CN106589326A - 二氟连二噻吩类聚合物及其制备方法与其在场效应晶体管中的应用 - Google Patents
二氟连二噻吩类聚合物及其制备方法与其在场效应晶体管中的应用 Download PDFInfo
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- CN106589326A CN106589326A CN201611102164.0A CN201611102164A CN106589326A CN 106589326 A CN106589326 A CN 106589326A CN 201611102164 A CN201611102164 A CN 201611102164A CN 106589326 A CN106589326 A CN 106589326A
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/34—Oxygen atoms in position 2
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- 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
- C08G61/124—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 nitrogen atom in the ring
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
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- H—ELECTRICITY
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- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K85/151—Copolymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2261/1412—Saturated aliphatic units
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/146—Side-chains containing halogens
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
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- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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Abstract
本发明公开了一种二氟连二噻吩类聚合物及其制备方法与其在场效应晶体管中的应用。二氟连二噻吩类聚合物的结构式如式I所示，其中n为5～100之间的自然数。本发明将氟原子引入至噻吩环上得到二氟连二噻吩(2FBT)，由于氟原子具有强的吸电子特性，原子半径小，与其它原子如氢原子或硫原子的相互作用也较强因此，氟原子的引入可以提高分子的平面性，促进分子堆积。以2FBT作为给体的聚合物具有较低的LUMO能级，传输层的电子注入较为容易，因而可以表现出双极性传输特性。本发明二氟连二噻吩类聚合物能够作为半导体材料层用于制备有机场效应晶体管。以本发明二氟连二噻吩聚合物为半导体层制备的有机场效应晶体管有较高的迁移率(μ)，在双极性OFETs中有良好的应用前景。
Description
技术领域
本发明涉及一种二氟连二噻吩类聚合物及其制备方法与其在场效应晶体管中的应用。
背景技术
有机场效应晶体管(Organic field-effect transistors,简称OFETs)是一种电压控制器件，它通过栅极电压调控源-漏电极间电流大小，有机半导体活性层是该器件的核心部分。相比无机场效应晶体管，有机场效应晶体管可溶液法加工，可大面积印刷制备柔性器件。有机场效应晶体管半导体层可以选用有机共轭小分子或共轭聚合物。聚合物由于具有更好的成膜性，种类更多，以聚合物作为半导体层来构筑OFETs是目前本领域的研究热点。
半导体层材料按其载流子传输特性可分为p型、双极性和n型材料，其载流子依次为空穴、空穴和电子、电子。目前聚合物半导体材料绝大部分是p型材料，这是因为聚合物中的吸电子受体如吡咯并吡咯二酮(即diketopyrrolopyrrole，简称DPP，Z.Yi.；S.Wang.；Y.Liu.Adv.Mater.2015,27,3589.)、异靛青等吸电子能力不强，其相应的聚合物LUMO能级较高，不利于传输层的电子注入。因此，需要得到更高性能的双极性材料需要对现有聚合物进行改进。
发明内容
本发明的目的是提供一种二氟连二噻吩(2FBT)类聚合物及其制备方法与其在场效应晶体管中的应用，本发明研究了所制备的2FBT类聚合物的OFETs性能，结果表明该类聚合物是一类高性能的双极性材料。
本发明首先提供了式1或式2所示化合物：
式1和式2中，R为碳原子总数为1～60的直链或支链烷基。
R优选为4-癸基十四烷基。
式1和式2所示化合物可按照如下步骤制备：
1)在碳酸钾存在的条件下，6-溴靛红与碘代烷进行反应得到式3所示6-溴-1-烷基吲哚-2,3-二酮；
式3中，R为碳原子总数为1～60的直链或支链烷基；
所述反应在N,N-二甲基甲酰胺和四氢呋喃的混合溶剂中进行，两者的体积比可为1：1；
2)在碳酸钾存在的条件下，6-溴-7-氟吲哚-2,3-二酮与碘代烷进行反应得到式4所示6-溴-7-氟-1-烷基吲哚-2,3-二酮；
所述反应在N,N-二甲基甲酰胺和四氢呋喃的混合溶剂中进行，两者的体积比可为1：1；
式4中，R的定义同式3；
3)式4所示6-溴-7-氟-1-烷基吲哚-2,3-二酮与水合肼经还原反应得到式5所示6-溴-7-氟-1-烷基吲哚-2-酮；
所述反应在1,4-二氧六环中进行；
式5中，R的定义同式3；
4)式3所示6-溴-1-烷基吲哚-2,3-二酮、式5所示6-溴-7-氟-1-烷基吲哚-2-酮与对甲苯磺酸进行反应得到式1所示化合物；
所述反应在醋酸溶液中进行；
5)式4所示6-溴-7-氟-1-烷基吲哚-2,3-二酮与式5所示6-溴-7-氟-1-烷基吲哚-2-酮与对甲苯磺酸进行反应得到式2所示化合物；
所述反应在醋酸溶液中进行。
上述的方法中，步骤1)中，所述6-溴靛红、所述碳酸钾与所述碘代烷的摩尔比可为1：1.0～4.0：1.0～3.0，优选1：2.4：1.2；
所述反应的温度可为20～80℃，时间可为2～24小时。
上述的方法中，步骤2)中，所述6-溴-7-氟吲哚-2,3-二酮、所述碳酸钾与所述碘代烷的摩尔比可为1：1.0～4.0：1.0～3.0，优选1：2.4：1.2；
所述反应的温度可为20～80℃，时间可为2～24小时。
上述的方法中，步骤3)中，式4所示6-溴-7-氟-1-烷基吲哚-2,3-二酮与所述水合肼的摩尔比可为1：20～300，优选1：180；
所述还原反应的温度可为80～120℃，时间可为2～48小时。
上述的方法中，步骤4)中，式3所示6-溴-1-烷基吲哚-2,3-二酮与式5所示6-溴-7-氟-1-烷基吲哚-2-酮与所述对甲苯磺酸的摩尔比可为1.0～2.0：1：0.01～0.2，优选1：1：0.096；
所述反应的温度可为80～130℃，时间可为2～48小时。
上述的方法中，步骤5)中，式4所示6-溴-7-氟-1-烷基吲哚-2,3-二酮与式5所示6-溴-7-氟-1-烷基吲哚-2-酮和对甲苯磺酸的摩尔比可为1.0～2.0：1：0.01～0.2，优选1：1：0.10；
所述反应的温度可为80～130℃，时间可为2～48小时。
本发明所提供的二氟连二噻吩类聚合物的结构式如式I所示：
式I中，n为5～100之间的自然数；
Acceptor基团选自如下A类基团中的任意一种：
所述A类基团中，表示取代的位置；
R为碳原子总数为1～60的直链或支链烷基。
R具体可为4-癸基十四烷基。
n为43～50、43或50。
本发明所提供的二氟连二噻吩类聚合物具体可为聚合物P1FIID-2FBT或P2FIID-2FBT；
其中，聚合物P1FIID-2FBT具体如式I-1所示，其中，n＝43：
所述聚合物P2FIID-2FBT具体如式I-2所示，其中，n＝50：
本发明进一步提供了所述二氟连二噻吩类聚合物的制备方法，包括如下步骤：
在催化剂和配体存在的条件下，式Ⅱ所示化合物与二溴化合物经聚合反应即得所述二氟连二噻吩类聚合物；
所述二溴化合物为所述A类基团的二溴取代物。
上述的制备方法中，所述催化剂可为四(三苯基膦)钯、二(三苯基膦)二氯化钯和三(二亚苄基丙酮)二钯中至少一种；
所述配体可为三苯基膦、三(邻甲苯基)膦和三苯基砷中至少一种。
上述的制备方法中，式Ⅱ所示化合物与所述二溴化合物的摩尔比可为1：0.95～1.05，具体可为1：1；
式Ⅱ所示化合物与所述催化剂的摩尔比可为1：0.01～0.10，具体可为1：0.03；
式Ⅱ所示化合物与所述配体的摩尔比可为1：0.08～0.80，具体可为1：0.24。
上述的制备方法中，所述聚合反应的温度可为90～140℃，时间可为2小时～80小时；
所述聚合反应在如下溶剂中进行：
甲苯、氯苯和二甲苯中至少一种。
上述制备方法还包括如下提纯步骤：
在所述聚合反应完毕后，所得反应体系冷却后依次加入浓盐酸和甲醇，室温下搅拌过滤，将所得沉淀用索氏提取器依次用甲醇、丙酮、正己烷抽提，抽提至无色后，除去小分子和催化剂，再用三氯甲烷抽提而得；其中，甲醇和盐酸的体积比具体可为20：1，盐酸的浓度具体可为12M。
本发明将氟原子引入至噻吩环上得到二氟连二噻吩(2FBT)，由于氟原子具有强的吸电子特性，原子半径小，与其它原子如氢原子或硫原子的相互作用也较强因此，氟原子的引入可以提高分子的平面性，促进分子堆积。以2FBT作为给体的聚合物具有较低的LUMO能级，传输层的电子注入较为容易，因而可以表现出双极性传输特性。
本发明提供的式I所示二氟连二噻吩类聚合物能够作为半导体材料层用于制备有机场效应晶体管。
本发明具有如下优点：
1、原料为商业化产品，合成路线简单，产率高，还可以推广到各种直链或支链二氟连二噻吩聚合物的合成；
2、二氟连二噻吩聚合物具有较低的LUMO能级，有利于半导体层电子的注入和传输，可用于双极性场效应晶体管中；
3.以本发明二氟连二噻吩聚合物为半导体层制备的有机场效应晶体管有较高的迁移率(μ)(空穴迁移率最高为5.54cm2V-1s-1；电子迁移率最高为6.64cm2V-1s-1)，在双极性OFETs中有良好的应用前景。
附图说明
图1为本发明聚合物P1FIID-2FBT和P2FIID-2FBT的紫外可见吸收光谱图。
图2为本发明聚合物P1FIID-2FBT和P2FIID-2FBT的循环伏安曲线图。
图3为有机场效应晶体管的结构示意图。
图4为以本发明聚合物P1FIID-2FBT为半导体层的聚合物场效应晶体管的输出特性曲线图(上图)和转移特性曲线图(下图)。
图5为以本发明聚合物P2FIID-2FBT为半导体层的聚合物场效应晶体管的输出特性曲线图(上图)和转移特性曲线图(下图)。
图6为本发明制备式1和式2所示化合物的路线图。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1、聚合物P1FIID-2FBT(式I-1)
反应方程式如图6所示。
1)6-溴-1-(4-癸基十四烷基)吲哚-2,3-二酮
向100mL二口瓶中加入6-溴靛红(2.00g，8.85mmol)，碳酸钾(2.93g,21.24mmol)，1-碘-4-癸基十四烷(4.93g,10.62mmol)，20mL无水N,N-二甲基甲酰胺，20mL无水四氢呋喃，通氩气保护。70℃下反应12h。用水和二氯甲烷萃取，干燥。溶液旋干后过柱(洗脱剂为石油醚：二氯甲烷＝2:1)，得到橙色固体4.09g。产率：82.1％。
结构表征数据如下：
质谱：HR-MALDI-TOF:[M+Na]+calcd for C32H52BrNNaO2:584.30794,found:584.30746.
核磁氢谱和碳谱：1H NMR(400MHz,CDCl3)δ7.46(d,J＝8.0Hz,1H),7.28(dd,J1＝8.0Hz,J2＝1.2Hz,1H),7.06(d,J＝1.2Hz,1H),3.67(t,J＝7.6Hz,2H),1.66(m,2H),1.40–1.11(m,39H),0.88(m,6H).13C NMR(100MHz,CDCl3)δ182.33,157.95,151.88,133.51,126.79,126.37,116.30,113.78,40.87,37.07,33.49,31.93,30.70,30.13,30.09,29.69,29.65,29.36,26.65,24.34,22.70,14.12.
2)6-溴-7-氟-1-(4-癸基十四烷基)吲哚-2,3-二酮
向100mL二口瓶中加入6-溴-7-氟吲哚-2,3-二酮(3.00g,12.29mmol)，碳酸钾(4.08g,29.51mmol)，1-碘-4-癸基十四烷(6.85g,14.75mmol)，20mL无水N,N-二甲基甲酰胺，20mL无水四氢呋喃，通氩气保护。50℃下反应12h。用水和二氯甲烷萃取，干燥。溶液旋干后过柱(洗脱剂为石油醚：二氯甲烷＝3:1)，得到橙色固体5.30g。产率：74.3％。
结构表征数据如下：
质谱：HR-MALDI-TOF:[M+Na]+calcd for C32H51BrFNNaO2:602.29852,found:602.29800.
核磁氢谱和碳谱：1H NMR(400MHz,CDCl3)δ7.33–7.27(m,2H),3.84(t,J＝7.6Hz,2H),1.68(m,2H),1.32–1.20(m,39H),0.88(m,6H).13C NMR(100MHz,CDCl3)δ181.75,181.72,157.66,146.12–143.65(d,JF–C 1＝247Hz),137.91–137.81(d,JF–C 2＝10Hz),128.23,122.03–121.84(d,JF–C 2＝19Hz),121.63–121.59(d,JF–C 3＝4.0Hz),119.32–119.30(d,JF–C 3＝2.0Hz),43.14,43.10,37.06,33.64,33.50,31.94,30.43,30.14,30.09,30.03,29.71,29.67,29.37,26.69,26.63,25.94,25.91,22.70,14.12.
3)6-溴-7-氟-1-(4-癸基十四烷基)吲哚-2-酮
向100mL二口瓶中加入6-溴-7-氟-1-(4-癸基十四烷基)吲哚-2,3-二酮(2.00g,3.44mmol)，20mL 80％水合肼,30mL 1,4-二氧六环，通氩气保护。120℃下反应24h。用水和二氯甲烷萃取，干燥。溶液旋干后过柱(洗脱剂为石油醚：二氯甲烷＝3:1)，得到液体1.53g。产率：78.6％。
结构表征数据如下：
质谱：HR-MALDI-TOF:[M+Na]+calcd for C32H53BrFNNaO:588.31926,found:588.31881。
核磁氢谱和碳谱：1H NMR(400MHz,CDCl3)δ7.18(m,1H),6.90(d,J＝8.0Hz,1H),3.80(t,J＝7.6Hz,2H),3.50(s,2H),1.64(m,2H),1.32–1.02(m,39H),0.88(m,6H).13C NMR(100MHz,CDCl3)δ174.02,145.52–142.28(d,JF–C 1＝324Hz),132.53–132.40(d,JF–C 2＝13.0Hz),126.51–126.46(d,JF–C 3＝5.0Hz),126.06,120.98–120.93(d,JF–C 3＝5.0Hz),109.38–109.12(d,JF–C 2＝26.0Hz),42.41–42.35(d,JF–C 4＝6.0Hz),37.08,35.77,33.51,31.95,30.41,30.11,29.72,29.67,29.38,26.63,26.20,26.17,22.71,14.13.
4)6,6’-二溴-7-氟-1,1’-二(4-癸基十四烷基)异靛青(式1)
向100mL二口瓶中加入6-溴-1-(4-癸基十四烷基)吲哚-2,3-二酮(0.59g,1.06mmol)，6-溴-7-氟-1-(4-癸基十四烷基)吲哚-2-酮(0.60g,1.06mmol)，对甲苯磺酸(20.2mg,0.106mmol)，20mL醋酸，通氩气保护。120℃下反应12h。用水和二氯甲烷萃取，干燥。溶液旋干后过柱(洗脱剂为石油醚：二氯甲烷＝5:1)，得到红色固体0.74g。产率：62.4％。
结构表征数据如下：
质谱：HR-MALDI-TOF:[M+Na]+calcd for C64H103Br2FN2NaO2:1133.62479,found:1133.62426。
核磁氢谱和碳谱：1H NMR(400MHz,CDCl3)δ9.06(d,J＝8.4Hz,1H),8.92(d,J＝8.7Hz,1H),7.16(m,2H),6.92(d,J＝1.8Hz,1H),3.90(t,J＝7.2Hz,2H),3.70(t,J＝7.5Hz,2H),1.66(m,4H),1.32–1.20(m,78H),0.88(m,12H).13C NMR(100MHz,CDCl3)δ167.47,167.30,145.93,145.26,142.05,133.77,132.32,132.19,132.05,132.01,131.40,127.28,126.31,125.73,125.23,123.38,123.33,120.30,114.41,114.16,111.40,42.69,40.66,37.11,33.54,31.94,30.81,30.55,30.11,29.71,29.67,29.37,26.68,26.66,26.13,24.45,22.70,14.13.
5)聚合物P1FIID-2FBT
将6,6’-二溴-7-氟-1,1’-二(4-癸基十四烷基)异靛青(100.0mg,0.090mmol)、5,5’-双(三甲基锡)-3,3’-二氟-2,2’-联二噻吩(47.5mg,0.090mmol)、催化剂三(二亚苄基丙酮)二钯(2.5mg，0.0027mmol)、配体三(邻甲苯基)膦(6.6mg，0.0216mmol)和甲苯(5mL)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120℃进行聚合反应12min。冷却后，加入5mL 12mol/L的浓盐酸，100mL甲醇，室温下搅拌3h，过滤。得到的沉淀物装入索氏提取器抽提。先用甲醇、丙酮、正己烷、三氯甲烷抽提至无色，除去小分子和催化剂，再用氯苯抽提得到最终产物86mg，产率80.1％。
结构表征数据如下：
分子量：GPC:Mn＝50.5kDa,PDI＝2.72，n＝43。
元素分析：Anal.calcd for C72H105F3N2O2S2:C 75.01,H 9.19,N 2.43,found:C75.04,H 9.13,N 2.47。
由上可知，该化合物结构正确，为式I-1所示化合物P1FIID-2FBT，结构式如下所示：
实施例2、聚合物P2FIID-2FBT(式I-2)
反应方程式如图6所示。
1)6,6’-二溴-7,7’-二氟-1,1’-二(4-癸基十四烷基)异靛青(式2)
向100mL二口瓶中加入6-溴-7-氟-1-(4-癸基十四烷基)吲哚-2,3-二酮(0.61g,1.06mmol)，6-溴-7-氟-1-(4-癸基十四烷基)吲哚-2-酮(0.60g,1.06mmol)，对甲苯磺酸(20.2mg,0.106mmol)，20mL醋酸，通氩气保护。120℃下反应12h。用水和二氯甲烷萃取，干燥。溶液旋干后过柱(洗脱剂为石油醚：二氯甲烷＝6:1)，得到红色固体0.70g。产率：58.7％。
结构表征数据如下：
质谱：HR-MALDI-TOF:[M+Na]+calcd for C64H102Br2F2N2NaO2:1151.61537,found:1151.61487。
核磁氢谱和碳谱：1H NMR(400MHz,CDCl3)δ8.89(d,J＝8.4Hz,2H),7.19(m,2H),3.90(t,J＝7.2Hz,4H),1.67(m,4H),1.32–1.20(m,78H),0.88(m,12H).13C NMR(100MHz,CDCl3)δ166.92,144.75–142.33(d,JF–C 1＝242Hz),133.04–133.01(d,JF–C 3＝3.0Hz),132.32–132.22(d,JF–C 2＝10.0Hz),126.33–126.30(d,JF–C 3＝3.0Hz),125.68,123.09–123.05(d,JF–C 3＝4.0Hz),114.76–114.57(d,JF–C 2＝19.0Hz),42.65,42.59,36.95,33.40,31.78,30.41,29.94,29.55,29.51,29.21,26.51,25.92,22.54,13.95.
2)聚合物P2FIID-2FBT
将6,6’-二溴-7,7’-二氟-1,1’-二(4-癸基十四烷基)异靛青(100.0mg,0.0885mmol)、5,5’-双(三甲基锡)-3,3’-二氟-2,2’-联二噻吩(46.7mg,0.0885mmol)、催化剂三(二亚苄基丙酮)二钯(2.4mg，0.00266mmol)、配体三(邻甲苯基)膦(6.5mg，0.0212mmol)和甲苯(5mL)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120℃进行聚合反应12min。冷却后，加入5mL 12mol/L的浓盐酸，100mL甲醇，室温下搅拌3h，过滤。得到的沉淀物装入索氏提取器抽提。先用甲醇、丙酮、正己烷、三氯甲烷抽提至无色，除去小分子和催化剂，再用氯苯抽提得到最终产物80mg，产率77.2％。
结构表征数据如下：
分子量：GPC:Mn＝59.0kDa,PDI＝2.48，n＝50。
元素分析：Anal.calcd for C72H104F4N2O2S2:C 73.86,H 8.96,N 2.39,found:C73.81,H 8.92,N 2.40。
由上可知，该化合物结构正确，为式I-2所示化合物P2FIID-2FBT，结构式如下所示：
实施例3、聚合物P1FIID-2FBT和P2FIID-2FBT的光谱性能、电化学性能和场效应晶体管性能
1)聚合物P1FIID-2FBT和P2FIID-2FBT的光谱和电化学性能
图1为聚合物P1FIID-2FBT(图1(A))和P2FIID-2FBT(图1(B))在溶液和薄膜中的紫外可见吸收光谱。
由图1可知，聚合物薄膜P1FIID-2FBT和P2FIID-2FBT的光学带隙分别为1.59eV和1.40eV(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)。由图1可知，两个聚合物都具有比较强的分子内电荷转移峰，表明该聚合物分子间作用力较强。
图2为聚合物P1FIID-2FBT(图2(A))和P2FIID-2FBT(图2(B))薄膜的循环伏安曲线。测定在CHI660c电化学工作站进行，用传统的三电极结构测试，铂为工作电极，铂丝为对电极，银/氯化银为参比电极，四丁基六氟磷酸铵作为支持电解质。测试在乙腈溶液中进行。循环伏安的条件为：扫描范围为-1.6～1.6伏特(vs.Ag/AgCl)，扫描速率为50毫伏每秒。两个聚合物都具有氧化峰和还原峰，可作为有机半导体材料。根据循环伏安曲线，聚合物P1FIID-2FBT和P2FIID-2FBT的HOMO能级分别为–5.63eV和–5.71eV，LUMO能级分别为–3.55eV和–3.64eV。聚合物具有合适的HOMO能级和LUMO能级，因而是双极性材料。
2)聚合物P1FIID-2FBT和P2FIID-2FBT的场效应晶体管性能
图3为有机场效应晶体管的结构示意图，如图3所示，采用二氧化硅作为基底，在二次水、乙醇、丙酮中超声清洗于80℃真空干燥。以的速度真空蒸镀5nm钛，30nm金作为源漏电极。实施例1～实施例2所得的聚合物为半导体层，将其浓度为10mg/ml的邻二氯苯溶液中通过匀胶的方法在OTS修饰过的二氧化硅上形成有源层，厚度为25nm，并在160℃热台上退火6分钟。
随后在实施例1～实施例2所得的聚合物薄膜表面通过匀胶形成1350纳米厚的聚甲基丙烯酸甲酯作为场效应管绝缘层，90℃除溶剂60分钟；在绝缘层上通过掩膜版热蒸镀50nm厚铝作为栅电极，完成场效应管制备。
在室温下用通过Keithley 4200SCS半导体测试仪测量了所制备的场效应器件的电学性能。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作用下，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4和图5分别为基于两个二氟连二噻吩聚合物所制备的场效应晶体管的转移特性曲线和输出特性曲线。两个聚合物场效应晶体管显示出了明显的双极性传输特性，说明二氟连二噻吩聚合物是一类双极性材料。
载流子迁移率可由方程计算得出：
IDS＝(W/2L)Ciμ(VG–VT)2(饱和区)
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，L为沟道长度，Ci为绝缘体电容。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。开关比可由图4和图5侧源漏电流的最大值与最小值之比得出。
实验结果表明二氟连二噻吩聚合物是一类优异的新型的双极性材料。
表1聚合物场效应晶体管的器件性能
本发明并不限于所报道的这两个材料，改变不同的侧链取代基可以得到一系列的聚合物，且本发明给出的合成方法简单、有效，对于合成新的双极性材料有很大的指导意义。
Claims (8)
1.式1或式2所示化合物：
式1和式2中，R为碳原子总数为1～60的直链或支链烷基。
2.式I所示二氟连二噻吩类聚合物：
式I中，n为5～100之间的自然数；
Acceptor基团选自如下A类基团中的任意一种：
所述A类基团中，表示取代的位置；
R为碳原子总数为1～60的直链或支链烷基。
3.权利要求2所述二氟连二噻吩类聚合物的制备方法，包括如下步骤：
在催化剂和配体存在的条件下，式Ⅱ所示化合物与二溴化合物经聚合反应即得所述二氟连二噻吩类聚合物；
所述二溴化合物为所述A类基团的二溴取代物。
4.根据权利要求3所述的制备方法，其特征在于：所述催化剂为四(三苯基膦)钯、二(三苯基膦)二氯化钯和三(二亚苄基丙酮)二钯中至少一种；
所述配体为三苯基膦、三(邻甲苯基)膦和三苯基砷中至少一种。
5.根据权利要求3或4所述的制备方法，其特征在于：式Ⅱ所示化合物与所述二溴化合物的摩尔比为1：0.95～1.05；
式Ⅱ所示化合物与所述催化剂的摩尔比为1：0.01～0.10；
式Ⅱ所示化合物与所述配体的摩尔比为1：0.08～0.80。
6.根据权利要求3-5中任一项所述的制备方法，其特征在于：所述聚合反应的温度为90～140℃，时间为2小时～80小时；
所述聚合反应在如下溶剂中进行：
甲苯、氯苯和二甲苯中至少一种。
7.权利要求2所述二氟连二噻吩类聚合物在制备有机场效应晶体管中的应用。
8.一种有机场效应晶体管，其半导体材料层为权利要求2所述二氟连二噻吩类聚合物。
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