CN105906788B - 含有吩嗪结构的聚合物及其制备方法和应用 - Google Patents

含有吩嗪结构的聚合物及其制备方法和应用 Download PDF

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CN105906788B
CN105906788B CN201610409666.1A CN201610409666A CN105906788B CN 105906788 B CN105906788 B CN 105906788B CN 201610409666 A CN201610409666 A CN 201610409666A CN 105906788 B CN105906788 B CN 105906788B
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韦玮
刘硕
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Nanjing Post and Telecommunication University
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Abstract

本发明提供了一种含有吩嗪结构的聚合物及其制备方法和应用，所述聚合物的结构如式Ⅰ所示：本发明将二噻吩并苯作为缺电子单元的主要骨架引入到吩嗪分子结构中，制备得到的聚合物因其具有平面性较强的五元环结构，有效的增加了分子的共轭程度，该类聚合物具有较宽的吸收光谱(光学能隙小于1.65eV)、较低的HOMO能级(均低于‑5.5eV)以及较高的迁移率(10‑4‑10‑3cm2/Vs)，应用于光伏器件中可获得大于6％的光电转换效率。

Description

含有吩嗪结构的聚合物及其制备方法和应用
技术领域
本发明属于光电功能材料技术领域，具体涉及一种含有吩嗪结构的聚合物及其制备方法和应用。
背景技术
随着全球经济的不断发展，能源危机和环境问题日益严峻，开发利用新能源迫在眉睫，太阳能作为一种丰富的绿色能源被视为未来能源的主力军。聚合物太阳能电池作为一种新型光伏器件，近年来其开发和应用受到了广泛的关注，目前已成为全球研究的热点。
光伏器件的光电转换效率是衡量电池优劣的标准，主要受开路电压、短路电流以及填充因子的影响。理论上，当电子受体材料选择富勒烯衍生物时，要求作为电子给体材料的聚合物应该具有较窄的光学能隙(可以吸收较多的光子进行光电转换)、较低的分子最高占有轨道(HOMO)能级(增大与富勒烯LUMO轨道能级差)，通过提高短路电流、开路电压和填充因子来进一步提升器件的光电转换效率。
近年来，基于二噻吩并苯(BDT)结构制备的聚合物，如PTB7等(ACSAppl.Mater.Interfaces2014,6,4074；Adv.Energy Mater.2014,1301404；J.Mater.Chem.A,2015,3,10660)以及苯取代结构的吩嗪类聚合物(Macromolecules 2014,47,2921-2928；J.Mater.Chem.A,2013,1,4508–4515)作为电子给体材料，应用于聚合物太阳能电池中均取得了优良的光电转换效率。在上述含有二噻吩并苯(BDT)结构的聚合物中，该结构通常作为给电单元引入到聚合物骨架中；同时在上述苯取代结构的吩嗪类聚合物中，吩嗪聚合物的C1-C4位也均为苯基取代。相反，将BDT作为聚合物缺电单元的主要骨架与喹喔啉结合形成含有噻吩取代的吩嗪结构(即C1-C4为噻吩取代)的聚合物，其制备方法及应用还未见报道。
发明内容
解决的技术问题：本发明针对当前电子给体材料存在的不足，将二噻吩并苯作为聚合物缺电单元的主要骨架，与喹喔啉结合制备含有吩嗪结构的聚合物，该聚合物因为具备较大的共轭体系，可以有效拓宽吸收光谱，吸收更多的光子进行光电转换；同时平面性较强的五元环在空间也有利于电荷的传输和迁移，这些都能提升光伏器件的性能参数，获得优良的光电转换效率。
技术方案：含有吩嗪结构的聚合物，其结构如式Ⅰ所示：
其中，R1为H或F，R2为C8-C20的直链或支链烷基。
当R1为H，R2为异辛基时，所述含有吩嗪结构的聚合物的结构如式Ⅱ所示：
当R1为F，R2为异辛基时，所述含有吩嗪结构的聚合物的结构如式Ⅲ所示：
当R1为F，R2为十二烷基时，所述含有吩嗪结构的聚合物的结构如式Ⅳ所示：
上述含有吩嗪结构的聚合物的制备方法，包括以下步骤：
步骤1，2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)及其衍生物的制备，将4-氟-5-R1-3,6-二烷氧基-苯二胺和4,5-二酮-2,7-二溴-二噻吩并苯溶于醋酸中，在60℃保温反应，得到2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二噻吩，将2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二噻吩和N-溴代琥珀酰亚胺溶于四氢呋喃和二甲基甲酰胺的混合溶剂中反应得到2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)；
步骤2，含有吩嗪结构的聚合物的制备，将缺电单元2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)和2,5-二(三甲基锡)噻吩溶解在甲苯中，氮气保护条件下加入催化剂三(二苯亚甲基丙酮)二钯和配体三邻甲苯基磷，回流反应，冷却至室温，将反应液滴入甲醇中沉降，过滤，收集所得滤饼进行干燥，依次用甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿提取液，用甲醇再次沉降，过滤，所得滤饼即为含有吩嗪结构的聚合物。
进一步地，步骤2中回流反应温度为100℃、时间为24h。
进一步地，步骤2中干燥条件为50℃、12h。
进一步地，步骤2中2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)、2,5-二(三甲基锡)噻吩、三(二苯亚甲基丙酮)二钯和三邻甲苯基磷摩尔比为1：1：0.02：0.08。
进一步地，步骤2中2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)在甲苯中的浓度为0.03mol/L。
上述含有吩嗪结构的聚合物在制备聚合物光伏电池中的应用。
有益效果：本发明将二噻吩并苯作为缺电子单元的主要骨架引入到吩嗪分子结构中，制备得到的聚合物因其具有平面性较强的五元环结构，有效的增加了分子的共轭程度，该类聚合物具有较宽的吸收光谱(光学能隙小于1.65eV)、较低的HOMO能级(均低于-5.5eV)以及较高的迁移率(10-4-10-3cm2/Vs)，应用于光伏器件中可获得大于6％的光电转换效率。
附图说明
图1为实施例2所得聚合物Ⅱ的UV-Vis图；
图2为实施例2所得聚合物Ⅱ的C-V图；
图3为实施例2所得聚合物Ⅱ的I-V图。
具体实施方式
下面通过具体实施方式对本发明作进一步详细说明。但本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂均为可以通过市购获得的常规产品。
实施例1
2-氟-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)的制备
将4-氟-3,6-二辛氧基-苯二胺(0.4g,1mmol)和4,5-二酮-2,7-二溴-二噻吩并苯(0.22g,1mmol)溶于醋酸(40mL)中，升温至60℃，保温反应3h。抽滤，乙醇洗涤滤饼，得2-氟-1,4-辛氧基吩嗪[6,7；8,9]并二噻吩(414mg，73％)。将所得产物溶于THF/DMF(5/10mL)中，40℃下加入NBS(265mg,1.5mmol)，反应5h后，水洗并用二氯甲烷萃取有机相，无水硫酸镁干燥，得到2-氟-1,4-辛氧基吩嗪[6,7；8,9]并二(5-溴噻吩)(360mg，68％)。
核磁表征数据为：1H NMR(CDCl3,500MHz，ppm)，δ＝7.23(s,2H),6.79(d,1H),3.77-4.02(m,4H)，1.96(m,2H),1.29-1.33(m,16H),0.94(t,12H)。
实施例2
式Ⅱ所示聚合物的制备
反应在氮气保护下进行，2-氟-1,4-辛氧基吩嗪[6,7；8,9]并二(5-溴噻吩)(222mg，0.3mmol)和2,5-双(三甲基锡)噻吩(198.6mg，0.3mmol)溶于10mL甲苯中，通氮气0.5h，加入催化剂三(二苯亚甲基丙酮)二钯(5.5mg，0.006mmol)和配体三邻甲苯基磷(9.8mg，0.0024mmol)，继续通气0.5h后开始加热，100℃回流反应24h，体系在室温下自然冷却，逐滴加至甲醇中沉降，过滤，收集滤渣在真空烘箱50℃烘12h，得到的聚合物依次用甲醇、正己烷、氯仿索氏提取，浓缩氯仿提取液，再次滴至甲醇中沉降，过滤，得到聚合物Ⅱ139mg，产率72％，数均分子量42.38kDa，分布系数2.53。
吸收光谱测试：将聚合物Ⅱ用氯仿完全溶解并于匀胶机上旋涂制膜，通过UnicoUV-2102型分光光度计分别对溶液和薄膜进行吸收光谱测试，结果如图1所示，室温下溶液和薄膜的吸收相近，吸收边(λonset)约为760nm，根据公式Eg＝1240/λonset计算得到该聚合物的光学能隙(Eg)为1.63eV。
电化学测试：采用CHI660D型电化学工作站，利用玻碳电极为工作电极，铂丝电极为对电极，Ag/Ag+电极为参比电极，Bu4N·PF6作电解质，在乙腈溶剂中，如图2所示，经循环伏安法测定聚合物Ⅱ薄膜的起始氧化电位为0.81V，按照HOMO能级的计算公式-(4.71+起始氧化电位/V)eV,得到聚合物Ⅱ的HOMO能级为-5.52eV。
光伏性能研究：采用ITO/PEDOT:PSS/聚合物Ⅱ:PC71BM/PFN/Al的三明治电池结构，将聚合物Ⅱ与电子受体材料PC71BM按照重量比1:3制成光伏电池，有效面积0.16cm2，在Newport Thermal Oriel 69911模拟太阳光源下进行电流-电压测试，利用Keithley 2611源表采集，结果如图3所示，开路电压为0.93V，短路电流密度11.08mA/cm2，填充因子63％，光电转换效率为6.49％。
空穴迁移率测试：制备相关器件，经过测试，根据Mott-Gurney定律，运用公式J＝9/8(ε0εμ)(V2/L3)计算得到相应材料的迁移率，其中，ε0为真空介电常数，ε为材料的相对介电常数，μ为载流子迁移率，V为电压，L为活性层的厚度。本实验中制备的器件结构为ITO/PEDOT:PSS/聚合物Ⅱ/Au，其中PEDOT:PSS的厚度控制在30nm左右，聚合物Ⅱ的膜厚约为100nm，Au的厚度为80nm，经过测试，通过空间电荷限制电流(SCLC)法，测试得到聚合物Ⅱ的迁移率为8.2×10-4cm2/V·s。
实施例3
式Ⅲ所示聚合物的制备
同实施例2，缺电子单元为2,3-二氟-1,4-辛氧基吩嗪[6,7；8,9]并二(5-溴噻吩)，采用完全相同的聚合方法得到聚合物Ⅲ，产率66％，数均分子量36.67kDa，分布系数2.75。
吸收光谱测试：将聚合物Ⅲ用氯仿完全溶解并与匀胶机上旋涂制膜，通过UnicoUV-2102紫外可见吸收光谱仪分别对溶液和薄膜进行吸收光谱测试，该聚合物Ⅲ的光学能隙(Eg)为1.67eV。
电化学测试：用CHI660D型电化学工作站，采用玻碳电极为工作电极，铂丝电极为对电极，Ag/Ag+电极为参比电极，Bu4N·PF6作电解质，在乙腈溶剂中，经循环伏安法测定聚合物Ⅲ薄膜的HOMO能为-5.58eV。
光伏性能研究：采用ITO/PEDOT:PSS/聚合物Ⅲ:PC71BM/LiF/Al的三明治电池结构，将聚合物Ⅲ与受体材料PC71BM按照一定的重量比制成光伏电池，有效面积0.16cm2，在Newport Thermal Oriel 69911模拟太阳光源下进行电流-电压测试，利用Keithley 2611源表采集，光电转换效率为6.70％。
空穴迁移率测试：制备相关器件，经过测试，根据Mott-Gurney定律，运用公式J＝9/8(ε0εμ)(V2/L3)计算得到相应材料的迁移率，其中，ε0为真空介电常数，ε为材料的相对介电常数，μ为载流子迁移率，V为电压，L为活性层的厚度。本实验中制备的器件结构为ITO/PEDOT:PSS/聚合物Ⅲ/Au，其中PEDOT:PSS的厚度控制在30nm左右，聚合物Ⅲ的膜厚约为100nm，Au的厚度为80nm，经过测试，通过空间电荷限制电流(SCLC)法，测试得到聚合物Ⅲ的迁移率为1.1×10-3cm2/V·s。
实施例4
式Ⅳ所示聚合物的制备
同实施例2，缺电单元为2,3-二氟-1,4-十二烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)，采用完全相同的聚合方法得到聚合物Ⅳ，产率61％，数均分子量33.67kDa，分布系数2.54。
吸收光谱测试：将聚合物Ⅳ用氯仿完全溶解并与匀胶机上旋涂制膜，通过UnicoUV-2102紫外可见吸收光谱仪分别对溶液和薄膜进行吸收光谱测试。得到该聚合物Ⅳ的光学能隙(Eg)为1.66eV。
电化学测试：用CHI660D型电化学工作站，采用玻碳电极为工作电极，铂丝电极为对电极，Ag/Ag+电极为参比电极，Bu4N·PF6作电解质，在乙腈溶剂中，经循环伏安法测定聚合物Ⅳ薄膜的HOMO能为-5.54eV。
光伏性能研究：采用ITO/PEDOT:PSS/聚合物Ⅳ:PC71BM/LiF/Al的三明治电池结构，将聚合物Ⅳ与受体材料PC71BM按照一定的重量比制成光伏电池，有效面积0.16cm2，在Newport Thermal Oriel 69911模拟太阳光源下进行电流-电压测试，利用Keithley 2611源表采集，光电转换效率为6.00％。
空穴迁移率测试：制备相关器件，经过测试，根据Mott-Gurney定律，运用公式J＝9/8(ε0εμ)(V2/L3)计算得到相应材料的迁移率，其中，ε0为真空介电常数，ε为材料的相对介电常数，μ为载流子迁移率，V为电压，L为活性层的厚度。本实验中制备的器件结构为ITO/PEDOT:PSS/聚合物Ⅳ/Au，其中PEDOT:PSS的厚度控制在30nm左右，聚合物Ⅳ的膜厚约为100nm，Au的厚度为80nm，经过测试，通过空间电荷限制电流(SCLC)法，测试得到聚合物Ⅳ的迁移率为1.3×10-3cm2/V·s。

Claims (7)

1.含有吩嗪结构的聚合物，其特征在于：其结构如式Ⅰ所示：
其中，R1为H或F，R2为C8-C20的直链或支链烷基。
2.权利要求1所述的含有吩嗪结构的聚合物的制备方法，其特征在于：包括以下步骤：
步骤1，2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)及其衍生物的制备，将4-氟-5-R1-3,6-二烷氧基-苯二胺和4,5-二酮-2,7-二溴-二噻吩并苯溶于醋酸中，在60℃保温反应，得到2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二噻吩，将2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二噻吩和N-溴代琥珀酰亚胺溶于四氢呋喃和二甲基甲酰胺的混合溶剂中反应得到2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)；
步骤2，含有吩嗪结构的聚合物的制备，将2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)和2,5-二(三甲基锡)噻吩溶解在甲苯中，氮气保护条件下加入三(二苯亚甲基丙酮)二钯和三邻甲苯基磷，回流反应，冷却至室温，将反应液滴入甲醇中沉降，过滤，收集所得滤饼进行干燥，依次用甲醇、正己烷、氯仿进行索氏提取，浓缩氯仿提取液，用甲醇再次沉降，过滤，所得滤饼即为含有吩嗪结构的聚合物。
3.根据权利要求2所述的含有吩嗪结构的聚合物的制备方法，其特征在于：步骤2中回流反应温度为100℃、时间为24h。
4.根据权利要求2所述的含有吩嗪结构的聚合物的制备方法，其特征在于：步骤2中干燥条件为50℃、12h。
5.根据权利要求2所述的含有吩嗪结构的聚合物的制备方法，其特征在于：步骤2中2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)、2,5-二(三甲基锡)噻吩、三(二苯亚甲基丙酮)二钯和三邻甲苯基磷摩尔比为1：1：0.02：0.08。
6.根据权利要求2所述的含有吩嗪结构的聚合物的制备方法，其特征在于：步骤2中2-氟-3-R1-1,4-烷氧基吩嗪[6,7；8,9]并二(5-溴噻吩)在甲苯中的浓度为0.03mol/L。
7.权利要求1所述的含有吩嗪结构的聚合物在制备聚合物光伏电池中的应用。
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