WO2013040786A1 - 含芴二氟代苯并三唑基共聚物及其制备方法和应用 - Google Patents

含芴二氟代苯并三唑基共聚物及其制备方法和应用 Download PDF

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WO2013040786A1
WO2013040786A1 PCT/CN2011/080102 CN2011080102W WO2013040786A1 WO 2013040786 A1 WO2013040786 A1 WO 2013040786A1 CN 2011080102 W CN2011080102 W CN 2011080102W WO 2013040786 A1 WO2013040786 A1 WO 2013040786A1
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fluorene
difluorobenzotriazole
based copolymer
compound
organic
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PCT/CN2011/080102
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English (en)
French (fr)
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周明杰
王平
张振华
梁禄生
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海洋王照明科技股份有限公司
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Priority to PCT/CN2011/080102 priority Critical patent/WO2013040786A1/zh
Priority to CN201180072280.1A priority patent/CN103687890A/zh
Priority to EP11872853.4A priority patent/EP2759557B1/en
Priority to JP2014531063A priority patent/JP2014531492A/ja
Priority to US14/234,333 priority patent/US20140163166A1/en
Publication of WO2013040786A1 publication Critical patent/WO2013040786A1/zh

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    • H—ELECTRICITY
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    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
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    • 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
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
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    • C08G2261/40—Polymerisation processes
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    • C08G2261/411—Suzuki reactions
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    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
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    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to the field of solar cell materials, and more particularly to a fluorene-containing difluorobenzotriazole-based copolymer and a preparation method and application thereof. Background technique
  • An object of the present invention is to provide a fluorene-containing difluorobenzotriazole-based copolymer having high energy conversion efficiency.
  • R 2 is d ⁇ C 2 .
  • the alkyl group, n is an integer from 10 to 100. In a preferred embodiment, n is preferably from 50 to 70.
  • Another object of the present invention is to provide a process for the preparation of the above-mentioned fluorene-containing difluorobenzotriazole-based copolymer, comprising the steps of:
  • the compound A and the compound B are added in a molar ratio of 1:1, added to an organic solvent containing a catalyst and an alkali solution, and subjected to a Suzuki coupling reaction at 70 to 130 ° C. After 96 hours, the fluorene-containing difluorobenzotriazole-based copolymer having the following structural formula (I) was obtained:
  • the preparation method of the above-mentioned fluorene-containing difluorobenzotriazole-based copolymer further comprises the following steps:
  • the ruthenium-containing difluorobenzotriazole-based copolymer obtained in the step S2 is subjected to purification treatment.
  • the catalyst is an organic palladium or a mixture of an organic palladium and an organic brick ligand; the organic palladium and the The molar ratio of the compound A is 1:20 to 1:100.
  • the organic solvent is selected from at least one of toluene, fluorene, fluorenyl-dimercaptoamide and tetrahydrofuran;
  • the alkali solution is selected from at least one of a sodium carbonate solution, a potassium carbonate solution, and a sodium hydrogencarbonate solution.
  • step S2 Preferably, in the step S2:
  • a further object of the present invention is to provide the use of the above-mentioned fluorene-containing difluorobenzotriazole-based copolymer in an organic solar cell.
  • the fluorene-containing difluorobenzotriazole-based copolymer provided by the present invention since the 1,2,3-benzotriazole polymer contains two fluorine atoms, the HOMO level thereof is lowered by O.lleV, and the fluorine is substituted.
  • 1, 2, 3-benzotriazole has two strong electron-withdrawing imine groups, difluorobenzotriazole is a heterocyclic compound with strong electron-withdrawing properties, and the NH bond of benzotriazole It is easy to introduce a radical chain on N.
  • the alkyl chain functional group can improve the energy conversion efficiency of solar energy, thereby solving the problem of low efficiency of the polymer solar cell, and at the same time, the alkyl chain functional group can also regulate the ruthenium-containing group.
  • the solubility of the difluorobenzotriazole-based copolymer makes the polymer advantageous for film formation and expands their application in the field of polymer solar cells.
  • FIG. 1 is a flow chart of a preparation process of a fluorene-containing difluorobenzotriazole-based copolymer of the present invention
  • FIG. 2 is a poly ⁇ 9,9-di-n-hexyl-2,7-fluorene-CO-2 prepared in Example 1. UV-visible absorption spectrum of n-octyl-4,7-dithienyl-5,6-difluorobenzotriazole ⁇ ;
  • 3 is a schematic structural view of an organic solar cell. detailed description
  • R 2 is d ⁇ C 2 .
  • the base, n is an integer from 10 to 100; preferably n is 50
  • R 2 is an alkyl group of d to C 20 ;
  • step S3 purifying the product in step S2:
  • the hydration alcohol was added to the reaction liquid of the step S2, followed by precipitation treatment, followed by filtration with a Soxhlet extractor, followed by extraction with decyl alcohol and n-hexane for 24 h; then, the chloroform was used as a solvent to extract the precipitate to be colorless.
  • the chloroform solution was collected and spun dry to obtain a red powder, and the red powder was dried under vacuum at 50 ° C for 24 h to obtain a purified fluorene-containing difluorobenzotriazole-based copolymer.
  • the catalyst is an organic palladium, for example, bistriphenylphosphine palladium dichloride, triphenylbenzylideneacetate Palladium or tetrakistriphenylphosphine palladium; the catalyst may also be a mixture of organopalladium and an organobrick ligand, such as a mixture of tris-benzylideneacetone dipalladium and tri-tert-butylphosphine;
  • the molar ratio of the compound A is 1:20 to 1:100; in the mixture of the organic palladium and the organic brick ligand, the molar ratio of the organic palladium to the organic brick ligand is 1:3 to 1:6.
  • the organic solvent is at least one selected from the group consisting of nonylbenzene, hydrazine, hydrazine-dimercaptoamide, and tetrahydrofuran; and the alkali solution is at least one selected from the group consisting of sodium carbonate solution, potassium carbonate solution, and sodium hydrogencarbonate solution.
  • step S2 Preferably, in the step S2:
  • the Suzuki coupling reaction temperature is 80 to 110 ° C; and the Suzuki coupling reaction time is 24 to 72 h.
  • the fluorene-containing difluorobenzotriazole-based copolymer provided by the present invention since the 1,2,3-benzotriazole polymer contains two fluorine atoms, the HOMO level thereof is lowered by O.lleV, and the fluorine is substituted.
  • 1, 2, 3-benzotriazole has two strong electron withdrawing imine groups, and difluorobenzotriazole is a strong electron withdrawing electron.
  • the alkyl chain functional group can also function to adjust the solubility of the fluorene-containing difluorobenzotriazole-based copolymer, making the polymer advantageous for film formation and expanding their application in the field of polymer solar energy.
  • the preparation method of the invention adopts a simpler synthesis route, thereby reducing the process flow, the material is cheap and easy to obtain, and the manufacturing cost is reduced.
  • the above-mentioned fluorene-containing difluorobenzotriazole-based copolymer can be used in an electron donor material of an active layer of an organic solar cell.
  • the technical examples of the present invention are further illustrated by specific examples and illustrations, including material preparation and device preparation, but these examples do not limit the present invention, wherein Monomers are commercially available, and monomers of Compound B can be synthesized by the method disclosed in the literature (j. Am. Chem. Soc. 2011, 133, 4625) or commercially available.
  • the fluorene-containing difluorobenzotriazole-based copolymer of the present embodiment that is, poly ⁇ 9,9-di-n-hexyl-2,7-fluorene-CO-2-n-octyl-4,7-dithienyl- 5,6-difluorobenzotriazole ⁇ , wherein, is a n-hexyl group, R 2 is a n-octyl group, and n is 70, and its structural formula is as follows:
  • 2,7-diboronic acid pinacol ester-9,9-di-n-hexyl hydrazine (176 mg, 0.3 mmol), 2-n-octyl-4,7-di(5-bromothienyl)-5,6 -difluoro-1,2,3-benzotriazole (176 8 mg, 0.3 mmol), tri-dibenzylideneacetone dipalladium (13.75 mg, 0.015 mmol) and tri-tert-butylphosphine (ie 2-dicyclohexyl) Brick-2,6,2-dimethoxybiphenyl) (2 mg) was added to a flask containing 12 mL of toluene and dissolved into a solution, then potassium carbonate (3 mL, 2 mol/L) solution was added. Into the solution, the flask was purged with nitrogen for about 30 minutes, and then stirred at 95 ° C and Suzuki coupling reaction for 48 h.
  • Example 2 is a poly ⁇ 9,9-di-n-hexyl-2,7-fluorene-co-2-n-octyl-4,7-dithienyl-5,6-difluorobenzotriazole prepared in Example 1. UV-visible absorption spectrum of the ⁇ ; It can be seen from Figure 2 that the conjugated polymer has a strong absorption peak at around 680 nm.
  • Example 2
  • the fluorene-containing difluorobenzotriazole-based copolymer of the present embodiment that is, poly ⁇ 9,9-dimercapto-2,7-fluorene-CO-2-n-icosyl-4,7-dithiophene a group of 5-,6-difluorobenzotriazole ⁇ , wherein, is a fluorenyl group, R 2 is a ruthenium, and n is 50, and the structural formula is as follows:
  • 2,7-diboronic acid pinacol ester-9,9-dimercaptopurine (89 mg, 0.2 mmol)
  • 2-n- 20-yl- 4,7-di(5-bromothienyl)-5 , 6-difluoro-1,2,3-benzotriazole (151.4 mg, 0.2 mmol) was added to a flask containing 15 ml of hydrazine, hydrazine-dihydrazinamide solvent, dissolved into a solution; Sodium carbonate (2 mL, 2 mol/L) solution was added to the solution, and the vacuum flask was deaerated and filled with argon.
  • the fluorene-containing difluorobenzotriazole-based copolymer of the present embodiment that is, poly ⁇ 9,9-di(n- 20 fluorenyl)-2,7-fluorene-co-2-mercapto-4,7- Dithienyl-5,6-difluorobenzotriazole ⁇ , wherein, is n-icosyl, R 2 is a fluorenyl group, and n is 58.
  • the structural formula is as follows:
  • 2,7-diboronic acid pinacol ester-9,9-di(icosyl)phosphonium (294 mg, 0.3 mmol)
  • 2-mercapto-4,7-di(5-bromothienyl)- 5,6-Difluoro-1,2,3-benzotriazole 147.3 mg, 0.3 mmol
  • a solution of sodium bicarbonate (3 mL, 2 mol/L) was added to the solution, and a mixture of nitrogen and argon was passed through the air for about 20 minutes.
  • reaction liquid 17 mg of tetrakistriphenylphosphine palladium was added to the two-necked bottle.
  • a mixture of nitrogen and argon gas was continuously exhausted for about 10 minutes, and then stirred at 80 ° and subjected to a Suzuki coupling reaction for 72 hours to obtain a reaction liquid.
  • the fluorene-containing difluorobenzotriazole-based copolymer of the present embodiment that is, poly ⁇ 9,9-di-n-hexyl-2,7-fluorene-co-2-n-dodecyl-4,7-dithiophene
  • a group of -5,6-difluorobenzotriazole ⁇ wherein, is a n-hexyl group, R 2 is a n-t-decyl group, and n is 10, and its structural formula is as follows:
  • reaction formula is as follows: 2,7-diboronic acid pinacol ester-9,9-di-n-hexyl hydrazine (117 mg, 0.2 mmol), 2-n-dodecyl-4,7-bis(5-bromothienyl)-5 , 6-difluoro-1,2,3-benzotriazole (128.6 mg, 0.2 mmol) was added to a flask containing 15 ml of hydrazine, hydrazine-dihydrazinamide solvent, dissolved into a solution; Sodium carbonate (2 mL, 2 mol/L) solution was added to the solution, and the vacuum flask was deoxygenated and filled with argon.
  • the fluorene-containing difluorobenzotriazole-based copolymer of the present embodiment that is, poly ⁇ 9,9-di(n-fluorenyl)-2,7-fluorene-CO-2-n-tetradecyl-4, 7-Dithienyl-5,6-difluorobenzotriazole ⁇ , wherein, is a n-decyl group, R 2 is a n-tetradecyl group, and n is 100, and its structural formula is as follows:
  • the organic solar cell of the sixth embodiment adopts the poly ⁇ 9,9-di-n-hexyl-2,7-fluorene-CO-2-n-octyl-4,7-dithienyl-5 obtained in the first embodiment.
  • 6-difluorobenzotriazole ⁇ ie DFBTz-Fl
  • DFBTz-Fl 6-difluorobenzotriazole ⁇
  • the organic solar cell includes 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 transparent anode 12 may be made of indium tin oxide (barrel called ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ ;
  • the intermediate auxiliary layer 13 is made of poly 3,4-ethylenedioxythiophene and polyphenylene.
  • Ethylene-sulfonic acid composite material (cylinder called PEDOT:PSS); active layer 14 includes electron donor material and electron acceptor material, electron donor material adopts the polymer prepared in Example 1 (ie DFBTz-Fl), electron accepting
  • the bulk material may be [6,6] phenyl-C 61 -butyric acid decanoate (cylinder called PCBM);
  • the cathode 15 may be an aluminum electrode or a bimetal electrode, such as Ca/Al or Ba/Al, etc., thickness thereof It is preferably 170 nm, 30 nm, 130 nm or 60 nm.
  • the glass base layer 11 can be used as a bottom layer.
  • ITO glass is selected, ultrasonically cleaned, treated with oxygen-Plasma, and an intermediate auxiliary layer 13 is coated on the ITO glass, and the polymer and electron acceptor prepared in Example 1 are further prepared.
  • the 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 organic solar cell.
  • the organic solar cell needs to be heated under a sealed condition of 110 degrees Celsius for 4 hours and then lowered to room temperature. After annealing, the device can effectively increase the order and regularity of the arrangement between the groups and molecular segments in the molecule, and improve the current carrying current.
  • the transfer rate and efficiency of the sub-mobility increase the photoelectric conversion efficiency.
  • the thickness of the cathode 15 A1 layer is 170 nm, respectively.
  • the conductive hole-type electroluminescent material in the active layer 14 absorbs light energy and generates excitons, which then migrate to electrons.
  • electrons are transferred to an electron acceptor material, such as PCBM, to effect charge separation, thereby forming free carriers, ie free electrons and holes.
  • an electron acceptor material such as PCBM
  • the electrons are transferred along the electron acceptor material to the metal cathode and collected by the cathode.
  • the free holes are transferred along the electron donor material to the no anode and collected by the anode, thereby forming photocurrent and photovoltage, realizing photoelectric conversion, external load. At 1600, it can be powered.
  • the conduction hole type electroluminescent material can more fully utilize the light energy due to its spectral response range of 4 ⁇ , thereby obtaining higher photoelectric conversion efficiency and increasing the power generation capability of the organic solar cell.
  • the organic material can also reduce the quality of the organic solar cell, and can be fabricated by techniques such as spin coating, which is convenient for mass production.
  • Table 1 shows the photovoltaic properties of the organic solar cell of Example 6. (Note: PCE is the energy conversion efficiency, V. c is the open circuit voltage, J sc is the short circuit current, and FF is the fill factor.)
  • Illuminance and spectral distribution its total solar irradiance is 1000 watts per square meter, and the solar cell is measured at 25 degrees; this standard is set by the International Electrotechnical Commission, which is currently used in China; specifically, one The standard sun is equivalent to the irradiation intensity of the AM1.5G standard light source, and AM 1.5G means that the zenith angle (the angle between the incident light source and the ground normal) is 48 degrees of sunlight, and the light intensity is 1000 W/m. 2 (ie AM 1.5, 100 mW/cm 2 illumination).

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Abstract

本发明属于太阳能电池领域，其公开了一种含芴二氟代苯并三唑基共聚物及其制备方法和应用；该共聚物具有结构式（I）。式（1）中，R1、R2均为C1~C20的烷基，n为10~100的整数。本发明提供的含芴二氟代苯并三唑基共聚物，由于1，2，3-苯并三唑聚合物含有两个氟原子，其HOMO能级将降低0.11eV，而氟取代的1，2，3-苯并三唑又有两个强吸电子的亚胺基，二氟代苯并三唑是一个有强吸电子性能的杂环化合物，且苯并三唑的N-H键的N上容易引入烷基链，该烷基链官能性基团可以提高太阳能的能量转换效率，从而解决聚合物太阳能电池低效率问题

Description

含芴二氟代苯并三唑基共聚物及其制备方法和应用 技术领域
本发明涉及太阳能电池材料领域， 尤其涉及一种含芴二氟代苯并三唑 基共聚物及其制备方法和应用。 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。 目前用于地面的硅晶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。 有机半导体材料以其原料易得、 廉价、 制 备工艺筒单、 环境稳定性好、 有良好的光伏效应等优点备受关注。 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， 但是仍比无机太阳能电池的转换效率低得多。 发明内容
本发明的目的在于提供一种能量转换效率较高的含芴二氟代苯并三唑 基共聚物。
一种具有下述结构式（I ) 的含芴二氟代苯并三唑基共聚物：
Figure imgf000002_0001
( 1 )；
式中， 、 R2均为 d ~ C2。的烷基， n为 10~100的整数。 在优选的实施例中， n优选为 50 ~ 70。
本发明的另一目的在于提供上述含芴二氟代苯并三唑基共聚物的制备 方法， 包括如下步骤：
Sl、 分别提供如下结构式表示的化合物 A和化合物 B ,
Figure imgf000003_0001
所述化合物 A中， 为 d ~ C2。的綻基； 所述化合物 B中， R2为 d ~ C20 的烷基；
S2、 在无氧环境下， 将所述化合物 A和化合物 B按照摩尔比 1:1加入 量，添加入含有催化剂和碱溶液的有机溶剂中，于 70 ~ 130°C下进行 Suzuki 耦合反应 12 - 96 小时后， 得到具有下述结构式（I ) 的所述含芴二氟代苯 并三唑基共聚物：
Figure imgf000003_0002
上述含芴二氟代苯并三唑基共聚物的制备方法还包括如下步骤：
S3、对步骤 S2中制得的所述含芴二氟代苯并三唑基共聚物进行纯化处 理。
在上述含芴二氟代苯并三唑基共聚物的制备方法， 所述步骤 S2中： 所述催化剂为有机钯， 或者是有机钯与有机磚配体的混合物； 所述有 机钯与所述化合物 A的摩尔比为 1:20~1 :100。
所述有机溶剂选自曱苯、 Ν,Ν-二曱基曱酰胺及四氢呋喃中的至少一种； 所述碱溶液选自碳酸钠溶液、 碳酸钾溶液及碳酸氢钠溶液中的至少一 种。
优选地， 所述步骤 S2中：
所述 Suzuki耦合反应温度为 80~110°C ; 所述 Suzuki耦合反应时间为 24~72h。 本发明的又一目的在于提供上述含芴二氟代苯并三唑基共聚物在有机 太阳能电池中的应用。 本发明提供的含芴二氟代苯并三唑基共聚物， 由于 1, 2, 3-苯并三唑聚 合物含有两个氟原子， 其 HOMO能级将降低 O.lleV, 而氟取代的 1, 2, 3- 苯并三唑又有两个强吸电子的亚胺基， 二氟代苯并三唑是一个有强吸电子 性能的杂环化合物， 且苯并三唑的 N-H键的 N上容易引入綻基链， 该烷基 链官能性基团可以提高太阳能的能量转换效率， 从而解决聚合物太阳能电 池低效率问题， 同时， 烷基链官能性基团还可以起到调节含芴二氟代苯并 三唑基共聚物的溶解性， 使得该聚合物有利于成膜加工， 扩大它们在聚合 物太阳能电池领域的应用范围。 附图说明
图 1为本发明含芴二氟代苯并三唑基共聚物的制备工艺流程图； 图 2为实施例 1制备的聚 {9,9-二正己基 -2,7-芴 -CO-2-正辛基 -4,7-二噻吩 基 -5,6-二氟苯并三唑 }的紫外可见吸收光谱图；
图 3为有机太阳能电池的结构示意图。 具体实施方式
本发明提供的具有下述结构式（I ) 的含芴二氟代苯并三唑基共聚物:
Figure imgf000005_0001
式中， 、 R2均为 d~C2。的綻基， n为 10~100的整数； 优选 n为 50
上述含芴二氟代苯并三唑基共聚物的制备方法， 如图 1 所示， 下步骤：
Sl、 分别提供如下结构式表示的化合物 A和化合物 B,
Figure imgf000005_0002
2, 3-苯并三唑；
其中， 化合物 A中， 为 d~C2。的綻基； 化合物 B中， R2为 d~C20 的烷基；
S2、 在无氧环境（如， 氮气、 氩气或氮气和氩气混合气等构成的无氧 环境） 下， 将所述化合物 A和化合物 B按照摩尔比 1:1加入量， 添加入含 有催化剂和碱溶液的有机溶剂中，于 70 ~ 130°C下进行 Suzuki耦合反应 12 ~ 96 小时后， 得到反应液， 该反应液中包含产物， 即具有下述结构式（I)的 所述含芴二氟代苯并三唑基共聚物：
Figure imgf000006_0001
S3、 对步骤 S2中的产物进行纯化处理：
往步骤 S2的反应液中加入曱醇， 进行沉析处理， 随后用索氏提取器过 滤， 之后依次用曱醇和正己烷抽提沉淀 24 h; 然后继续以氯仿为溶剂抽提 沉淀至无色，收集氯仿溶液并旋干得到红色粉末，将红色粉末在真空下 50°C 干燥 24 h后， 得到纯化的含芴二氟代苯并三唑基共聚物。
在上述含芴二氟代苯并三唑基共聚物的制备方法， 所述步骤 S2中： 所述催化剂为有机钯， 如， 双三苯基膦二氯化钯、 三二亚苄基丙酮二 钯或四三苯基膦钯； 所述催化剂也可以为有机钯与有机磚配体的混合物， 如， 三二亚苄基丙酮二钯与三叔丁基膦的混合物； 所述有机钯与所述化合 物 A的摩尔比为 1:20~1:100； 有机钯与有机磚配体的混合物中， 有机钯与 有机磚配体的摩尔比为 1:3 ~ 1:6。
所述有机溶剂选自曱苯、 Ν,Ν-二曱基曱酰胺及四氢呋喃中的至少一种； 所述碱溶液选自碳酸钠溶液、 碳酸钾溶液及碳酸氢钠溶液中的至少一 种。
优选地， 所述步骤 S2中：
所述 Suzuki耦合反应温度为 80~110°C ; 所述 Suzuki耦合反应时间为 24~72h。 本发明提供的含芴二氟代苯并三唑基共聚物， 由于 1, 2, 3-苯并三唑聚 合物含有两个氟原子， 其 HOMO能级将降低 O.lleV, 而氟取代的 1, 2, 3- 苯并三唑又有两个强吸电子的亚胺基， 二氟代苯并三唑是一个有强吸电子 性能的杂环化合物， 且苯并三唑的 N-H键的 N上容易引入綻基链， 该烷基 链官能性基团可以提高太阳能的能量转换效率， 从而解决聚合物太阳能电 池低效率问题， 同时， 烷基链官能性基团还可以起到调节含芴二氟代苯并 三唑基共聚物的溶解性， 使得该聚合物有利于成膜加工， 扩大它们在聚合 物太阳能领域的应用范围。
另外， 本发明的制备方法， 采用较筒单的合成路线， 从而减少工艺流 程， 材料价廉易得， 降低制造成本。 上述含芴二氟代苯并三唑基共聚物可以应用在有机太阳能电池活性层 的电子给体材料中。 为了更好地理解本发明专利的内容， 下面通过具体的实例和图例来进 一步说明本发明的技术案， 具体包括材料制备和器件制备， 但这些实施实 例并不限制本发明， 其中， 化合物 A的单体从市场上购买得到， 化合物 B 的单体可参照文献（ j. Am. Chem. Soc. 2011,133,4625 )公开的方法合成或者 从市场上购买得到。 实施例 1
本实施例的含芴二氟代苯并三唑基共聚物，即聚 {9,9-二正己基 -2, 7-芴 -CO-2- 正辛基 -4,7-二噻吩基 -5,6-二氟苯并三唑 } , 其中， 为正己綻基， R2为正辛 綻基， n为 70, 其结构式如下：
Figure imgf000007_0001
上述聚合物的制备步骤如下:
Figure imgf000008_0001
将 2, 7-二硼酸频哪醇酯 -9,9-二正己基芴（176 mg, 0.3 mmol)、2-正辛基 -4, 7-二 (5-溴噻吩基) -5,6-二氟 -1, 2, 3-苯并三唑 (176 8 mg, 0.3 mmol)、 三二亚苄 基丙酮二钯 (13.75 mg, 0.015mmol)和三叔丁基膦（即 2-双环己基磚 -2，， 6，-二 曱氧基联苯）（2 mg)加入盛有 12 mL曱苯的烧瓶中， 并溶解成溶液， 然后再 将碳酸钾 (3 mL, 2mol/L)溶液加入到溶液中， 向烧瓶中通氮气排空气约 30 min后， 在 95°C下搅拌、 Suzuki耦合反应 48 h, 降温后停止聚合反应， 获 得反应液。
向烧瓶中加入 40 mL曱醇， 对反应液进行沉析处理， 接着通过索氏提 取器过滤， 之后依次用曱醇和正己烷抽提沉淀 24 h; 然后继续以氯仿为溶 剂抽提沉淀至无色， 收集氯仿溶液并旋干得到红色粉末， 最后将收集后的 红色粉末在真空下 50°C干燥 24 h后即为聚 {9,9-二正己基 -2,7-芴 -CO-2-正辛 基 -4,7-二噻吩基 -5,6-二氟苯并三唑 }产物， 产率为 75%。
测试结果为： Molecular weight ( GPC, THF, R. I): Mn =48.1 kDa, Mw/Mn =2.0。
图 2为实施例 1制备的聚 {9,9-二正己基 -2,7-芴 -co-2-正辛基 -4,7-二噻吩 基 -5,6-二氟苯并三唑 }的紫外可见吸收光谱图； 由图 2可以看出共轭聚合物 在 680 nm左右处有较强的吸收峰。 实施例 2
本实施例的含芴二氟代苯并三唑基共聚物， 即聚 {9,9-二曱基 -2, 7-芴 -CO-2-正二十烷基 -4,7-二噻吩基 -5,6-二氟苯并三唑 } , 其中， 为曱基， R2 为正二十綻基， n为 50, 其结构式如下：
Figure imgf000009_0001
上述聚合物的制备步骤如下:
反应式如下所示：
Figure imgf000009_0002
将 2, 7-二硼酸频哪醇酯 -9,9-二曱基芴 (89 mg, 0.2mmol)、 2-正二十綻基 —4,7-二 (5-溴噻吩基) -5,6-二氟 -1,2,3-苯并三氮唑 (151.4 mg, 0.2mmol)加入盛 有 15ml的 Ν,Ν-二曱基曱酰胺溶剂的烧瓶中，溶解成溶液； 然后再将碳酸钠 (2 mL, 2mol/L)溶液加入到溶液中， 抽真空烧瓶除氧并充入氩气， 然后加入 5 mg 双三苯基膦二氯化钯， 加热到 110°C搅拌、 Suzuki耦合反应 24 h, 降 温后停止聚合反应， 获得反应液。
向烧瓶中加入 50 mL曱醇， 对反应液进行沉析处理， 接着通过索氏提 取器过滤， 之后依次用曱醇和正己烷抽提沉淀 24 h; 然后继续以氯仿为溶 剂抽提沉淀至无色， 收集氯仿溶液并旋干得到红色粉末， 最后将收集后的 红色粉末在真空下 50°C干燥 24 h后即为聚 {9,9-二曱基 -2, 7-芴 -co-2-正二十 烷基 -4,7-二噻吩基 -5,6-二氟苯并三唑 }产物， 产率 77%。
测试结果为： Molecular weight ( GPC, THF, R. I): Mn = 39.5 kDa, Mw/Mn =2.1。 实施例 3
本实施例的含芴二氟代苯并三唑基共聚物， 即聚 {9,9-二（正二十綻基） -2, 7-芴 -co-2-曱基 -4,7-二噻吩基 -5,6-二氟苯并三唑 } , 其中， 为正二十烷 基， R2为曱綻基， n为 58, 其结构式如下：
Figure imgf000010_0001
上述聚合物的制备步骤如下:
反应式如下所示：
Figure imgf000010_0002
将 2, 7-二硼酸频哪醇酯 -9,9-二 (二十烷基） 芴 (294 mg, 0.3 mmol), 2- 曱基— 4,7-二 (5-溴噻吩基) -5,6-二氟 -1, 2, 3-苯并三氮唑 (147.3 mg, 0.3 mmol)加 入盛有 15 mL四氢呋喃的 50 mL规格的两口瓶中， 溶解成溶液， 然后再将 碳酸氢钠 (3 mL, 2mol/L)溶液加入到溶液中， 通氮气和氩气混合气， 排空气 约 20 min后， 然后将 17 mg四三苯基膦钯加入两口瓶中， 再充分通氮气和 氩气混合气，继续排空气约 10 min后， 在 80 下搅拌、 Suzuki耦合反应 72h, 获得反应液。
向烧瓶中加入 40 mL曱醇， 对反应液进行沉析处理， 接着通过索氏提取 器过滤，之后依次用曱醇和正己烷抽提沉淀 24 h; 然后继续以氯仿为溶剂抽 提沉淀至无色， 收集氯仿溶液并旋干得到红色粉末， 最后将收集后的红色 粉末在真空下 50°C干燥 24 h后即为聚 {9,9-二（二十烷基） -2, 7-芴 -co-2-曱 基 -4,7-二噻吩基 -5 ,6-二氟苯并三唑 }产物， 产率为 72%。
测试结果为： Molecular weight ( GPC, THF, R. I): Mn = 61.3 kDa, Mw/Mn =2.0。 实施例 4
本实施例的含芴二氟代苯并三唑基共聚物， 即聚 {9,9-二正己基 -2, 7- 芴 -co-2-正十二烷基 -4,7-二噻吩基 -5,6-二氟苯并三唑 } , 其中， 为正己基， R2为正十二綻基， n为 10, 其结构式如下：
Figure imgf000011_0001
上述聚合物的制备步骤如下:
反应式如下所示：
Figure imgf000012_0001
将 2, 7-二硼酸频哪醇酯 -9,9-二正己基芴（117 mg, 0.2mmol)、 2-正十二烷 基—4,7-二 (5-溴噻吩基) -5,6-二氟 -1,2,3-苯并三氮唑 (128.6 mg, 0.2mmol)加入 盛有 15ml的 Ν,Ν-二曱基曱酰胺溶剂的烧瓶中，溶解成溶液； 然后再将碳酸 钠 (2 mL, 2mol/L)溶液加入到溶液中， 抽真空烧瓶除氧并充入氩气， 然后加 入（ 0.01 mmol, 7.02 mg )双三苯基膦二氯化钯， 加热到 130°C、 Suzuki耦合 反应 12 h, 降温后停止聚合反应， 获得反应液。
向烧瓶中加入 50 mL曱醇， 对反应液进行沉析处理， 接着通过索氏提 取器过滤， 之后依次用曱醇和正己烷抽提沉淀 24 h; 然后继续以氯仿为溶 剂抽提沉淀至无色， 收集氯仿溶液并旋干得到红色粉末， 最后将收集后的 红色粉末在真空下 50°C干燥 24 h后即为聚 {9,9-二正己基基 -2, 7-芴 -co-2- 正十二烷基 -4,7-二噻吩基 -5,6-二氟苯并三唑 }产物， 产率 71%。
测试结果为： Molecular weight ( GPC, THF, R. I): Mn = 10.7 kDa, Mw/Mn =2.3。 实施例 5
本实施例的含芴二氟代苯并三唑基共聚物，即聚 {9,9-二（正癸綻基） -2, 7-芴 -CO-2-正十四綻基 -4,7-二噻吩基 -5,6-二氟苯并三唑 } , 其中， 为正癸烷 基， R2为正十四綻基， n为 100, 其结构式如下：
Figure imgf000013_0001
将 2, 7-二硼酸频哪醇酯 -9,9-二 (正癸烷基） 芴 (294 mg, 0.3 mmol), 2- 正十四綻基 -4,7-二 (5-溴噻吩基) -5,6-二氟 -1, 2, 3-苯并三氮唑 (147.3 mg, 0.3 mmol)加入盛有 15 mL四氢呋喃的 50 mL规格的两口瓶中， 溶解成溶液， 然后再将碳酸氢钠 (3 mL, 2mol/L)溶液加入到溶液中，通氮气和氩气混合气， 排空气约 20 min后， 然后将 (0.003 mmol, 3.7 mg)四三苯基膦钯加入两口瓶 中，再充分通氮气和氩气混合气，继续排空气约 10 min后， 在 70 下搅拌、 Suzuki耦合反应 96 h , 获得反应液。
向烧瓶中加入 40 mL曱醇， 对反应液进行沉析处理， 接着通过索氏提取 器过滤，之后依次用曱醇和正己烷抽提沉淀 24 h; 然后继续以氯仿为溶剂抽 提沉淀至无色， 收集氯仿溶液并旋干得到红色粉末， 最后将收集后的红色 粉末在真空下 50°C干燥 24 h后即为聚 {9,9-二（正癸烷基） -2, 7-芴 -co-2-十 四烷基 -4,7-二噻吩基 -5,6-二氟苯并三唑 }产物， 产率为 85%。
测试结果为： Molecular weight ( GPC, THF, R. I): Mn = 95.8 kDa, Mw/Mn =1.9。
实施例 6
本实施例 6的有机太阳能电池， 其采用实施例 1制得的聚 {9,9-二正己 基 -2, 7-芴 -CO-2-正辛基 -4,7-二噻吩基 -5,6-二氟苯并三唑 } (即 DFBTz-Fl ) 为活性层的电子给体材料。
请参阅图 3, 该有机太阳能电池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以及阴极 15。 透明阳极 12可采用氧化铟 锡（筒称为 ITO ) , 优选为方块电阻为 10-20 Ω/口的氧化铟锡； 中间辅助层 13 采用聚 3,4-亚乙二氧基噻吩与聚苯乙烯-磺酸复合材料 （筒称为 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 料采用实施例 1制备的聚合物（即 DFBTz-Fl ) , 电子受体材料可以是 [6,6] 苯基 -C61 -丁酸曱酯（筒称为 PCBM )； 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， 其厚度优选为 170 nm、 30 nm、 130 nm或 60 nm。
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,再将实施例 1制备的 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,获得上述有机太阳能 电池。 该有机太阳能电池还需经过 110摄氏度密闭条件下加热 4小时， 再 降到室温， 器件经过退火后能有效增加分子内各基团和分子链段间排列的 有序性和规整度， 提高载流子迁移率的传输速度和效率， 进而提高光电转 换效率。 在本实施例中， 阴极 15 A1层的厚度分别为 170nm。
如图 3所示， 在光照下， 光透过玻璃基层 11和 ITO电极 12, 活性层 14中的传导空穴型电致发光材料吸收光能， 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 no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， 传导空穴 型电致发光材料由于其具有 4艮宽的光谱响应范围， 能够更充分地利用光能， 以获得更高的光电转换效率， 增加有机太阳能电池的产电能力。 而且这种 有机材料还能减轻有机太阳能电池的质量， 并通过旋涂等技术即可制作， 便于大批量的制备。
表 1为本实施例 6的有机太阳能电池的光伏属性。 （注： PCE为能量转 换效率， V。c为开路电压， Jsc为短路电流， FF为填充因子。）
表 1
V0C(V) Jsc(mA/cm2) FF ( % ) PCE(%)
DFBTz-Fl/PCBM 0.70 10.7 54.5 4.1
表 1结果表明， 在 AMI .5、 100 mW/cm2光照下， 基于 DFBTz-Fl为电 子给体材料的本体异质结太阳能电池的能量转换效率为 4.1%; 其中， AM 为大气质量是指太阳光束穿过大气层的光学路径， 以该光学路径与太阳在 天顶时其光束到达海平面所通过的光学路径的比值表示； AM1.5 条件是指 标定和测试地面用太阳能电池所规定的辐照度和光谱分布； 其太阳能总辐 照度为 1000瓦每平方米， 太阳能电池的测量温度为 25度； 此标准为国际 电工委员会制定， 我国目前采用的是此标准； 具体一点来说， 一个标准太 阳相当于 AM1.5G标准光源的辐照强度， AM 1.5G表示天顶角 （入射光线 于入射光源与地面法线间的夹角）为 48度的太阳光，光强是 1000 W/m2(即 AM 1.5、 100 mW/cm2光照） 。
应当理解的是， 上述针对本发明较佳实施例的表述较为详细， 并不能 因此而认为是对本发明专利保护范围的限制， 本发明的专利保护范围应以 所附权利要求为准。

Claims

权利要求书
1、一种含芴二氟代苯并三唑基共聚物， 其特征在于， 具有下述结构式（I):
Figure imgf000016_0001
式中， 、 R2均为 d~C2。的烷基， n为 10~100的整数。
2、 根据权利要求 1所述的含芴二氟代苯并三唑基共聚物， 其特征在于， n 为 50~70。
3、 一种含芴二氟代苯并三唑基共聚物的制备方法， 其特征在于， 包括如下 步骤：
Sl、 分别提供如下结构式表示的化合物 A和化合物 B,
Figure imgf000016_0002
其中， 所述化合物 A中， 为 d ~ C2。的烷基； 所述化合物 B中， R2 为 d~C2Q的烷基;
S2、 在无氧环境下， 将所述化合物 A和化合物 B按照摩尔比 1:1加入 量， 添加入含有催化剂和碱溶液的有机溶剂中， 于 70~130°C下进行 Suzuki 耦合反应 12-96 小时后， 得到具有下述结构式（I) 的所述含芴二氟代苯 并三唑基共聚物： 式中， n为 10~100的整数。
4、 根据权利要求 3所述的含芴二氟代苯并三唑基共聚物的制备方法， 其特 征在于， 还包括如下步骤：
S3、对步骤 S2中得到的所述含芴二氟代苯并三唑基共聚物进行纯化处 理。
5、 根据权利要求 3或 4所述的含芴二氟代苯并三唑基共聚物的制备方法， 其特征在于， 所述步骤 S2中， 所述催化剂为有机钯， 或者所述催化剂为有 机钯与有机磷配体的混合物。
6、 根据权利要求 5所述的含芴二氟代苯并三唑基共聚物的制备方法， 其特 征在于， 所述步骤 S2中， 所述有机钯与所述化合物 A的摩尔比为
1:20~1:100。
7、 根据权利要求 3或 4所述的含芴二氟代苯并三唑基共聚物的制备方法， 其特征在于， 所述步骤 S2中， 所述有机溶剂选自曱苯、 Ν,Ν-二曱基曱酰胺 及四氢呋喃中的至少一种。
8、 根据权利要求 3或 4所述的含芴二氟代苯并三唑基共聚物的制备方法， 其特征在于， 所述步骤 S2中， 所述碱溶液选自碳酸钠溶液、 碳酸钾溶液及 碳酸氢钠溶液中的至少一种。
9、 根据权利要求 3或 4所述的含芴二氟代苯并三唑基共聚物的制备方法， 其特征在于， 所述步骤 S2中， 所述 Suzuki耦合反应温度为 80~110°C ; 所 述 Suzuki耦合反应时间为 24~72h。
10、 权利要求 1所述的含芴二氟代苯并三唑基共聚物在有机太阳能电池中 的应用。
PCT/CN2011/080102 2011-09-23 2011-09-23 含芴二氟代苯并三唑基共聚物及其制备方法和应用 WO2013040786A1 (zh)

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