CN107698743A - 一类含有氟代苯乙烯噻吩结构共轭聚合物及其在场效应晶体管中的应用 - Google Patents
一类含有氟代苯乙烯噻吩结构共轭聚合物及其在场效应晶体管中的应用 Download PDFInfo
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 26
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 25
- -1 2-decyltetradecyl Chemical group 0.000 claims description 23
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 18
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
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- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
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- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 12
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
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- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
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- IMOLPSNRLZLWQR-UHFFFAOYSA-N 4-bromo-2,3-difluorobenzaldehyde Chemical compound FC1=C(F)C(C=O)=CC=C1Br IMOLPSNRLZLWQR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006284 3-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(F)=C1[H])C([H])([H])* 0.000 description 1
- SWHUROFMIMHWKS-UHFFFAOYSA-N 4-bromo-3-fluorobenzaldehyde Chemical compound FC1=CC(C=O)=CC=C1Br SWHUROFMIMHWKS-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- 241000248771 Amphiops mater Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
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- 238000009987 spinning Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- 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
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Abstract
本发明公开了一种含有氟代苯乙烯噻吩结构共轭聚合物及其制备方法与应用。该共轭聚合物的结构如式I所示。该类聚合物具有较宽的紫外‑可见‑近红外吸收光谱、良好的热学稳定性，具有合适的前沿轨道能级，有利于空穴和电子注入，可以制备较空气稳定的双极性场效应晶体管。该化合物的合成路线简单、有效；原料为商业化的廉价产品，合成成本低；合成方法具有普适性。以本发明含有氟代苯乙烯噻吩结构共轭聚合物为有机半导体层制备的PFET的迁移率和开关比都比较高，式(I)的迁移率最高为0.53cm2V‑ 1s‑1，开关比大于104；在PFET器件中有良好的应用前景。
Description
技术领域
本发明属于有机半导体材料技术领域，具体涉及一类含有氟代苯乙烯噻吩结构共轭聚合物及其在场效应晶体管中的应用。
背景技术
有机场效应晶体管是一种通过电场来控制材料导电能力的有源器件。以π-共轭的聚合物为载流子传输层的场效应晶体管亦称之为聚合物场效应晶体管(Polymer field-effect transistors,简称PFETs)，近年来相关研究取得了飞速的发展。相比传统的无机半导体材料，有机半导体材料，特别是聚合物半导体材料具有众多独特优势，诸如材料种类繁多，可以通过分子设计来调控材料的各种化学、物理特性，从而调控半导体器件的性能；具有良好的柔韧性和弹性，与轻质塑料衬底具有良好的兼容性，可以低温制备柔性有机光电子器件；可以采用溶液旋涂、打印或者印刷加工技术，大面积制备低成本的有机光电子器件与电路，有望成为下一代柔性显示中电路的关键元器件，在电子商标、智能卡、存储器、电子纸、传感器和有源矩阵显示器等方面，具有广阔的应用前景和巨大的经济价值。
相比p-型和n-型聚合物材料，尽管双极性聚合物半导体材料的研究工作也取得了较大进展，但双极性聚合物半导体材料的稳定性，迁移率与p-型和n-型有较大的差距。目前，具有较高空穴迁移率和电子迁移率的双极性聚合物半导体材料仍然局限于少数吡咯并吡咯二酮(DPP)结构单元衍生聚合物，并且大部分双极性材料的空穴迁移率和电子迁移率比值较大，很少能得到在空气中迁移率平衡的双极性材料。(B.Kang,R.Kim,S.B.Lee,S.K.Kwon,Y.H.Kim and K.Cho,J Am ChemSoc,2016,138,3679-3686.K.Kawabata,M.Saito,I.Osaka and K.Takimiya,J Am ChemSoc,2016,138,7725-7732.)。开发高性能、空气稳定的双极性聚合物半导体材料的最大难点在于前沿轨道能级的精确调控，例如：可以引入强吸电子的氟原子，氰基，氮杂环等。因为只有合适的最高占有轨道(HOMO)能级(-5.1±0.3eV)和最低未占有轨道(LUMO)能级(-4.0eV左右)，才有利于空穴和电子的有效注入，从能获得较高的载流子迁移率，另外也有利于获得高空气稳定的聚合物场效应晶体管器件(Salleo,A.Mater.Today2007,10,38；Wang,C.L.；Dong,H.L.；Hu,W.P.；Liu,Y.Q.；Zhu,D.B.Chem.Rev.2012,112,2208)。对供-受型(D-A)聚合物半导体材料来说，尽管人们已经发现其HOMO能级主要取决于供电单元的HOMO能级，而其LUMO能级主要取决于受电单元的LUMO能级,但是双极性聚合物材料的研发依然受困于不可预知的供、受体间的电子推拉作用力大小，材料分子在薄膜中的聚集态结构等等。
鉴于以上原因，特提出本发明。
发明内容
本发明的目的是提供一类含有氟代苯乙烯噻吩结构共轭聚合物及其在场效应晶体管中的应用。
本发明的第一目的提供一类含有氟代苯乙烯噻吩结构共轭聚合物，所述的含有氟代苯乙烯噻吩结构共轭聚合物的结构式如式I所示：
所述式I中，R为C1-C100的直链或支链烷烃基；
X、Y和Z均选自氢原子、氟原子、氯原子和三氟甲基中的任意一种；
n＝10-200。
具体的，所述式I中，n为10-50，具体可为10-20，更具体为11-12；
R可为C1-C30的直链或支链烷烃基，再具体可为C1-C25的直链或支链烷烃基，更具体可为2-癸基十四烷基，也即
具体的，所述式I所示共轭聚合物具体为式I所示PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN化合物中的任意一种：
所述PD-BTAN中，R为2-癸基十四烷基，X＝Y＝Z＝H；
所述PD-3-FBTAN中，R为2-癸基十四烷基，X＝Z＝H，Y＝F；
所述PD-23-FBTAN中，R为2-癸基十四烷基，X＝Y＝H，Y＝H；
所述PD-25-FBTAN中，R为2-癸基十四烷基，X＝Z＝F，Y＝H；
本发明的第二目的在于提供一种制备上述含有氟代苯乙烯噻吩结构共轭聚合物的方法，所述方法包括如下步骤：
将式IV所示化合物、式V所示化合物、催化剂和配体进行Stille聚合反应，反应完毕后得到所述式I所示共轭聚合物；
所述式IV和式V中，R、X、Y和Z的定义与式I相同。
上述方法中，上述催化剂为钯催化剂；所述钯催化剂具体为三(二亚苄基丙酮)二钯或四(三苯基膦)钯；
所述配体为三(邻甲苯基)膦或三苯基膦。
所述式IV所示化合物、式V所示化合物、催化剂和配体的摩尔比为1：0.95～1.05：0.01～0.10：0.02～0.60，具体可为1：1：0.03：0.25；
所述Stille聚合反应步骤中，温度为60～120℃，具体为115℃；时间为24～72小时，具体为72小时。
所述聚合反应在有机溶剂中进行；
所述有机溶剂具体为甲醇、甲苯或氯苯。
本发明的第四目的在于提供一种制备式I所示化合物的中间体化合物，也即式IV所示化合物：
所述式IV中，X、Y和Z的定义与式I中的定义相同。
本发明的第五目的在于提供一种制备式IV所示化合物的方法，包括如下步骤：
将式II所示化合物和式III所示化合物溶于溶剂中，再滴加甲醇钠的甲醇溶液进行脑文格(Knoevenagel)反应，反应完毕得到所述式IV所示化合物；
所述式III中，X、Y和Z的定义与式I相同。
上述方法中，式II所示化合物、式III所示化合物和甲醇钠的投料摩尔用量比为1.0：1.05～1.1：1.05～1.1。
所述滴加步骤中，滴加速率为5mL/min；
所述溶剂为甲醇；
所述反应步骤中，温度为25-100℃，具体为25℃；时间为24-48小时，具体为24小时；
本发明的第六目的在于提供上述式I所示共轭聚合物在制备有机场效应晶体管中的应用以及一种半导体层由式I所示共轭聚合物构成的有机场效应晶体管。
采用上述技术方案，本发明的有益效果如下：
(1)本发明所述的含有氟代苯乙烯噻吩结构共轭聚合物具有较宽的紫外-可见-近红外吸收光谱、良好的热学稳定性，具有合适的前沿轨道能级，有利于空穴和电子注入，可以制备较空气稳定的双极性场效应晶体管。
(2)本发明的含有氟代苯乙烯噻吩结构共轭聚合物的合成步骤少、收率高、聚合物度高、纯化工艺简单易行，适合大规模工业合成。
(3)以本发明含有氟代苯乙烯噻吩结构共轭聚合物半导体材料为半导体层制备的有机场效应晶体管具有优秀的电子迁移率(μe)和开关比(最优为μe为0.53cm2V-1s-1，开关比为103-104)，具有广阔的应用前景。
附图说明
图1为制备含有氟代苯乙烯噻吩结构共轭聚合物的化学反应方程式；
图2为本发明实施例1-4所得共轭聚合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN的合成路线图；
图3为以本发明提供的PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN四种聚合物的薄膜紫外可见吸收光谱图。
图4为以本发明提供的PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN四种聚合物的溶液紫外可见吸收光谱图。
图5为以本发明提供PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN四种聚合物的循环伏安图。
图6为以本发明提供的PD-3-FBTAN在不同栅压下的转移曲线。
图7为以本发明提供的PD-3-FBTAN在不同栅压下的输出曲线。
具体实施方式
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径获得。
实施例1、聚合物PD-BTAN合成步骤
1)式IV所示(4-溴苯甲基)-3-(5-溴噻吩-2-基)丙烯腈的合成
5-溴噻吩-2-乙腈(1.00g，4.93mmol)和4-溴苯甲醛(912.15mg，4.93mmol)溶于甲醇(50.00mL)中搅拌，然后缓慢滴加甲醇钠的甲醇溶液(5.40M，0.91mL，4.93mmol)，滴加速率为5mL/min，进行脑文格(Knoevenagel)反应24h，通过TLC监测反应进程。当原料点消失即停止反应，过滤，用甲醇洗，干燥得0.92g产物，产率50.58％。
结构表征数据如下：
质谱：Calcd for C13H7Br2NS,366.867；found,366.863。
核磁氢谱和碳谱：1H NMR(400MHz,CDCl3)δ7.68(d,J＝7.7Hz,2H),7.56(d,J＝7.7Hz,2H),7.13(d,J＝4.2Hz,2H),7.03(d,J＝3.5Hz,1H).13C NMR(101MHz,CDCl3)δ140.05(s),138.17(s),132.35(s),131.96(s),131.11(s),130.46(s),127.73(s),125.18(s),115.94(s),113.83(s),106.11(s).
2)Stille聚合方法
将式IV所示(4-溴苯甲基)-3-(5-溴噻吩-2-基)丙烯腈(73.81mg，0.20mmol)、式V所示2,5-双(2-葵基十四烷基)-3,6-双(5-(三甲基锡)噻吩-2-基)-2,5-吡咯并[3,4-c]吡咯-1,4-二酮(259.85mg，0.20mmol)、催化剂Pd2(dba)3(6mg，0.006mmol)、配体P(o-tol)3(16.2mg，0.05mmol)、氯苯(8mL)加入到反应瓶中在氩气中进行三次冷冻-抽气-解冻循环除氧，然后将反应混合物加热到115℃进行Stille聚合反应72h。冷却后，加入200mL甲醇/6MHCl混合物(v/v 20:1)，室温下搅拌2h，过滤。得到的聚合物用甲醇洗两遍，然后装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色，除去小分子和催化剂，再用三氯甲烷提取得到聚合物(138.54mg，产率58.26％.
GPC：Mn＝9.69kDa，PDI＝2.41，n＝11。
核磁氢谱：1H NMR(400MHz,CDCl3)δ:9.16-7.52(s,11H),4.01(d,4H),1.32-1.22(m,82),0.87(s,12).
实施例2、聚合物PD-3-FBTAN合成步骤
1)式IV所示(4-溴-3-氟苯甲基)-3-(5-溴噻吩-2-基)丙烯腈的合成
将4-溴-3-氟苯甲醛(1.00g，4.93mmol)和5-溴噻吩-2-乙腈(1.00g，4.93mmol)溶于甲醇(50.00mL)中搅拌，然后缓慢滴加甲醇钠的甲醇溶液(5.40M，0.91mL，4.93mmol)，滴加速率为5mL/min，进行脑文格(Knoevenagel)反应24h，通过TLC监测反应进程。当原料点消失即停止反应，过滤，用甲醇洗，干燥得1.18g产物，产率62.2％。
结构表征数据如下：
质谱：Calcd for C13H6Br2FNS,386.8551；found,386.8543。
核磁氢谱和碳谱：1H NMR(300MHz,CD2Cl2)δ7.71–7.61(m,2H),7.50(dd,J＝8.4,2.1Hz,1H),7.18(d,J＝3.6Hz,2H),7.09(d,J＝4.0Hz,1H).13C NMR(CD2Cl2,ppm)δ:160.78,157.49,139.78,136.84,168.80,134.47,134.37,134.15,131.29,128.19,126.08,126.03,116.40,116.08,115.58,114.26,111.56,111.28,107.23.
2)Stille聚合方法
将式IV所示(4-溴-3-氟苯甲基)-3-(5-溴噻吩-2-基)丙烯腈(77.41mg，0.20mmol)、式V所示2,5-双(2-葵基十四烷基)-3,6-双(5-(三甲基锡)噻吩-2-基)-2,5-吡咯并[3,4-c]吡咯-1,4-二酮(259.85mg，0.20mmol)、催化剂Pd2(dba)3(6mg，0.006mmol)、配体P(o-tol)3(16.2mg，0.05mmol)、氯苯(8mL)加入到反应瓶中在氩气中进行三次冷冻-抽气-解冻循环除氧，然后将反应混合物加热到115℃进行Stille聚合反应72h。冷却后，加入200mL甲醇/6M HCl混合物(v/v 20:1)，室温下搅拌2h，过滤。得到的聚合物用甲醇洗两遍，然后装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色，除去小分子和催化剂，再用三氯甲烷提取得到聚合物(148.50mg,产率61.83％)。
GPC：Mn＝10.69kDa，PDI＝2.41，n＝12。
核磁氢谱：1H NMR(300MHz,CDCl3)δ8.85(s,1H),7.53(s,1H),6.83(s,1H),5.22(s,1H),3.95(s,1H),3.41(s,1H),2.32–2.05(m,1H),2.00–0.50(m,87H).
实施例3：聚合物PD-23-FBTAN合成步骤
1)式IV所示(4-溴-2，3-二氟苯甲基)-3-(5-溴噻吩-2-基)丙烯腈的合成
将4-溴-2，3-二氟苯甲醛(1.00g，4.53mmol)和5-溴噻吩-2-乙腈(1.00g，4.53mmol)溶于甲醇(50.00mL)中搅拌，然后缓慢滴加甲醇钠的甲醇溶液(5.4M，0.84mL，4.53mmol)，滴加速率为5mL/min，进行脑文格(Knoevenagel)反应24h，通过TLC监测反应进程。当原料点消失即停止反应，过滤，用甲醇洗，干燥得1.12g产物，产率61.06％。
结构表征数据如下：
质谱：Calcd for C13H5Br2F2NS[M+]:404.8457Found 404.8450.
核磁氢谱和碳谱：1H NMR(300MHz,CD2Cl2)δ7.86(ddd,J＝8.5,6.9,1.6Hz,1H),7.46(ddd,J＝8.5,6.3,2.0Hz,1H),7.37(s,1H),7.22(d,J＝4.0Hz,1H),7.11(d,J＝4.0Hz,1H).3C NMR(75MHz,CD2Cl2)δ150.61(s),150.04(s),139.62(s),131.33(s),129.96–129.01(m),128.51(d,J＝24.7Hz),123.17(s),115.33(s),114.97(s),112.60(s),109.06(s),54.16(s),53.80(s),53.44(s),52.90(d,J＝26.9Hz),52.32–51.70(m).
2)Stille聚合方法
将式IV所示(4-溴-2，3氟苯甲基)-3-(5-溴噻吩-2-基)丙烯腈(,81.01mg，0.20mmol)、式V所示2,5-双(2-葵基十四烷基)-3,6-双(5-(三甲基锡)噻吩-2-基)-2,5-吡咯并[3,4-c]吡咯-1,4-二酮(259.85mg，0.20mmol)、催化剂Pd2(dba)3(6mg，0.006mmol)、配体P(o-tol)3(16.2mg，0.05mmol)、氯苯(8mL)加入到反应瓶中在氩气中进行三次冷冻-抽气-解冻循环除氧，然后将反应混合物加热到115℃进行Stille聚合反应72h。冷却后，加入200mL甲醇/6M HCl混合物(v/v 20:1)，室温下搅拌2h，过滤。得到的聚合物用甲醇洗两遍，然后装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色，除去小分子和催化剂，再用三氯甲烷提取得到聚合物(141.58mg,产率58.26％)。
GPC：Mn＝10.95kDa，PDI＝2.22，n＝12。
核磁氢谱：1H NMR(300MHz,CDCl3)δ8.96(s,1H),7.61(s,1H),6.91(s,1H),5.30(s,1H),4.05(s,1H),2.37(s,1H),1.88(s,1H),1.21(t,J＝105.6Hz,149H).
实施例4：聚合物PD-25-FBTAN合成步骤
1)式IV所示(4-溴-2，5-二氟苯甲基)-3-(5-溴噻吩-2-基)丙烯腈的合成
将4-溴-2，3-二氟苯甲醛(1.00g，4.53mmol)和5-溴噻吩-2-乙腈(1.00g，4.53mmol)溶于甲醇(50.00mL)中搅拌，然后缓慢滴加甲醇钠的甲醇溶液(5.4M，0.84mL，4.53mmol)，滴加速率为5mL/min，进行脑文格(Knoevenagel)反应24h，通过TLC监测反应进程。当原料点消失即停止反应，过滤，用甲醇洗，干燥得1.07g产物，产率58.34％。
结构表征数据如下：
质谱：Calcd for C13H5Br2F2NS[M+]:404.8457Found 404.8446.
核磁氢谱和碳谱：1H NMR(300MHz,CD2Cl2)δ7.98(dd,J＝9.2,6.4Hz,1H),7.43(dd,J＝9.3,5.7Hz,1H),7.35(s,1H),7.22(d,J＝4.0Hz,1H),7.10(d,J＝4.0Hz,1H).13C NMR(CD2Cl2,ppm)δ:157.99,157.95,157.18,,157.14,154.63,154.59,153.94,153.90,139.59,131.34,128.68,128.53,128.50,128.45,128.42,122.09,121.99,121.90,121.80,121.00,120.64,115.23,114.96,114.72,114.69,1c14.37,114.34,112.02,111.88,111.70,111.56,108.81,108.78.
2)Stille聚合方法
将式IV所示(4-溴-2，,5-二氟苯甲基)-3-(5-溴噻吩-2-基)丙烯腈(81.01mg，0.20mmol)、式V所示2,5-双(2-葵基十四烷基)-3,6-双(5-(三甲基锡)噻吩-2-基)-2,5-吡咯并[3,4-c]吡咯-1,4-二酮(259.85mg，0.20mmol)、催化剂Pd2(dba)3(6mg，0.006mmol)、配体P(o-tol)3(16.2mg，0.05mmol))、氯苯(8mL)加入到反应瓶中在氩气中进行三次冷冻-抽气-解冻循环除氧，然后将反应混合物加热到进行Stille聚合115℃反应72h。冷却后，加入200mL甲醇/6M HCl混合物(v/v 20:1)，室温下搅拌2h，过滤。得到的聚合物用甲醇洗两遍，然后装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色，除去小分子和催化剂，再用三氯甲烷提取得到聚合物(137.50mg,产率56.4％)。
GPC：Mn＝10.99kDa，PDI＝2.27，n＝12。
核磁氢谱：1H NMR(300MHz,CDCl3)δ8.93(s,1H),7.61(s,1H),6.91(s,1H),5.30(s,1H),4.04(s,1H),2.33(s,1H),1.96(d,J＝45.9Hz,3H),1.22(dd,J＝109.9,99.1Hz,125H).
由上可知，该化合物结构正确，为式I所示化合物。
实施例5、化合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN的光谱性能和场效应晶体管性能
1)化合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN的光谱性能。
图3和图4为化合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN在氯苯溶液中和薄膜的紫外可见吸收光谱。
由图3和图4可知，化合物PD-BTAN在氯苯溶液的吸收峰位置为646纳米左右，薄膜吸收峰位置为672和736纳米，化合物PD-3-FBTAN在氯苯溶液的吸收峰位置为694纳米左右，薄膜吸收峰位置为693.03和759.22纳米；PD-23-FBTAN在氯苯溶液的吸收峰位置为706纳米左右，薄膜吸收峰位置为699.83和750.53纳米；PD-25-FBTAN在氯苯溶液的吸收峰位置为700纳米左右，薄膜吸收峰位置为706.34和766.48纳米；根据其薄膜吸收边带计算化合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN的光学带隙分别为1.59、1.40、1.41和1.44电子伏特(光学带隙根据公式Eg＝1240/λ计算，其中Eg为光学带隙，λ为紫外吸收曲线的边界值)。
2)化合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN的电化学性能。
图5为化合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN在乙腈溶液(0.1M四丁基六氟磷酸铵作为支持电解质)中的循环伏安曲线。化合物的前线轨道能级可由公式E＝-(Eonset+4.4eV)得到。
由图5可知，聚合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN的HOMO分别为-5.49、-5.46、-5.51和-5.47电子伏特，LUMO分别为-3.35、-3.40、-3.53和-3.54电子伏特；
3)化合物PD-BTAN、PD-3-FBTAN、PD-23-FBTAN和PD-25-FBTAN的场效应晶体管性能。
有机场效应晶体管制作过程：采用高掺杂的硅片作为衬底和栅电极，300纳米厚的二氧化硅作为绝缘层，金为源电极和漏电极。源漏电极通过光刻制备，基底在丙酮、二次水、乙醇中超声清洗后与80℃真空干燥，并用等离子体处理15分钟。用十八烷基三氯化硅烷(OTS)对二氧化硅表面进行修饰，聚合物为半导体层。聚合物材料在真空度接近10-4帕下蒸镀到被OTS修饰的二氧化硅表面上。将聚合物材料溶于邻二氯苯或氯仿中通过甩膜的方法在OTS修饰的基底上形成薄膜(厚度为40nm)，并在热台上退火5分钟。
在室温下用通过Keithley 4200SCS半导体测试仪测量了所制备的OFET器件的电性质。决定OFET的性能的两个关键参数是：载流子的迁移率(μ)和器件的开关比(Ion/Ioff)。迁移率是指：在单位电场下，载流子的平均漂移速度(单位是cm2V-1s-1),它反映了在电场下空穴或电子在半导体中的迁移能力。开关比定义为：晶体管在“开”状态和“关”状态下的电流之比，它反映了器件开关性能的优劣。对于一个高性能的场效应晶体管，其迁移率和开关比应尽可能的高。
图6和图7为基于PD-3-FBTAN所制备的场效应晶体管在不同栅极电压VG(0到–80V)下的转移曲线和输出特性曲线。输出曲线显示了很好的线性区和饱和区，说明基于PD-3-FBTAN的OFET器件具有很好的场效应调控性能。
载流子迁移率可由方程计算得出：
IDS＝(W/2L)Ciμ(VG–VT)2(饱和区，VDS＝VG–VT)
其中，IDS为漏极电流，μ为载流子迁移率，VG为栅极电压，VT为阈值电压，W为沟道宽度(W＝1400微米)，L为沟道长度(L＝10或20微米)，Ci为绝缘体单位面积电容(SiO2相对介电常数3.9，SiO2层300nm)。利用(IDS，sat)1/2对VG作图，并作线性回归，可由此回归线的斜率推算出载流子迁移率(μ)，由回归线与X轴的截点求得VT。迁移率可以根据公式从转移曲线的斜率计算得出，上述各例中制备的聚合物场效应晶体管的器件性能如表1所示。
含有氟代苯乙烯噻吩聚合物为共聚单元的聚合物为有机层做成了20个有机场效应晶体管器件，在这些器件中，其中，PD-25-FBTAN由图中的数据可计算得到场效应晶体管的迁移率为0.53cm2V-1s-1和开关比为104。
表1、聚合物场效应晶体管的器件性能
Claims (10)
1.式I所示共轭聚合物，
所述式I中，R为C1-C100的直链或支链烷烃基；
X、Y和Z均选自氢原子、氟原子、氯原子和三氟甲基中的任意一种；
n＝10-200。
2.根据权利要求1所述的共轭聚合物，其特征在于：所述式I中，n为10-50或11-12；
R为C1-C30的直链或支链烷烃基或2-癸基十四烷基。
3.一种制备权利要求1或2所述共轭聚合物的方法，包括如下步骤：
将式IV所示化合物、式V所示化合物、催化剂和配体进行Stille聚合反应，反应完毕后得到所述式I所示共轭聚合物；
所述式IV和式V中，R、X、Y和Z的定义与权利要求1相同。
4.根据权利要求3所述的方法，其特征在于：所述催化剂为钯催化剂；所述钯催化剂具体为三(二亚苄基丙酮)二钯或四(三苯基膦)钯；
所述配体为三(邻甲苯基)膦或三苯基膦。
5.根据权利要求3或4所述的方法，其特征在于：所述式IV所示化合物、式V所示化合物、催化剂和配体的摩尔比为1：0.95～1.05：0.01～0.10：0.02～0.60，具体可为1：1：0.03：0.25；
所述Stille聚合反应步骤中，温度为60～120℃，具体为115℃；时间为24～72小时，具体为72小时。
6.根据权利要求3-5中任一所述的方法，其特征在于：所述聚合反应在有机溶剂中进行；
所述有机溶剂具体为甲醇、甲苯或氯苯。
7.式IV所示化合物，
所述式IV中，X、Y和Z的定义与权利要求1相同。
8.一种制备权利要求7所述式IV所示化合物的方法，包括如下步骤：
将式II所示化合物和式III所示化合物溶于溶剂中，再滴加甲醇钠的甲醇溶液进行脑文格反应，反应完毕得到所述式IV所示化合物；
所述式III中，X、Y和Z的定义与权利要求1相同。
9.根据权利要求8所述的方法，其特征在于：所述式II所示化合物、式III所示化合物和甲醇钠的投料摩尔用量比为1.0：1.05～1.1：1.05～1.1；
所述滴加步骤中，滴加速率为5mL/min；
所述溶剂为甲醇；
所述反应步骤中，温度为25-100℃；时间为24-48小时。
10.权利要求1或2任一所述式I所示共轭聚合物在制备有机场效应晶体管中的应用；或者，
一种半导体层由权利要求1或2任一所述式I所示共轭聚合物构成的有机场效应晶体管。
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| CN115340664A (zh) * | 2022-08-16 | 2022-11-15 | 珠海创杰斯特科技有限公司 | 一种新型共聚产物PDPPTT-vinylene及其制备方法与应用 |
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