CN107236068B - 一类有机晶体管存储驻极体材料及其制备方法和应用 - Google Patents
一类有机晶体管存储驻极体材料及其制备方法和应用 Download PDFInfo
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Abstract
Description
技术领域
本发明属于有机半导体材料技术领域,具体涉及一类电荷存储材料的制备合成方法,并涉及这些材料在有机晶体管电存储等领域的应用。
背景技术
PVK(聚乙烯基咔唑)一直被用作高效的光电材料,最早被合成于1937年,它的使用可追溯的二战时期,自从在上世纪60年代被发现具有光电效应以后,对它的研究一直经久不衰。主要集中在发光及储存器方面研究,在发明主要关注PVK在存储器方面的应用。历来对PVK材料电荷产生的原因和传导机制都有大量研究,在二极管存储器的应用领域PVK也常被用作电荷存储材料[Ling Q,Song Y,Ding S J,Zhu C,Chan D S H,Kwong D L,etal.Adv.Mater.2005,17(13):455-459.]。在晶体管存储器中也有单独使用PVK做驻极体层的报道[Yi M,Xie M,Shao Y,Li W,Ling H,Xie L,et al.J.Mater.Chem.C2015,3(20):5220-5225.],被认为是既能捕获电荷又能起绝缘作用的材料。π堆积聚合物比共轭聚合物有更灵活的构象变化和对外界刺激的快速响应,从这个层次上来讲,堆积聚合物是探索构象关系的优秀材料,然而OFET型存储器驻极体层对电荷捕获的解释还没有从π堆积结构探索过。PVK作为优秀的π堆积材料之一,它在电场下堆积结构的变化已被广泛研究。因此,PVK也有希望作为驻极体层探索构效关系。
同时,由于组成聚合物PVK的咔唑基团本身3,6位的具有很强活性,通过傅克反应能快速引入指定的功能基团,这是一种简单有效的方式,因此我们选择傅克反应来制备基于PVK的一类有机晶体管存储材料。并且可以通过调整功能基团的种类和数量,定性定量来调控其存储行为,是一类非常具有应用前景的有机光电功能材料与方法。
发明内容
技术问题:本发明的目的在于提供一类有机晶体管存储驻极体材料及其制备方法和应用,开发一系列具有改善PVK存储能力的PVK衍生物材料。此外,指出了该类半导体材料在有机场效应晶体管存储器的应用。
技术方案:本发明的一类有机晶体管存储驻极体材料的结构通式如下:
式中:x,m为10~1000的自然数,y为1~500的自然数,Ar为叔醇类芳香基团。
所述的Ar为以下结构中的一种:
以上各式中R1-R10为氢或具有1至22个碳原子的直链、支链或者环状烷基链或其烷氧基;W原子为S或Se。
本发明的一类有机晶体管存储驻极体材料的制备方法是:各类叔醇通过三氟化硼乙醚催化的傅-克反应,实现PVK(聚乙烯基咔唑)与功能基团的共价键连接,其反应路线通式为:
式中:n为10~1000的自然数,x,m为10~1000的自然数,y为1~500的自然数,BF3Et2O为三氟化硼乙醚,CH2Cl2为二氯甲烷,R.T.为搅拌,Ar为以下结构中的一种:
以上各式中R1-R10为氢或具有1至22个碳原子的直链、支链或者环状烷基链或其烷氧基;W原子为S或Se。常温常压条件下反应,溶有三氟化硼乙醚的二氯甲烷(CH2Cl2)溶液缓慢滴入功能基团与PVK的混合二氯甲烷溶液中,数小时滴完即可完成反应。
所述的材料应用于有机晶体管存储器,其中半导体层为并五苯,在并五苯之下充当捕获电荷的驻极体材料。
所述的材料应用于信息存储器件,其中存储器件的结构低栅顶接触,顺序为基底、栅极、遂穿层、有机半导体、源极和漏极。
本发明的一类有机晶体管存储驻极体材料的应用,其特征在于所述的材料作为驻极体层,起捕获、存储电荷的作用,通过溶液旋涂方式制备。
有益效果:通过核磁共振氢谱和碳谱(1H NMR、13C NMR)、飞行时间质谱(MALDI-TOFMS)等表征被引入功能基团的结构。通过凝胶色谱鉴定材料聚合物分子量,通过热重分析和差热分析测试了材料的热稳定性,通过循环伏安法表征了它们的电化学性质,通过紫外吸收光谱分析材料光学性质,通过原子力显微镜观察材料成膜性,通过器件制备及数据分析判断材料在有机存储器
领域中的应用前景。
通过以上手段对所述材料的测试,其结果表明该类后修饰材料很好的热稳定性,较高的玻璃化转变温度,良好的电化学稳定性。该类聚合物薄膜具有极小的粗糙度,说明所述材料可以通过大规模旋涂方式有机场效应晶体管存储器;该类聚合物材料具有相对于PVK具有可忽略的带隙差,因此是研究材料结构-器件性能的良好载体。该类材料所引入功能基团可以有效改善后修饰材料的存储能力。
本发明的主要优点在于:
(1)后修饰材料是由傅-克反应制备得到,反应条件温和,操作简单,毒性小,成本低廉;同时引入基团之上的烷基链或氧烷基链极大增强聚合物溶解性,使得材料更适宜溶液加工,拓展材料的应用范围。
(2)后修饰材料具有良好的光谱、热和电化学稳定性;
(3)后修饰材料作为驻极体材料在有机晶体管中具有优良的双极性存储性能,如大的负向存储窗口和有梯度的正向存储窗口,同时器件还有较高存储开关比和较好的维持时间。
附图说明
图1后修饰材料薄膜状态的紫外吸收和荧光发射光谱,
图2所述材料用于晶体管存储的器件结构,
图3后修饰材料作为驻极体层的有机晶体管存储器的负向写入窗口,
图4后修饰材料作为驻极体层的有机晶体管存储器的维持时间。
具体实施方式
本发明的一类PVK后修饰材料,因引入基团不同而使材料具有不同性能,其特征在于功能基团的引入改善材料存储能力。其结构如结构通式:
式中:x,m为10~1000的自然数,y为1~500的自然数,Ar为以下结构中的一种:
以上各式中R1-R10为氢或具有1至22个碳原子的直链、支链或者环状烷基链或其烷氧基;W原子为S或Se。
本发明的后修饰材料,其特征在于当W为S;R1~R5为氧辛基链时,部分后修饰聚合物其结构分别如下:
本发明的后修饰材料制备方法,其关键步骤是通过格式反应,铃木偶联反应制得功能基团,之后再次通过傅-克反应把功能基团接入PVK体系。以后修饰材料P1、P2、P3为例,具体反应如下:
下面结合实施例来进一步描述本发明的技术方案,但这些实施例并非限制本发明的实施方式。本发明具有多种不同的实施方式,并不只限于本说明书中所述内容。本领域的技术人员在不违背本申请发明精神的情况下,所完成的方案应在本发明的范围内。
实例实施1、单溴芴(10g,41mmol)四丁基溴化铵(1.03g,3.2mmol)投入250mL三口瓶;N2氛围下依次加入1-溴辛烷(31.67g,164mmol)、50%氢氧化钠水溶液20mL、1,4-二氧六环50mL。100℃下反应7h,检测单溴芴反应完全时停止实验,冷却装置。1,4-二氧六环用减压蒸馏蒸出再萃取,合并有机相并用无水硫酸钠干燥。湿法装柱,以石油醚为洗脱剂,最后得无色粘稠液体产物18g(产率93%)。1H NMR(400MHz,CDCl3,δ):7.71(t,J=7.6Hz1H),7.60(d,J=8.0Hz,1H),7.55(d,J=1.6Hz,1H),7.51(dd,J=8.0,1.6Hz,1H),7.34–7.40(m,3H),1.95–2.09(m,4H),1.07–1.33(m,20H),0.90(t,J=7.00Hz,6H),0.75–0.61(m,4H).
实例实施2、THF:Tol=1:1的溶剂80mL置于100mL锥形瓶,DC8BrF(1.6g,3.42mmol)溶于此有机溶剂;新配置的K2CO3/KF(2M)水溶液也置于另一100mL锥形瓶,均鼓泡除氧2h。DBC8OPFOH(1g,1.57mmol),双(三苯基膦)二氯化钯(0.22g,0.314mmol)加入干燥两口瓶中。N2氛围下将DC8BrF溶液注入两口瓶,升温至90℃,体系回流后注入K2CO3/KF(2M)水溶液5mL。反应48h后检测反应完成,加水淬灭,二氯甲烷多次萃取,合并油相后无水硫酸钠干燥,柱层析以石油醚:二氯甲烷=3:1为洗脱剂,得淡黄色油状产物1.2g(产率61%)。1H NMR(400MHz,CDCl3,δ):7.81(d,J=8.0Hz,2H),7.70-7.77(m,8H),7.59(dd,J=7.2,1.6Hz,4H),7.49(d,J=9.2Hz,2H),7.31-7.40(m,6H),6.88(d,J=9.2Hz,2H),3.94(t,J=6.6Hz,2H),2.69(s,1H).2.08-1.90(m,8H),1.72-1.81(m,2H),1.03-1.50(m,45H),0.80-0.98(m,20H),0.64-0.77(m,8H).
实例实施3、所有玻璃仪器均已提前干燥,加入Mg(0.924g,38.5mmol),I2(0.01g)到250mL两口瓶中,然后双排管排尽空气。THF与对溴辛氧基苯(BOB)同时少量注入两口瓶,磁力搅拌。引发完成后,迅速移至冰水浴中,继续滴加BOB(10g,35mmol),THF(50mL)。冰水浴中搅拌反应30min,之后常温反应6h。Mg反应完后,抽出格氏试剂注入N2保护下装有芴酮(2.1g,11.65mmol)的两口瓶,之后装置移入60℃油浴锅反应3h。冷却装置,饱和NH4Cl溶液淬灭,二氯甲烷多次萃取,合并有机相,有机相以无水硫酸钠干燥。柱层析时,以PE:DCM=3:1为洗脱剂分离产物,得淡黄色油状产物3g(产率66.6%)。1H NMR(400MHz,CDCl3,δ):7.68(d,J=7.6Hz,2H),7.30-7.40(m,6H),7.28(td,J=7.4,1.2Hz,2H),6.82(d,J=8.8Hz,2H),3.93(t,J=6.6Hz,2H),2.79(s,1H).1.85-1.75(m,2H),1.55-1.35(m,10H),0.99(t,J=7.0Hz,3H).
实例实施4、250mL三口瓶倒入150mL干燥二氯甲烷,加入C8PFOH(2g,5.18mmol)、2-溴噻吩(1.26g,7.72mmol)。强力搅拌下逐滴滴入三氟化硼乙醚(2.2g,15.54mmol)。反应1h后检测C8PFOH反应完全,加水淬灭40min。分离油相,水相再次用二氯甲烷萃取,之后合并油相,以无水硫酸钠干燥。柱层析以石油醚为洗脱剂,得油状产物1.98g(产率72%)。1H NMR(400MHz,CDCl3,δ):7.77(d,J=7.2Hz,2H),7.49(d,J=7.2Hz,2H),7.40(td,J=7.4,1.2Hz,2H),7.32(td,J=7.4,1.2Hz,2H),7.17(d,J=8.8Hz,2H),6.84(d,J=4Hz,1H),6.77(d,J=7.2Hz,2H),6.63(d,J=3.6Hz,1H),3.90(t,J=6.4Hz,2H),1.72–1.80(m,2H),1.41–1.48(m,2H),1.28-1.36(m,8H),0.91(t,J=7.0Hz,3H).
实例实施5、THF:Tol=1:1的溶剂80mL置于100mL锥形瓶,BrC8OPTF(1g,1.88mmol)溶于此有机溶剂;新配置的K2CO3/KF(2M)水溶液也置于另一100mL锥形瓶,均鼓泡除氧2h。DBC8OPFOH(0.5g,0.784mmol),双(三苯基膦)二氯化钯(0.09g,0.0784mmol)加入干燥两口瓶中。N2氛围下将BrC8OPTF溶液注入两口瓶,升温至90℃,体系回流后注入K2CO3/KF(2M)水溶液5mL。反应48h后检测反应完成,加水淬灭,二氯甲烷多次萃取,合并油相后无水硫酸钠干燥,柱层析以石油醚:二氯甲烷=1:1为洗脱剂,得褐色油状产物0.82g(产率82%)。1HNMR(400MHz,CDCl3,δ):7.75(d,J=7.6Hz,4H),7.54-4.46(m,8H),7.41(d,J=1.6Hz,2H),7.37(td,J=7.6,1.2Hz,4H),7.29(t,J=7.2Hz,4H),7.26(d,J=8.8Hz,2H),7.15(d,J=8.8Hz,4H),7.04(d,J=3.6Hz,2H),6.78-6.71(m,8H),3.88(t,J=6.4Hz,6H),2.43(s,1H),1.68-1.76(m,6H),1.21-1.44(m,27H),0.84-0.91(m,12H).
实例实施6、THF:Tol=1:1的溶剂80mL置于100mL锥形瓶,DC8BrF(1.6g,3.42mmol)溶于此有机溶剂;新配置的K2CO3/KF(2M)水溶液也置于另一100mL锥形瓶,均鼓泡除氧2h。DBC8OPFOH(1g,1.57mmol),双(三苯基膦)二氯化钯(0.22g,0.314mmol)加入干燥两口瓶中。N2氛围下将DC8BrF溶液注入两口瓶,升温至90℃,体系回流后注入K2CO3/KF(2M)水溶液5mL。反应48h后检测反应完成,加水淬灭,二氯甲烷多次萃取,合并油相后无水硫酸钠干燥,柱层析以石油醚:二氯甲烷=3:1为洗脱剂,得淡黄色油状产物1.2g(产率61%)。1H NMR(400MHz,CDCl3,δ):7.81(d,J=8.0Hz,2H),7.70-7.77(m,8H),7.59(dd,J=7.2,1.6Hz,4H),7.49(d,J=9.2Hz,2H),7.31-7.40(m,6H),6.88(d,J=9.2Hz,2H),3.94(t,J=6.6Hz,2H),2.69(s,1H).2.08-1.90(m,8H),1.72-1.81(m,2H),1.03-1.50(m,45H),0.80-0.98(m,20H),0.64-0.77(m,8H).
后修饰一般性合成步骤:
PVK(0.279g,3.1nmol)与C8OPFOH(0.5g,1.29mmol)投入500mL三口瓶,倒入200mL干燥二氯甲烷,强力搅拌。三氟化硼乙醚(0.55g,3.87mmol)注入装有100mL干燥二氯甲烷的恒压滴液漏斗中;逐滴滴入三氟化硼乙醚溶液,3h滴完,继续反应21h后加水淬灭反应。有机相浓缩至少量,在250mL甲醇中沉降,强力搅拌过夜;抽滤得黄色固体,之后用索氏抽提器抽提3天。得黄色固体P1共0.5g(64%)。P2、P3制备步骤同上,投料与产量不同,具体数据如下:
P2:PVK(0.093g,1.02nmol)与C8OPFOHDDC8F(0.5g,0.43mmol),三氟化硼乙醚(0.18g,1.29mmol),产率0.25g(49%)。
P3:PVK(0.167g,1.85nmol)与C8PFOHDTC8PF(0.78mmol,1g),三氟化硼乙醚(0.33g,2.34mmol),产率0.3g(26%)。
实施实例7、本发明提供了一种晶体管存储器件制备方法,器件被制备在重掺杂的n型硅片上,生长在Si片上的300nm厚的SiO2作为栅极绝缘层。Si/SiO2基片分别在甲苯、丙酮和乙醇中超声情况下清洗20min,基片最后用去离子水清洗,让后放入80℃烘箱干燥30min。PVK,P1,P2和P3的甲苯溶液旋涂在基片上形成20nm厚薄膜,各溶液对应浓度分别为8mgmL-1,6mgmL-1,5mgmL-1和8mgmL-1。然后这些旋有薄膜的基片放入80℃烘箱30min。随后把硅片取出放上掩膜版放入真空蒸镀台,分阶段加热蒸镀台至工作稳定,在压力5×10-4Pa,沉积速度条件下蒸上50nm厚度的并五苯,最后在并五苯上面蒸上金电极。
Claims (4)
2.一种如权利要求1所述的一类有机晶体管存储驻极体材料的应用,其特征在于所述的材料应用于有机晶体管存储器,其中半导体层为并五苯,在并五苯之下充当捕获电荷的驻极体材料。
3.如权利要求2所述的一类有机晶体管存储驻极体材料的应用,其特征在于所述的材料应用于信息存储器件,其中存储器件的结构低栅顶接触,顺序为基底、栅极、遂穿层、有机半导体、源极和漏极。
4.如权利要求2所述的一类有机晶体管存储驻极体材料的应用,其特征在于所述的材料作为驻极体层,起捕获、存储电荷的作用,通过溶液旋涂方式制备。
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