CN108084409B - 一种宽带隙有机半导体材料及其制备方法和应用 - Google Patents

一种宽带隙有机半导体材料及其制备方法和应用 Download PDF

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CN108084409B
CN108084409B CN201711418999.1A CN201711418999A CN108084409B CN 108084409 B CN108084409 B CN 108084409B CN 201711418999 A CN201711418999 A CN 201711418999A CN 108084409 B CN108084409 B CN 108084409B
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黄飞
谢锐浩
应磊
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Dongguan volt ampere Photoelectric Technology Co., Ltd
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Abstract

本发明公开了一种宽带隙有机半导体材料及其制备方法和应用，该材料结构式如式I，其中，R1、R2和R3为氢或具有1‑30个碳原子的烷基，或者是具有1‑30个碳原子的烷基中一个或多个碳原子被卤素原子、氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基或硝基取代形成的基团；π单元为苯、萘、噻吩、并噻吩、硒吩、碲吩、呋喃、吡咯、吡啶、噻咯、噻唑、恶唑、三唑及它们的衍生物中的一种；n为半导体材料的聚合度，n为1到10000的自然数。该材料在有机太阳电池中表现出优异的器件性能，具有宽的带隙，较深的HOMO能级，能与非富勒烯受体很好的匹配，材料应用于制备有机太阳电池的活性层，在非富勒烯太阳电池器件中获得了较高的能量转换效率。
Figure DDA0001522642650000011

Description

一种宽带隙有机半导体材料及其制备方法和应用
技术领域
本发明属于有机太阳电池技术领域，具体涉及到一种宽带隙有机半导体材料的制备方法，及其在有机光伏器件中的应用。
背景技术
有机太阳能电池(OSCs)是目前新材料、新能源领域研究的热点之一，其具有独特的质轻、柔性、成本低、半透明、可溶液加工、可通过卷对卷(roll to roll)大面积制备柔性器件等优点。近两年来，以有机共轭聚合物为电子给体，非富勒烯为电子受体的聚合物/非富勒烯共混本体异质结(bulk heterojunction,BHJ)太阳能电池发展最为迅速，而且，经过实验室研究人员的共同努力，单层BHJ和叠层BHJ太阳能电池均取得了超过13％的最高能量转化效率(J.Am.Chem.Soc.,2017,139(21),pp 7148–7151.DOI:10.1021/jacs.7b02677；J.Am. Chem.Soc.,2017,139(21),pp 7302–7309.DOI:10.1021/jacs.7b01493)，显示着巨大的应用前景。
而且，非富勒烯受体材料发展的同时也带动了给体材料的发展新方向，非富勒烯小分子受体材料带隙窄，吸收好，为了与其吸收进行互补匹配，人们开发发展了大量的宽带隙聚合物给体材料。Li课题组将宽带隙聚合物J51和J61分别作为给体，ITIC作为受体，制备了效率达到9.26％和9.53％的有机太阳电池器件。Yan课题组使用ITIC为受体，通过调整聚合物的结晶性及结晶尺寸，制备的非富勒烯太阳电池超过10％。Hou课题组报道了 PBQ-4F:ITIC体系的非富勒烯聚合物太阳电池，该体系表现出极低的能量损失(给受体 HOMO能级差约0.04eV)，可以采用低毒溶剂进行加工制备，且器件无需在惰性气体保护下制备，太阳电池器件效率高达11.34％。同一课题组，对ITIC分子末端的受体单元进行甲基的修饰，有效的调节了其HOMO/LUMO能级，采用光谱互补的给体材料PBDB-T，获得12.05％的效率[93]。因此，开发更高性能的宽带隙共轭聚合物非常必要。(Nature Communications,2016,7:13094；Advanced Materials,2017,29(5):1604241；Advanced Materials,2016,28(42):9423-9429；Advanced Materials,2017,1700144.)
发明内容
本发明的目的在于针对已有技术的缺点，提供一种宽带隙有机半导体材料的制备方法，及其在有机光伏器件中的应用。本发明提供的是一种宽带隙有机半导体材料，该类材料具有较宽的光学带隙，光谱能与非富勒烯受体小分子材料的进行很好的匹配，能够有效提高器件的短路电流密度。该类聚合物材料作为电子给体材料，可以应用于有机光伏器件中，并获得了优异的器件效果。
本发明的目的在于提供了所述的宽带隙有机半导体材料的制备方法。
本发明的目的还在于提供所述的宽带隙有机半导体材料在有机光电转换器件中的应用。
本发明的目的通过如下技术方案实现：
一种宽带隙有机半导体材料，所述材料结构式为式(1)所示：
Figure BDA0001522642630000021
其中，R1、R2和R3为氢或具有1-30个碳原子的烷基，或者是所述具有1-30个碳原子的烷基中一个或多个碳原子被卤素原子、氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基或硝基取代形成的基团；π为连接苯并二噻吩单体和含吡咯并[3,4-f]苯并三唑-5,7-二酮单元的桥键单元，包括苯、萘、噻吩、并噻吩、硒吩、碲吩、呋喃、吡咯、吡啶、噻咯、噻唑、恶唑、三唑及它们的衍生物；n为所述聚合物半导体材料的聚合度，n 为1到10000的自然数。
所述的宽带隙有机半导体材料，其特征在于所述π单元优选自以下未取代或取代的结构：
Figure BDA0001522642630000022
R为氢或具有1-30个碳原子的烷基，或者是所述具有1-30个碳原子的烷基中一个或多个碳原子被卤素原子、氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基或硝基取代形成的基团。
所述的宽带隙聚合物的合成方法，包括如下步骤：将聚合单体溶于反应溶剂中，浓度为0.005～0.05mol/L，在保护气氛下，采用零价钯作为催化剂，采用油浴加热或者微波加热，进行聚合反应；所述油浴加热温度为90-180℃，微波反应的温度为100-200℃；所述油浴加热的时间为12-72小时，微波反应的时间为20分钟到4小时。反应结束，将反应液滴入甲醇中析出聚合物，通过在索氏提取器中洗涤提纯，最后得到聚合物。
宽带隙有机半导体材料在制作聚合物有机太阳电池中的应用。应用于聚合物本体异质结太阳电池的给体相，与电子受体材料ITIC、ITIC-4F、PCBM或其衍生物、有机电子受体材料或无机纳米晶混合制成溶液，涂覆在玻璃或缓冲层上，制备成薄膜，然后在薄膜上蒸镀金属制备成器件。
与现有技术相比，本发明的主要优点在于：
本发明通过氟代苯环侧链的苯并二噻吩单体和含吡咯并[3,4-f]苯并三唑-5,7-二酮单元进行共聚，获得宽带隙有机半导体材料，该材料在有机太阳电池中表现出优异的器件性能，具有宽的光学带隙(～1.8eV)，能与非富勒烯受体很好的匹配，能够有效提高器件的短路电流密度；较深的HOMO能级有利于获得更高的开路电压。本发明所制备的宽带隙有机半导体材料应用于制备有机太阳电池的活性层，在非富勒烯太阳电池器件中获得了较高的能量转换效率。
附图说明
图1为实施例11、12所得有机半导体材料的薄膜吸收光谱图。
图2为实施例11、12所得有机半导体材料的氧化还原电势曲线图。
图3为实施例11所得有机半导体材料制备的有机太阳电池器件J-V曲线图。
具体实施方式
以下结合具体实施例来对本发明公开的宽带隙有机半导体材料的制备与应用作进一步的说明。但本发明所要求的保护范围并不局限于实施例所涉及的范围。
实施例1、二甲基-4,7-二(噻吩-2-基)-2,1,3-苯并噻二唑-5,6-二羧酸酯(2)
Figure BDA0001522642630000041
将化合物1(6.92g,22.61mmol)和丁炔二酸二甲酯(6.42g,45.23mmol)溶于80ml二甲苯中，在惰性气体氮气的保护下，加热回流24h。然后用旋转蒸发仪在减压的条件下旋至剩1/3溶剂时，加入硅胶，再旋干溶剂，得到的固体粉末用200-300目的硅胶过柱后，得到黄色目标产物8.4g，产率约为89％。
实施例2、4,7-二(噻吩-2-基)-2,1,3-苯并噻二唑-5,6-二羧酸(3)
Figure BDA0001522642630000042
将化合物2(8.4g,20.2mmol)悬浮在150ml乙醇溶液中，缓慢加入NaOH(12.9g,323.2 mmol)的水溶液(20％)，氮气保护下，回流24h。然后再加入10％的盐酸水溶液直至混合液显酸性，常温条件下，搅拌6h。将反应液用布氏漏斗抽滤，收集滤渣，用水和甲醇洗后得到黄色固体，然后将此粗产物用真空干燥箱在40℃干燥，干燥完可以直接往下一步反应，因为此产物溶解性很差，所以难于对其进一步提纯。
实施例3、,7-二(噻吩-2-基)-2,1,3-苯并噻二唑-5,6-二羧酸酐(4)
Figure BDA0001522642630000043
将化合物3(7.16g,18.45mmol)悬浮在160ml二甲苯中，加入55g乙酸酐，氮气保护下，回流过夜。减压蒸馏除去溶剂，将粗产物用乙醇重结晶，得到红色固体5.86g，产率约为86％。
实施例4、N-辛基-4,7-二(噻吩-2-基)-2,1,3-苯并噻二唑-5,6-二酰亚胺(5)
Figure BDA0001522642630000051
将化合物4(3,36g,9.07mmol)悬浮在150ml冰乙酸中，加入辛胺(2.8g,21.7mmol)，氮气保护下，110℃过夜。然后再加入65ml乙酸酐，110℃下继续搅拌6h。减压蒸馏除去溶剂，干法上柱，将粗产物硅胶层析过柱后得到橙色目标产物4.05g，产率约为92％。
实施例5、N-辛基-4,7-二(噻吩-2-基)-5,6-二氨基-异吲哚啉-1,3-二酮(6)
Figure BDA0001522642630000052
将化合物5(0.87g,1.82mmol)和铁粉(1.22g,21.8mmol)悬浮在30ml冰乙酸中，氮气保护下，回流5h。然后冷却至室温，将混合物倒入水中，析出固体，用布氏漏斗抽滤，收集滤渣，用水和甲醇洗后，所得固体滤渣用200-300目的硅胶层析过柱，最终得到0.6g 黄色固体目标产物，产率约为73％。
实施例6、4,8-二(噻吩-2-基)-1H-6-辛基-5H-吡咯并[3,4-f]-苯并三唑-5,7(6H)-二酮(7)
Figure BDA0001522642630000053
将化合物6(2g,4.4mmol)溶于四氢呋喃中，逐滴加入NaNO2(1.25g,18.24mmol)的水溶液，常温搅拌6h。反应完毕后用二氯甲烷萃取有机相，浓缩有机相，无水硫酸镁干燥，抽滤，旋干溶剂，得到淡黄色固体，真空干燥箱干燥后，所得粗产物可以不经过进一步提纯直接往下一步反应。
实施例7、4,8-二(噻吩-2-基)-6-辛基-2-辛基-5H-吡咯并[3,4-f]-苯并三唑-5,7(6H)-二酮(TZBI)
Figure BDA0001522642630000061
将化合物7(1.7g,3.66mmol)悬浮于甲醇中，加入叔丁醇钾(0.5g,4.4mmol)，等固体溶解后再加入溴辛烷(0.85g,4.4mmol)，氮气保护下，回流24h。反应完毕后用二氯甲烷萃取有机相，浓缩有机相，无水硫酸镁干燥，抽滤，将滤液用旋转蒸发仪在减压条件下旋至剩1/3溶剂时，加入硅胶，再旋干溶剂，得到的固体粉末用200-300目的硅胶过柱后，得到0.75g黄色目标产物，产率约为35％。
实施例8、4,8-二(5-溴噻吩-2-基)-6-辛基-2-辛基-5H-吡咯并[3,4-f]-苯并三唑-5,7(6H)-二酮(Br2-TZBI)
Figure BDA0001522642630000062
将化合物TZBI(0.83g,1.44mmol)溶于30ml氯仿和10ml冰乙酸中，加入NBS(0.64g,3.6mmol)，避光条件下，常温搅拌过夜。反应完后用二氯甲烷萃取有机相，浓缩有机相，无水硫酸镁干燥，抽滤，旋干溶剂，将粗产物硅胶层析过柱后，再用乙醇重结晶得到橙色固体产物0.92g，产率约为88％。
实施例9、4,8-二(5-溴呋喃-2-基)-6-辛基-2-辛基-5H-吡咯并[3,4-f]-苯并三唑-5,7(6H)-二酮(Br2-TZBIF)
Figure BDA0001522642630000071
合成步骤请参考实施例1-7。
实施例10、Sn2-DFPhBDT的合成
Figure BDA0001522642630000072
氮气保护，-78℃下，将2.8ml n-BuLi(2.5M,4.44mmol)逐滴加入到化合物8(0.89g, 1.39mmol)的30ml四氢呋喃溶液中。-78℃下反应半小时后，升到0℃再反应半小时。然后再冷却到-78℃，一次性加入5ml三甲基氯化锡(1M,5mmol)的THF溶液，常温反应过夜。反应完毕后倒入水中淬灭反应，用二氯甲烷萃取有机相，浓缩有机相，无水硫酸镁干燥，抽滤，旋干溶剂，再用乙醇重结晶3次得到白色粉末1.2g，产率约为90％。
实施例11、聚合物PTzBI-1的合成
Figure BDA0001522642630000073
25ml两口圆底烧瓶中依次加入Br2-TZBI(124.8mg,0.17mmol)，Sn2-DFPhBDT(163.0mg,0.17mmol)，6ml无水甲苯，1ml DMF，然后以氩气为惰性气体，用长针头排气泡20 分钟，快速加入3-5mg四合三苯基膦钯催化剂，再用长针头排气20分钟，氩气保护下，避光加热回流48h。反应完毕后，停止加热，反应液温度为室温后，用玻璃滴管将反应液逐到200ml左右无水甲醇中，析出的固体用玻璃漏斗常压过滤，再将固体聚合物用索氏抽提器进行抽提，抽提溶剂顺序为甲醇、丙酮、正己烷，抽提完后，剩余固体用氯仿溶解后，再次用甲醇析出，过滤，真空干燥后得到金属光泽固体160mg，产率约为80％。
实施例12、聚合物PTzBI-2的合成
Figure BDA0001522642630000081
25ml两口圆底烧瓶中依次加入Br2-TZBIF(70.2mg,0.1mmol)，Sn2-DFPhBDT(96.5mg,0.1mmol)，3ml无水甲苯，0.5ml DMF，然后以氩气为惰性气体，用长针头排气泡20 分钟，快速加入3-5mg四合三苯基膦钯催化剂，再用长针头排气20分钟，氩气保护下，避光加热回流48h。反应完毕后，停止加热，反应液温度为室温后，用玻璃滴管将反应液逐到200ml左右无水甲醇中，析出的固体用玻璃漏斗常压过滤，再将固体聚合物用索氏抽提器进行抽提，抽提溶剂顺序为甲醇、丙酮、正己烷，抽提完后，剩余固体用氯仿溶解后，再次用甲醇析出，过滤，真空干燥后得到金属光泽固体158mg，产率约为81％。
图1为实施例11、12所得有机半导体材料的薄膜吸收光谱图。从图1可以看出，聚合物PTzBI-1和PTzBI-2的吸收边大概在670-700纳米波长的位置，通过计算，该类材料是一类宽带隙聚合物材料。
图2为实施例11、12所得有机半导体材料的氧化还原电势曲线图。可以计算得出PTzBI-1和PTzBI-2的HOMO/LUMO能级分别为–5.38/–3.08eV和–5.40/–3.22eV。本发明公开的有机半导体材料，具有较深的HOMO能级，应用于有机太阳电池器件中，有利于提高其开路电压。
图3为实施例11所得有机半导体材料制备的有机太阳电池器件J-V曲线图。为了研究目标聚合物材料PTzBI-1在有机太阳电池的光伏性能，我们制备了正装的有机太阳电池器件，以聚合物PTzBI-1作为给体材料，ITIC-2F作为受体材料，给受体质量比为1:1，加工溶剂为氯苯，器件结构为：ITO/PEDOT:PSS/PTzBI-1:ITIC-2F/PFNBr/Ag。器件制作过程为: 以预先清洗的ITO玻璃为阳极。在ITO玻璃上旋涂40纳米的水溶性聚合物PEDOT:PSS, 干燥后继续旋涂聚合物太阳电池活性层(PTzBI-1:ITIC-2F)。干燥后接着旋涂水醇溶聚合物 PFN-Br的甲醇溶液,控制厚度为5纳米,最后真空蒸镀100纳米的Ag金属阴极。在ITO和 Ag金属电极间施加正偏压,在100毫瓦每平方厘米的AM1.5模拟太阳光的照射下测量其电池特性。
经过器件的表征，基于PTzBI-1:ITIC-2F的光伏器件，能量转换效率高达13.0％，其中短路电流密度(Jsc)为20.25mA cm-2，开路电压(Voc)为0.87V，填充因子(FF)为73.78％。表现出了非常优异的光伏性能，是一类非常有应用前景的聚合物给体材料。
所述ITIC-4F的分子结构式如下所示：
Figure BDA0001522642630000091

Claims (3)

1.一种宽带隙有机半导体材料，其特征在于，所述材料结构式如下：
Figure FDA0002330517170000011
其中，R1、R2和R3为氢或具有1-30个碳原子的烷基，或者是所述具有1-30个碳原子的烷基中一个或多个碳原子被卤素原子、氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基或硝基取代形成的基团；π单元选自以下结构：
Figure FDA0002330517170000012
n为所述有机半导体材料的聚合度，n为1到10000的自然数。
2.权利要求1所述宽带隙有机半导体材料在有机太阳电池中的应用。
3.根据权利要求2所述的应用，其特征在于，将所述有机半导体材料与电子受体材料ITIC、ITIC-4F、PCBM或其衍生物、或无机纳米晶溶于加工溶剂制成活性层溶液，涂覆在玻璃或缓冲层上，制备成薄膜，然后在薄膜上蒸镀金属制备成器件。
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