CN105837598A - 并噻吩并吡咯醌式化合物、制备方法及包含该材料的半导体设备 - Google Patents
并噻吩并吡咯醌式化合物、制备方法及包含该材料的半导体设备 Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明公开了一类并噻吩并吡咯醌式化合物、制备方法及其作为半导体活性层在有机场效应晶体管中的应用。该类化合物具有分子骨架平面性好、自组装能力强、LUMO能级低、能级带隙窄、对氧气和水不敏感等特点,吡咯结构的引入便于通过对取代基的修饰而调节样品溶解性,利于进行溶液加工。由旋涂法制备以化合物Ia为半导体层的有机场效应晶体管具有优良的双极型场效应性能(μh=5.3×10‑3cm2V‑1s‑1,μe=7.7×10‑3cm2V‑1s‑1)。其开关电流比在104以上,且在空气中稳定,具有重要的应用价值。
Description
技术领域
本发明涉及有机场效应晶体管的半导体材料,尤其是涉及一种并噻吩并吡咯醌式化合物、制备方法及包含该材料的半导体设备。
背景技术
近几十年,随着新型有机半导体材料的设计合成以及器件制备技术的优化,有机场效应晶体管(OFET)在器件性能方面取得了突飞猛进的发展。其中,p-型半导体的发展最快,其最高场效应迁移率已经可与传统无机硅材料相媲美,且其空气稳定性较好。n-型半导体通常场效应迁移率较低,空气稳定性差,因而其发展一直较为滞后。双极型半导体的报道则更为稀少。鉴于双极型半导体在构筑逻辑互补电路中的重要作用,空气稳定的高性能双极型半导体材料越来越引起学者的注意。
醌式化合物通常具有骨架极其平面、LUMO能级低、能级带隙窄、对氧气和水不敏感等特点,是一类很有潜力的有机半导体材料。在已报道的文献中,大部分醌式化合物只存在电子传输,也即n-型半导体,例如,2014年,朱道本等人报道了二维联三噻吩型四氰基醌式化合物,该类化合物在有机场效应晶体管中取得迄今为止最高的电子迁移率3.0cm2V–1s–1(参见:Zhu D.,et al.,J.Am.Chem.Soc.2014,136,16176–16184)。
在醌式化合物的研究过程中,研究者们也发现在部分器件当中也会出现双极型电荷传输的现象。例如,Reid J.Chesterfield等人首次发现联三噻吩型四氰基醌式化合物在高温情况下表现出双极型电荷传输,然而其双极型场效应迁移率较低(参见:Reid J.Chesterfield,et al.Adv.Mater.2003,15(15),1278–1282)。此后,以醌式化合物为半导体层的双极型有机场效应晶体管虽有报道(参见:Handa S.,et al.Chem.Comm.2009(26):3919),但数量十分有限。
发明内容
本发明的目的是提供一种并噻吩并吡咯醌型结构化合物、制备方法及包含该材料的半导体设备。
本发明涉及一类如通式I所示的并噻吩并吡咯醌式化合物。
其中,R独立的选自一价可溶性基团。
在本发明的一个实施方案中,本发明的化合物是:
本发明提供的制备上述式I所示化合物的方法,包括下述步骤:
(1)将化合物II与丙二腈负离子进行偶联反应,制得化合物III;
(2)将化合物III进行氧化反应,即可。
其中,R基团的选自碳原子总数为C1-C60的烷基或芳基,优选2-己基癸基,对2-己基癸氧基苯基;X为卤素,优选碘。
所述的制备方法中,步骤(1)中所述的偶联反应包含下列步骤:有机溶剂中,将化合物II在磷配体配位的零价钯试剂的催化下与丙二腈负离子进行反应,即可;其中,所述的有机溶剂为烷氧醚类溶剂;所述的磷配体配位的零价钯试剂为四(三苯基膦)钯;所述的磷配体配位的零价钯试剂与化合物II的摩尔比为0.01:1~0.5:1;所述的丙二腈负离子与化合物II的摩尔比为2:1~10:1;所述的反应的温度为80~100℃;所述的反应时间以检测反应完成为止。
所述的制备方法中,步骤(1)中的丙二腈负离子由丙二腈和强碱在有机溶剂中反应制得;其中,所述的有机溶剂为烷氧醚类溶剂;所述的强碱为活泼金属氢化物;所述的强碱与丙二腈的摩尔比为2:1~5:1;所述的反应温度为-10℃~10℃;所述的反应时间为30min~1h。
所述的制备方法中,步骤(2)中所述的氧化反应包含下列步骤:将化合物III直接暴露于空气中与氧气反应,即可。
上述由本发明提供的式I所示化合物构成的有机场效应晶体管的半导体层,也属于本发明的保护范围。
本发明还提供了一种双极型有机场效应晶体管,由下至上依次由衬底、绝缘体层、半导体层和位于同一层的源电极层和漏电极层组成;所述源电极层和漏电极层不接触。其中,构成所述半导体层的材料为前述本发明所提供的式I所示化合物。
上述双极型有机场效应晶体管可通过本领域常规方法制备,其含有上述内容所描述的化合物。
本发明的积极进步效果在于:本发明提供的并噻吩并吡咯醌式化合物具有分子骨架平面性好、自组装能力强、LUMO能级低、能级带隙窄、对氧气和水不敏感等特点,吡咯结构的引入便于通过对取代基的修饰而调节样品溶解性,利于进行溶液加工。因此,该类化合物是一类具有很大应用前景的有机半导体材料。由旋涂法制备半导体层的有机场效应晶体管具有优良的双极型场效应性能(μh=5.3×10-3cm2V-1s-1,μe=7.7×10-3cm2V-1s-1)。其开关电流比在104以上,且在空气中稳定,具有重要的应用价值。
附图说明
图1为化合物Ia的1H-NMR谱图。
图2为化合物Ia的13C-NMR谱图。
图3为化合物IIa的1H-NMR谱图。
图4为化合物IIa的13C-NMR谱图。
图5为化合物IV的1H-NMR谱图。
图6为化合物IV的13C-NMR谱图。
图7为化合物Ib的1H-NMR谱图。
图8为化合物VII的1H-NMR谱图。
图9为化合物VII的13C-NMR谱图。
图10为化合物Ia的紫外-可见吸收谱图。
图11为以化合物Ia为半导体层的有机场效应晶体管的结构示意图。
图12和图13为以化合物Ia为半导体层的有机场效应晶体管的输出曲线。
图14和图15为以化合物Ia为半导体层的有机场效应晶体管的转移曲线。
具体实施方式
下面结合实施例子进一步说明本发明以及本发明方法进行的方式。这些实施例子仅是为了进一步阐述本发明而非本发明的保护仅限于此。本发明中所述的原料或试剂除特别说明之外,均市售可得。
实施例1:化合物Ia的合成
在0℃、氮气保护下,向装有氢化钠(56.0mg,60wt%,1.4mmol)和1,2-二甲氧基乙烷(5mL)的20mL三口烧瓶中一次性加入丙二腈(46.2mg,0.7mmol),泡沫消除后升至室温反应30分钟。将所制得的丙二腈阴离子溶液通过插管转移到装有化合物IIa(136.5mg,0.14mmol)、四(三苯基膦)钯(32.4mg,0.028mmol)和1,2-二甲氧基乙烷(10mL)的50mL三口烧瓶中,在氮气保护下加热回流反应3小时。随后将反应温度降至室温,并暴露于空气中,加入稀盐酸(10mL,1M),在冰水浴中搅拌30分钟,用乙醚萃取(30mL×3),合并有机相并用饱和食盐水洗涤,以无水硫酸镁干燥,旋转蒸发除去有机溶剂,残留物经硅胶柱色谱分离(洗脱剂:正己烷/二氯甲烷=1/4)后得到化合物Ia(蓝色固体,90.0mg,收率:75%)。1H NMR(400MHz,CDCl3)δ6.39(s,1H),3.85(d,J=8.0Hz,4H),1.95(m,2H),1.28–1.23(m,48H),0.89–0.86(m,12H);13C NMR(100MHz,CDCl3)δ172.2,163.8,136.1,134.6,127.1,114.4,114.2,101.1,65.0,53.4,38.2,31.8,31.7,31.0,30.0,29.6,29.5,29.3,26.2,22.7,22.6,14.14,14.07;HRMS(ESI,m/z)calcd for C50H69N6S3:849.4740[M+H]+;found:849.4740.
实施例2:化合物IIa的合成
在-78℃、氮气保护下,向装有化合物IV(130.2mg,0.18mmol)和四氢呋喃(2mL)的10mL三口烧瓶中缓慢滴加正丁基锂(1.6M in hexane,248μL,0.396mmol),保持低温搅拌30分钟,加入单质碘(100.5mg,0.396mmol),升至室温,继续搅拌2小时后,加入饱和硫代硫酸钠溶液(10mL)进行淬灭,用乙醚萃取(30mL×3),合并有机相并用饱和食盐水洗涤,以无水硫酸镁干燥,旋转蒸发除去溶剂,得到粗产品化合物IIa(黄色油状物,173.8mg,收率:99%)。1H NMR(400MHz,CDCl3)δ7.14(s,2H),4.17(d,J=8.0Hz,4H),1.99(m,2H),1.26–1.12(m,48H),0.89–0.80(m,12H);13C NMR(100MHz,CDCl3)δ144.0,129.9,121.2,120.8,116.3,68.8,53.5,39.0,31.9,31.7,31.0,29.9,29.6,29.4,29.3,26.13,26.09,22.7,22.6,14.2,14.1;HRMS(ESI,m/z)calcd for C44H69I2N2S3:975.2712[M+H]+;found:975.2710.
实施例3:化合物IV的合成
向50mL三口烧瓶中分别加入化合物V(282.0mg,0.5mmol)、叔丁醇钠(768.8mg,8.0mmol)、二(二亚苄基丙酮)钯(28.8mg,0.05mmol)、1,1'-双(二苯基膦)二茂铁(110.9mg,0.2mmol)和甲苯(10mL),在25℃下搅拌20分钟后加入化合物VI(280.1mg,1.16mmol),加热至110℃反应10小时。冷却至室温后,加入水(20mL),用乙醚萃取(30mL×3),合并有机相并用饱和食盐水洗涤,以无水硫酸镁干燥,旋转蒸发除去有机溶剂,残留物经硅胶柱色谱分离(洗脱剂:正己烷)后得到化合物IV(白色固体,181.0mg,收率:50%)。1H NMR(400MHz,CDCl3)δ7.06(d,J=4.8Hz,2H),6.98(d,J=5.6Hz,2H),4.26(d,J=8.0Hz,4H),2.06(m,2H),1.25–1.11(m,48H),0.89–0.81(m,12H);13C NMR(100MHz,CDCl3)δ144.4,130.6,121.5,116.6,116.1,111.5,53.5,39.1,31.9,31.7,31.2,29.9,29.6,29.4,29.3,26.23,26.19,22.7,22.6,14.2,14.1,one aliphatic peak is not shown due to accidental degeneracy;HRMS(ESI,m/z)calcd for C44H71N2S3:723.4774[M+H]+;found:723.4774.
实施例4:化合物Ib的合成
在-78℃、氮气保护下,向装有化合物VII(181.5mg,0.2mmol)和四氢呋喃(2mL)的10mL三口烧瓶中缓慢滴加正丁基锂(1.6M in hexane,275μL,0.44mmol),保持-78℃反应30分钟,加入单质碘(111.7mg,0.44mmol),升至室温,继续搅拌2小时后,加入饱和硫代硫酸钠溶液(10mL)进行淬灭,用乙醚萃取(30mL×3),合并有机相并用饱和食盐水洗涤,以无水硫酸镁干燥,旋转蒸发除去有机溶剂,得到粗产品化合物IIb,并将其直接用于下一步反应。
在0℃、氮气保护下,向装有氢化钠(80.0mg,60wt%,2.0mmol)和1,2-二甲氧基乙烷(2mL)的10mL三口烧瓶中一次性加入丙二腈(66.1mg,1.0mmol),泡沫消除后升至室温,搅拌反应30分钟。将所制得的丙二腈阴离子溶液通过插管转移到装有化合物IIb、四(三苯基膦)钯(23.1mg,0.02mmol)和1,2-二甲氧基乙烷(2mL)的20mL三口烧瓶中,在氮气保护下加热回流反应3小时。随后将反应降至室温,并暴露于空气中,加入稀盐酸(5mL,1M),在冰水浴中搅拌30分钟,用乙醚萃取(30mL×3),合并有机相并用饱和食盐水洗涤,以无水硫酸镁干燥,旋转蒸发除去有机溶剂,残留物经硅胶柱色谱分离(洗脱剂:正己烷/二氯甲烷=1/4)后得到化合物Ib(蓝色固体,148.0mg,收率:73%)。1H NMR(400MHz,THF-d8)δ7.04(d,J=8.8Hz,4H),6.62(d,J=8.8Hz,4H),6.15(s,2H),3.83(d,J=6.0Hz,4H),1.85(m,2H),1.51–1.35(m,48H),0.91–0.90(m,12H);HRMS(ESI,m/z)calcd for C62H77N6O2S3:1033.5270[M+H]+;found:1033.5265.
实施例5化合物VII的合成
向50mL三口烧瓶中分别加入化合物V(282.0mg,0.5mmol)、叔丁醇钠(768.8mg,8.0mmol)、二(二亚苄基丙酮)钯(28.8mg,0.05mmol)、1,1'-双(二苯基膦)二茂铁(110.9mg,0.2mmol)和甲苯(10mL),在25℃下搅拌20分钟后加入化合物VIII(386.9mg,1.16mmol),加热至110℃反应10小时。冷却至室温后,加入水(20mL),用乙醚萃取(30mL×3),合并有机相并用饱和食盐水洗涤,以无水硫酸镁干燥,旋转蒸发除去有机溶剂,经硅胶柱色谱分离(洗脱剂:正己烷/二氯甲烷=10/1)后得到化合物VII(白色固体,318.0mg,收率:70%)。1H NMR(400MHz,CDCl3)δ7.06–7.01(m,6H),6.85(d,J=5.2Hz,2H),6.50(dd,J=6.8,2.0Hz,4H),3.73(d,J=6.4Hz,4H),1.80–1.79(m,2H),1.45–1.30(m,48H),0.92–0.87(m,12H);13C NMR(100MHz,CDCl3)δ157.7,144.8,132.6,130.0,125.6,122.1,117.4,116.9,114.5,112.1,71.6,38.0,32.0,31.4,30.2,29.9,29.8,29.5,29.0,27.0,26.9,22.79,22.78,14.21,14.20;HRMS(ESI,m/z)calcd for C56H79N2O2S3:907.5304[M+H]+;found:907.5300.
效果实施例1化合物Ia的紫外-可见吸收光谱。
图10给出了化合物Ia的紫外-可见吸收光谱。化合物Ia的最大吸收波长位置分别为712nm。光学能级带隙分别为1.59eV。
效果实施例2化合物Ia的电化学性质。
循环伏安法测试在计算机控制的BAS100B电化学分析仪上进行,采用传统的三电极测试体系,即玻碳电极为工作电极,铂电极为对电极,Ag/Ag+电极为参比电极。样品溶于新蒸的二氯甲烷(摩尔浓度为10-3M),Bu4NPF6(0.1M)作为支持电解质;扫描速度为50mV/s,以二茂铁为参比,真空条件下二茂铁的能级为-4.8eV。因二氯甲烷中测得二茂铁相对SCE参比电极的半波氧化电位为0.455V,材料的HOMO和LUMO能级根据以下能级公式计算:
HOMO=-[Eox-0.455+4.8]eV;
LUMO=-[Ered-0.455+4.8]eV
电化学测试显示化合物Ia的半波氧化电位分别为1.175V,由此计算出三个化合物的HOMO能级分别为-5.52eV。
电化学测试显示化合物Ia的半波还原电位分别为-0.255V,由此计算出三个化合物的LUMO能级分别为-4.09eV。
根据下述能级公式计算化合物的电化学能级带隙:
Bandgap=LUMO-HOMO
根据公式计算得出化合物Ia的电化学能级带隙分别为1.43eV。
效果实施例3化合物Ia作为半导体层制备的有机薄膜场效应晶体管的性能。
图11给出了以化合物Ia作为半导体层制备的有机薄膜场效应晶体管的结构示意图。如图11所示,本发明中OTFT器件的制备方法如下:将化合物Ia溶于氯仿配成5mg/mL的溶液,滴在OTS修饰的SiO2/Si基底上(以高掺杂的硅衬底为栅极,热氧化二氧化硅绝缘层的厚度为300nm),制成有机半导体薄膜,在该薄膜上利用掩膜板沉积金源漏电极,从而制得底栅顶电极接触结构的OFET器件。该器件半导体沟道长度为31μm,沟道宽度为273μm。本发明中,OFET的器件性能用Keithley 4200半导体测试仪在空气中室温下测定。
图12和图13分别给出了用化合物Ia制备的一个OFET器件的输出曲线。图14和图15是器件相应的转移曲线。本发明用化合物Ia作为有机半导体层制备了多个OTFT器件,这些器件表现出非常平衡的双极型电荷迁移特性,最高电荷迁移率为μh=5.3×10-3cm2V-1s-1,μe=7.7×10-3cm2V-1s-1,开关比大于104。
Claims (8)
1.具有下述通式I的并噻吩并吡咯醌式化合物:
其中,R选自一价可溶性基团。
2.根据权利要求1的并噻吩并吡咯醌式化合物,其中一价可溶性基团选自碳原子总数为C1-C60的烷基或芳基,其任选被取代。
3.根据权利要求1或2的并噻吩并吡咯醌式化合物,其是:
4.根据权利要求1~3的并噻吩并吡咯醌式化合物的制备方法,其包括下述步骤:
(1)将化合物II与丙二腈负离子进行偶联反应,制得化合物III;
(2)将化合物III进行氧化反应,即可;
其中,R基团的定义如权利要求1~3所述任一项;X为卤素,优选碘。
5.根据权利要求4所述的制备方法,其特征在于,步骤(1)中所述的偶联反应包含下列步骤:有机溶剂中,将化合物II在磷配体配位的零价钯试剂的催化下与丙二腈负离子进行反应,即可;其中,所述的有机溶剂为烷氧醚类溶剂;所述的磷配体配位的零价钯试剂为四(三苯基膦)钯;所述的磷配体配位的零价钯试剂与化合物II的摩尔比为0.01:1~0.5:1;所述的丙二腈负离子与化合物II的摩尔比为2:1~10:1;所述的反应的温度为80~100℃;所述的反应时间以检测反应完成为止。
6.根据权利要求4所述的制备方法,其特征在于,步骤(1)中的丙二腈负离子由丙二腈和强碱在有机溶剂中反应制得;其中,所述的有机溶剂为烷氧醚类溶剂;所述的强碱为活泼金属氢化物;所述的强碱与丙二腈的摩尔比为2:1~5:1;所述的反应温度为-10℃~10℃;所述的反应时间为30min~1h。
7.根据权利要求4所述的制备方法,其特征在于,步骤(2)中所述的氧化反应包含下列步骤:将化合物III直接暴露于空气中与氧气反应。
8.权利要求1~3所述式I化合物作为半导体层的材料应用于有机场效应晶体管的半导体层。
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