙醚萃取， 盐水洗涤一次， 无水硫酸镁干燥， 将滤液收集旋蒸。 以石油 酸 /乙酸乙酯（9/1 ) 为淋洗剂进行硅胶柱层析分离， 然后用曱醇 /四氢呋喃重结 晶得到白色针状结晶， 产率为 75%。
测试结果为： MALDI-TOF-MS (m/z)： 642.5 (M+)。
第二步， 制备化合物 B, 其中， 化合物 B以 2, 5-二溴噻吩 [3, 2-b]并噻。分为 例， 其结构式为：
Figure imgf000012_0001
具体制备过程如下： 在冰浴、 避光条件下， 将 2.15 g ( 12.10 mmol ) NBS和 10 mL DMF加入至盛有 0.84 g ( 6.00 mmol )噻吩 [3, 2-b]并噻吩和 20 mL DMF的 两口烧瓶中， 搅拌 4个小时。 反应结束， 将反应液倒入冰水中淬灭， 二氯曱烷萃 取， 再用去离子水洗涤一次， 无水硫酸镁干燥， 将滤液收集旋蒸， 之后用中性 氧化铝层析柱进行分离， 得到淡黄色固体产物， 产率为 81%。
测试结果为： MALDI-TOF-MS (m/z): 298.1 (M+)。
第三步， 制备化合物 C, 其中， 化合物 C以 4, 7-二溴 -2, 1, 3-苯并噻二唑例， 其结构式为：
Figure imgf000012_0002
具体制备过程如下：称取 13.6 g( 100.00 mmol )苯并噻二唑，溶于 20 mL 45% 氢溴酸中， 加热搅拌至回流， 滴加 48 g ( 300.00 mmol )溴。 滴加完毕， 补加 10 mL氢溴酸并继续回流 3小时。 反应混合物趁热过滤， 冷却， 再过滤， 水洗涤， 干燥， 氯仿重结晶， 得到固体产物， 产率为 82%。
测试结果为： MALDI-TOF-MS (m/z): 293.9 (M+)。
第三步， 含芴共轭聚合物的形成， 本实施例的含芴共轭聚合物结构式为：
Figure imgf000012_0003
具体形成过程如下： 在氮气保护下， 往含有 0.321 g ( 0.50 mmol ) 2, 7-双 ( 4 4, 5, 5-四曱基 -1, 3, 2-二杂氧戊硼烷基 ) - 9, 9-二辛基芴、 0.0745 g ( 0.25 mmol ) 2, 5-二溴噻吩 [3, 2-b]并噻吩、 0.0735 g ( 0.25 mmol ) 4, 7-二溴 -2, 1, 3-苯并噻二 唑、 0.00416 g ( 0.0036 mmol ) Pd(PPh3)4的反应器中加入 10 mL Na2C03 ( 2 M ) 水溶液和曱苯 (20 mL)。 氮气置换 1小时后， 加热至回流， 反应 48小时。 在回 流状态下加入 0.0942 g ( 0.60 mmol )溴苯反应 12小时后， 加入 0.0793 g ( 0.65 mmol )苯硼酸继续反应 12小时。 将反应产物依次经减压蒸去曱苯， 氯仿 /水萃 取， 饱和食盐水洗涤， 无水硫酸钠干燥。 减压除去大量氯仿至 3-5 mL溶液， 再 经曱醇沉降， 抽滤。 以氯仿为淋洗剂进行氧化铝柱层析分离， 旋蒸， 曱醇沉降， 抽滤， 所得固体用丙酮索氏提取三天。 曱醇沉降， 抽滤， 真空干燥得到固体产 物， 产率为 74%。
测试结果为： GPC: Mn = 28300, PDI = 1.6。
在上述含芴共轭聚合物中， 所含的芴或其衍生物具有优异的光稳定性和热 稳定性， 而且该聚合物主链中引入噻。分基团， 由于噻。分是五元环结构， 符合休 克儿规则， 具有适中的能带隙， 较宽的光谱响应， 较好的热稳定性和环境稳定 性， 有助于加宽聚合物的光语响应范围。 同时该聚合物主链中还引入苯并噻二 唑基团， 具有五元环结构以及共轭双烯结构， 不仅能产生与噻吩类似的作用， 还能发挥共轭双烯的作用， 进一步加宽聚合物的光谱响应范围。 另外， 这些引 入的基团具有大环和 /或稠环结构， 能增大聚合物骨架的电子云密度， 使得含芴 共轭聚合物的吸收光谱可以在很大范围内进行调节， 这就使得这类材料可以具 有更宽的光谱响应范围， 用作光电材料时， 可更好的匹配太阳发射光谱， 充分 利用太阳能。 在上述含芴共轭聚合物制备方法中， 采用较简单的合成路线， 基 本上是一步合成， 从而减少工艺流程， 降低制造成本。 上述太阳能电池器件通 过采用了含芴共轭聚合物， 不仅能提高其光电转换效率， 而且能减轻太阳能电 池器件的质量， 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、 一种含芴共轭聚合物， 其包含如下结构式（1 )表示的聚合物:
Figure imgf000014_0001
式中： R2、 R3、 R4为相同或不同的表示为 11或 d-C^的烷基， x+y=l , x≠0, y≠0, n为 1-1000之间的自然数， Αι^为含噻吩的基团。
2、 如权利要求 1所述的含芴共轭聚合物， 其特征在于， 所述 X和 y的取值 范围分别为： x=20%-80%, y=20%-80%。
3、 如权利要求 1所述的含芴共轭聚合物， 其特征在于， 所述 1^和 均为 C8H17, 所述 和1^均为氢。
4、 如权利要求 1所述的含芴共轭聚合物， 其特征在于， 所述 ^选自如下 结构式表示的基团中的至少一种：
Figure imgf000014_0002
R7、 R8、 R9、 R10为相同或不同的表示为 H或 -C2。的烷基， Ru、 R12、 R13 、 R14、 R15为相同或不同的表示为 CrC2。的烷基， m为 1-20之间的自然数。
5、 如权利要求 1所述的含芴共轭聚合物， 其特征在于， 所述 ^是结构式 为 " R8 的基团， 其中， R7、 R8为相同或不同的表示为 H或 -C: 的烷基。
6、 一种含芴共轭聚合物制备方法， 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,
Figure imgf000015_0001
、 R2、 R3、 R4为相同或不同的表示为 H或 d-C^的烷基， 化合物 B和 C的 反应计量占两者总量的摩尔分数分别为 X和 y, x+y=l , x≠0, y≠0, 入 为含 噻吩的基团；
在催化剂、 溶剂和碱性溶液存在的条件下， 将化合物 、 B、 C进行 Suzuki 聚合反应， 获得如下结构式 1)表示的聚合物：
Figure imgf000015_0002
(1) , 结构式 (1) 中的 n为 1-1000之间的自然数。
7、 如权利要求 6所述的含芴共轭聚合物制备方法， 其特征在于， 进一步对 反应产物进行如下提纯步骤： 减压去除溶剂， 用氯仿 /水萃取， 洗涤， 干燥， 减 压除去氯仿， 用曱醇沉降， 抽滤， 取滤出沉降物以氯仿为淋洗剂进行氧化铝柱 层析分离， 旋蒸， 用曱醇沉降， 抽滤， 所得固体用丙酮索氏提取三天， 再用曱 醇沉降， 抽滤， 真空干燥滤出沉降物， 得到固态的含芴共轭聚合物。
8、如权利要求 6所述的含芴共轭聚合物制备方法，其特征在于，所述 Suzuki 聚合反应温度为 30- 150 °C , 反应时间为 1 -7天。
9、 如权利要求 6所述的含芴共轭聚合物制备方法， 其特征在于， 所述催化 剂为有机钯催化剂， 所述碱性溶液为无机碱水溶液或有机碱水溶液； 所述溶剂 为弱极性或极性非质子性有机溶剂或其混合溶剂。
10、 一种太阳能电池器件， 其包括依次层叠的玻璃基层、 透明阳极、 中间 辅助层、 活性层及阴极， 所述活性层包括电子给体材料和电子受体材料， 其特 征在于， 所述电子给体材料为如权利要求 1-5任一项所述的含芴共轭聚合物。
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