CN102405247B - 含有咔唑的导电聚合物、以及使用其的有机光伏器件 - Google Patents
含有咔唑的导电聚合物、以及使用其的有机光伏器件 Download PDFInfo
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- CN102405247B CN102405247B CN201080017043.0A CN201080017043A CN102405247B CN 102405247 B CN102405247 B CN 102405247B CN 201080017043 A CN201080017043 A CN 201080017043A CN 102405247 B CN102405247 B CN 102405247B
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- carbazole
- photoelectric conversion
- conductive polymers
- organic photovoltaic
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 67
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000013086 organic photovoltaic Methods 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
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- 239000002904 solvent Substances 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 5
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- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
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- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
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- Photovoltaic Devices (AREA)
Abstract
本发明涉及由以下化学式1表示的含有2,7-咔唑基团的导电聚合物和使用所述导电聚合物作为光电转换材料的有机光伏器件。本发明提供导电聚合物,其中特定量的咔唑化合物引入到单独地包含给体官能团、包含各种类型的芳族单体的一种或多种的聚合物中、或者引入到其中重复的受体基团引入到给体官能团中的给体-受体型聚合物中,由此改善所述导电聚合物的光子吸收率和空穴迁移率。因此,本发明的导电聚合物可用作用于有机薄膜晶体管(OTFT)或者有机发光二极管(OLED)的光电转换材料。此外,本发明提供使用所述含有咔唑化合物的导电聚合物作为电子给体的有机光伏器件,以由此在有机薄膜太阳能电池中实现改善的光电转换效率。
Description
技术领域
本发明涉及由式1表示的含有2,7-咔唑的导电聚合物以及包括所述导电聚合物作为光电转换材料的有机光伏器件,并且更具体地涉及通过将少量咔唑引入包含一种或多种芳族单体的聚合物中而制备的具有改善的空穴迁移率的导电聚合物、以及包括所述导电聚合物作为光电转换材料的具有改善的能量转换效率的有机光伏器件。
背景技术
有机薄膜太阳能电池使用有机材料作为光活性层并且具有如下优点:它们具有几百nm或更小的薄的厚度、使用相对便宜的材料作为光活性层并且可制造成柔性器件。由于这样的优点,已经进行了许多对有机薄膜太阳能电池的研究。
光活性层通常由两种具有不同的电子亲和性的材料制成,其中所述光活性材料之一通过吸收光而激发以形成激子,和在较低电子亲和性材料(给体)中的电子越过所述两种材料之间的界面移向较高电子亲和性材料(受体),使得激子分离为空穴和电子。此处,激子可移动的距离为约10nm,尽管其取决于材料而变化。因此,如果光吸收位置与所述两种具有不同电子亲和性的材料的界面之间的距离为约10nm或者更小,则激子分离为电子和空穴可以最高的效率实现。因此,主要使用包括给体和受体材料的混合物的体异质结结构(bulk heterojunction structure)。
制造有机太阳能电池的方法大致分成两种方法:通过热沉积给体和受体材料制造薄膜的方法,和使用溶液工艺制造薄膜的方法。
具体地,在采用热沉积的方法中,给体和受体材料两者均为单体,而在采用溶液工艺的方法中,给体材料通常为聚合物,和受体材料为聚合物、富勒烯衍生物、二萘嵌苯衍生物、无机量子点纳米颗粒等。因此,当使用采用聚合物的溶液工艺时,与热沉积单体时相比,可以便宜的方式制造大面积的器件。因此,近年来,已经积极地进行对采用聚合物的溶液工艺的研究。
迄今为止,使用富勒烯衍生物作为受体材料已显示出最高效率[J.Am.Chem.Soc.,2008,130(48),16144]。为了提高光电转换效率,还已经开发了串联型器件,其包括夹在两种吸收不同区域中的光的聚合物之间的中间电极[Science,2007,317,222]。
有机太阳能电池应满足高的光电转换效率。为了实现高的光电转换效率,应满足以下要求。首先,在光吸收层中应吸收大量光子。第二,被吸收并且激发的激子应移向给体/受体界面使得它们有效地分离为空穴和电子。第三,所分离的空穴和电子应无损失地移向正极和负极。
当使用富勒烯衍生物作为体异质结结构中的受体材料时,第二激子的分离看上去定量地发生。因此,为了在有机薄膜太阳能电池中实现高的光电转换效率,作为给体材料使用的聚合物应满足吸收大量光子的性质和使空穴移动的能力两者。
因此,本发明人已进行了大量努力以在有机薄膜太阳能电池中实现高的光电转换效率,且结果已经设计出使用由于高的空穴迁移率在有机发光二极管(OLED)和有机薄膜晶体管(OTFT)中经常使用的咔唑基团的电子给体的分子设计,从而完成本发明。
发明内容
本发明的一个目的是提供具有增强的光子吸收能力和空穴迁移率的导电聚合物、以及其作为光电转换材料的用途。
本发明的另一目的是提供包括所述导电聚合物作为电子给体的有机光伏器件。
为了实现以上目的,本发明提供由下式1表示的含有2,7-咔唑的导电聚合物:
[式1]
其中l是单体X的摩尔分数并且m为单体Y的摩尔分数并且n为咔唑的摩尔分数并且 X和Y各自为具有给体、受体或光吸收功能的单体结构,和R1为C1-C20烷基、C1-C20烷氧基、C3-C20环烷基、C1-C20杂环烷基、芳基、杂芳基、CN、C(O)R或C(O)OR,其中R为C1-C20烷基、C1-C20杂环烷基、芳基、或杂芳基。
而且,当X和Y之一为给体单体结构时,另一个为受体单体结构。
而且,本发明提供用于有机光伏器件、有机发光二极管或有机薄膜晶体管的光电转换材料,其包括由式1表示的含有2,7-咔唑的导电聚合物。
此外,本发明提供有机光伏器件,其包括基底、第一电极、缓冲层、光电转换层和第二电极,其中光电转换层由光电转换材料制成,所述光电转换材料为作为电子给体的本发明的式1的含有2,7-咔唑的导电聚合物与作为电子受体的C60富勒烯衍生物或C70富勒烯衍生物的混合物。
在本发明的有机光伏器件中,光电转换层由光电转换材料制成,所述光电转换材料为作为电子给体的式1的含有2,7-咔唑的导电聚合物与作为电子受体的C60富勒烯衍生物或C70富勒烯衍生物的混合物,其中所述电子给体和所述电子受体以1∶0.5-1∶4的重量比彼此混合。
而且,所述光电转换材料是通过将其溶解在选自氯苯、1,2-二氯苯和氯仿的任意一种溶剂中以达到1.0-3.0重量%的固含量而作为溶液制备的。
根据本发明,可通过将少量咔唑引入包含一种或多种芳族单体的聚合物中而提供具有高的光子吸收效率和提高的空穴迁移率的导电聚合物。
由于其高的光子吸收效率和空穴迁移率,所述含有咔唑的导电聚合物可用作有机光伏器件中的电子给体。而且,其可有利地用于各种领域,包括有机薄膜晶体管(OTFT)和有机发光二极管(OLED)。
此外,根据本发明,可通过使用所述含有咔唑的导电聚合物作为电子给体和C60富勒烯衍生物或C70富勒烯衍生物作为电子受体而提供构成有机光伏器件的光电转换层。
附图说明
由结合附图考虑的以下具体描述,将更清楚地理解本发明的以上和其它目的、特征和优点,其中:
图1是根据本发明一个实施方式制造的有机光伏器件的示意图;
图2显示根据本发明优选实施方式制造的有机光伏器件的电流密度-电压的测量结果;和
图3显示根据本发明的其它优选实施方式制造的有机光伏器件的电流密度-电压的测量结果。
具体实施方式
下文中,将详细描述本发明。
本发明提供由下式1表示的含有2,7-咔唑的导电聚合物:
[式1]
其中l为单体X的摩尔分数并且m为单体Y的摩尔分数并且n为咔唑的摩尔分数并且 X和Y各自为具有给体、受体或光吸收功能的单体结构,和R1为C1-C20烷基、C1-C20烷氧基、C3-C20环烷基、C1-C20杂环烷基、芳基、杂芳基、CN、C(O)R或C(O)OR,其中R为C1-C20烷基、C1-C20杂环烷基、芳基、或杂芳基。
式1的导电聚合物包括引入仅由给体官能团构成且包含一种或多种芳族单体的聚合物中、或者引入包含引入给体官能团中的重复的受体基团的给体-受体型聚合物中的高的空穴迁移率的咔唑基团。如果导电聚合物中2,7-咔唑基团的含量过高,则由于咔唑基团相对低的吸光度(吸收率,absorbance)而难以实现作为所需化合物的导电聚合物的高吸光度。因此,将咔唑基团引入本发明的式1的导电聚合物中,由此可获得可改善空穴迁移率且同时可实现高吸光度的导电聚合物。
而且,为了引入提高吸光度的功能和实现聚合物自组装的功能两者,根据本发明的式1的导电聚合物中的X、Y或者X和Y的组合是重要的。当X和Y的任一个为给体单体结构时,另一个应具有受体单体结构。
所述给体单体优选为选自由以下式2~式10表示的化合物的任一种:
[式2]
[式3]
[式4]
[式5]
[式6]
[式7]
[式8]
[式9]
[式10]
其中R2或R3为C1-C20烷基、C1-C20杂环烷基、芳基、或杂芳基。
而且,所述受体单体优选为选自由以下式11~16表示的化合物的任一种:
[式11]
[式12]
[式13]
[式14]
[式15]
[式16]
其中R4或R5为C1-C20烷基、C1-C20杂环烷基、芳基、或杂芳基。
根据本发明的式1的导电聚合物中的X或Y可不仅为给体单体或受体单体,而且可为选自各种已知的导电官能团或具有光吸收功能的单体的任意一种单体结构。优选地,X和Y两者可为结晶噻吩衍生物。更优选地,X具有给体官能团,和Y具有受体官能团,使得可提供给体-受体型的低带隙聚合物。
本发明提供下式1的含有2,7-咔唑的导电聚合物作为在有机光伏器件中起到电子给体作用的光电转换材料的用途:
[式1]
其中l、m、n、X、Y和R1如上定义。
在本发明的一个实施方式中,根据以下反应方案1制备在芴和二噻吩基苯并噻二唑的共聚物中包含咔唑基团的优选的导电聚合物:
[反应方案1]
在另一实施方式中,根据以下反应方案2制备在二噻吩并噻咯(dithiophenesilole)和苯并噻二唑的共聚物中包含咔唑基团的导电聚合物:
[反应方案2]
根据本发明,可通过将2,7-咔唑基团以20摩尔%或更少、并且优选10摩尔%或更少的量引入导电聚合物的主链中而制备具有改善的空穴传输性能的导电聚合物。
当使用本发明的含有咔唑的导电聚合物作为电子给体并且使用富勒烯衍生物作为受体时,有机薄膜太阳能电池显示出高的光电转换效率(表1和2),从而满足高的光子吸收效率和空穴迁移率两者。
因此,本发明提供式1的含有2,7-咔唑的导电聚合物作为在有机光伏器件、有机发光二极管(OLED)或者有机薄膜晶体管(OTFT)中作为非线性光学材料有用的光电转换材料的用途。
本发明还提供有机光伏器件,其包括基底、第一电极、缓冲层、光电转换层和第二电极,其中所述光电转换层由光电转换材料制成,所述光电转换材料为作为电子给体的本发明的式1的含有2,7-咔唑的导电聚合物与作为电子受体的C60富勒烯衍生物或C70富勒烯衍生物的混合物。
图1是显示根据本发明的优选实施方式制造的有机光伏器件的示意图。如图1中所示,根据本发明的有机光伏器件100从下到上包括基底110、第一电极120、缓冲层130、光电转换层140和第二电极150,其中所述光电转换层由光电转换材料形成,所述光电转换材料为作为电子给体的式1的含有2,7-咔唑的导电聚合物与作为电子受体的C60富勒烯衍生物或C70富勒烯衍生物的混合物。
而且,在本发明的有机光伏器件中,可在光电转换层140和第二电极150之间引入电子传输层、空穴阻挡层或者光学间隔层(光学空间层,opticalspace layer)。
由于用作本发明的有机光伏器件中的电子给体的导电聚合物含有咔唑,本发明的有机光伏器件可具有高的光子吸收效率和改善的空穴迁移率,从而在有机薄膜太阳能电池中实现高的光电转换效率(图2和3)。
用作本发明有机光伏器件中的电子给体的导电聚合物中的咔唑的含量优选为 并且更优选
本发明有机光伏器件中使用的基底110的材料优选为透明材料,并且其实例包括玻璃或塑性材料,例如PET(聚对苯二甲酸乙二醇酯)、PEN(聚萘二甲酸乙二醇酯)、PP(聚丙烯)、PI(聚酰胺)、TAC(三乙酰基纤维素)等,并且优选玻璃。
可通过经由溅射、旋涂等在基底110的一个表面上施加透明材料或透明材料的膜形成第一电极120。第一电极120起到阳极的作用。作为第一电极120的材料,可使用任何材料而没有特别限制,只要其为具有比如下所述的第二电极150的功函低的功函的透明的导电材料。第一电极120的材料的实例包括ITO(氧化铟锡)、FTO(氟掺杂的氧化锡)、ZnO-(Ga2O3或Al2O3)、SnO2-Sb2O3等。更优选地,使用ITO。
形成于第一电极120上的缓冲层130可由可提高空穴迁移率的掺杂有聚磺苯乙烯的聚(3,4-亚乙基二氧噻吩)[PEDOT:PSS]制成。缓冲层130可通过例如旋涂的方法形成。
同时,在缓冲层130上沉积光电转换层140。光电转换层140具有电子给体和电子受体的结结构(junction structure)并且通过电子给体和电子受体之间的快速电荷转移提供光伏效应。
在本发明中,使用根据本发明的式1的含有2,7-咔唑的导电聚合物作为光电转换层140中的电子给体,并且使用C60富勒烯衍生物或C70富勒烯衍生物作为电子受体。
而且,在本发明的光电转换层140的光电转换材料中,式1的含有2,7-咔唑的导电聚合物和C60富勒烯衍生物或C70富勒烯衍生物之间的混合比优选为1∶0.5-1∶4的重量比。如果富勒烯衍生物以小于0.5使用,则由于结晶化的富勒烯衍生物的含量的缺乏,所产生电子的移动不足;和如果富勒烯衍生物超过4的重量比,则吸收光的导电聚合物的量将减少,使得未实现光的有效吸收。
将由含有咔唑的导电聚合物和C60富勒烯衍生物或C70富勒烯衍生物的混合物组成的光电转换材料溶解在单一有机溶剂或具有不同沸点的两种或更多种有机溶剂中以制备溶液。具体地,将光电转换材料溶解在选自氯苯、1,2-二氯苯和氯仿的任意一种溶剂中以达到1.0-3.0重量%的固含量。如果溶液的固含量低于1.0重量%,则在将光电转换层的厚度保持在70nm或更大方面存在问题;和如果固含量超过3.0重量%,则将有显著量的导电聚合物和C70富勒烯衍生物未溶解。
然后,通过选自旋涂、丝网印刷、喷墨印刷和刮刀涂布的方法施加或涂布光电转换材料的溶液,从而形成具有约70nm或更大、并且优选80-200nm的厚度的光电转换层140。
在光电转换层140上可通过在约10-7托或更低的真空下热沉积金属材料例如铝至100-200nm的厚度而形成第二电极150。
可用于形成第二电极150的材料的实例包括金、铝、铜、银、或者它们的合金、钙/铝合金、镁/银合金、铝/锂合金等。优选地,使用铝或者铝/钙合金。
下文中,将参照实施例更详细地描述本发明。然而,将理解,这些实施例用于说明目的并且本发明的范围不限于此。
实施例1:聚合物-2的合成
将0.300g(0.429mmol)2,7-二(4′,4′,5′,5′-四甲基-1′,3′,2′-二氧杂环戊硼烷-2′-基)-9,9-二癸基芴、0.187g(0.409mmol)4,7-二-2′-(5′-溴)-噻吩基-2,1,3-苯并噻二唑、和0.0106g(0.0215mmol)N-十二烷基-2,7-二溴咔唑加入到反应烧瓶中并且在真空中保持1小时,之后向其中加入7ml甲苯,并且将混合物搅拌30分钟。在向其中加入1.5ml乙醇和1.5ml 20重量%Et4NOH之后,将该溶液用氮气鼓泡以除去溶解在溶剂中的氧气。然后,加入2.9mg(0.0129mmol)Pd(OAc)2和10.8mg(0.0386mmol)三环己基膦,和在将外部油浴的温度保持在120℃的同时使该混合物在氮气气氛中回流2天。将0.05g苯基硼酸加入其中并且使其反应3小时,然后加入0.12g溴苯并且使其反应4小时。将反应溶液滴入300ml甲醇中,并且将所得粗制固体聚合物在索氏(Soxhlet)装置中用甲醇洗涤24小时。将溶剂用氯仿替代以溶解该聚合物,然后蒸发溶剂以留下仅最少量的溶剂,并且将残留物在300ml甲醇中沉淀。然后,滤出固体,之后除去溶剂,并且将残留物溶解在最少量的氯仿中,再次在300ml甲醇中沉淀,过滤并且在真空下干燥,从而获得200mg聚合物[Mw=5,448g/mol(PDI=2.0)]。
实施例2:聚合物-3的合成
重复实施例1的程序,除了将0.300g(0.429mmol)2,7-二(4′,4′,5′,5′-四甲基-1′,3′,2′-二氧杂环戊硼烷-2′-基)-9,9-二癸基芴、0.177g(0.386mmol)4,7-二-2′-(5′-溴)-噻吩基-2,1,3-苯并噻二唑、和0.0212g(0.0429mmol)N-十二烷基-2,7-二溴咔唑加入到反应烧瓶中并且在真空中保持1小时,之后向其中加入7ml甲苯,并且将混合物搅拌30分钟之外,从而获得200mg聚合物[Mw=6,796g/mol(PDI=2.0)]。
实施例3:聚合物-4的合成
重复实施例1的程序,除了将0.400g(0.573mmol)2,7-二(4′,4′,5′,5′-四甲基-1′,3′,2′-二氧杂环戊硼烷-2′-基)-9,9-二癸基芴、0.210g(0.458mmol)4,7-二-2′-(5′-溴)-噻吩基-2,1,3-苯并噻二唑、和0.0106g(0.0215mmol)N-十二烷基-2,7-二溴咔唑加入到反应烧瓶中并且在真空中保持1小时,之后向其中加入8ml甲苯,并且将混合物搅拌30分钟之外,从而获得200mg聚合物[Mw=5,125g/mol(PDI=2.0)]。
对比例1:聚合物-1的合成
重复实施例1的程序,除了将0.300g(0.429mmol)2,7-二(4′,4′,5′,5′-四甲基-1′,3′,2′-二氧杂环戊硼烷-2′-基)-9,9-二癸基芴、0.197g(0.429mmol)4,7-二-2′-(5′-溴)-噻吩基-2,1,3-苯并噻二唑加入到反应烧瓶中并且在真空中保持1小时,之后向其中加入7ml甲苯,并且将混合物搅拌30分钟之外,从而获得120mg聚合物[Mw=5,015g/mol(PDI=1.8)]。
对比例2:聚合物-5的合成
重复实施例1的程序,除了将0.3g(0.429mmol)2,7-二(4′,4′,5′,5′-四甲基-1′,3′,2′-二氧杂环戊硼烷-2′-基)-9,9-二癸基芴、0.137g(0.300mmol)4,7-二-2′-(5′-溴)-噻吩基-2,1,3-苯并噻二唑、和0.064g(0.129mmol)N-十二烷基-2,7-二溴咔唑加入到反应烧瓶中并且在真空中保持1小时,之后向其中加入7ml甲苯并且将混合物搅拌30分钟之外,从而获得260mg聚合物[Mw=8,521g/mol(PDI=2.4)]。
对比例3:聚合物-6的合成
重复实施例1的程序,除了将0.3g(0.429mmol)2,7-二(4′,4′,5′,5′-四甲基-1′,3′,2′-二氧杂环戊硼烷-2′-基)-9,9-二癸基芴、0.118g(0.258mmol)4,7-二-2′-(5′-溴)-噻吩基-2,1,3-苯并噻二唑、和0.084g(0.172mmol)N-十二烷基-2,7-二溴咔唑加入到反应烧瓶中并且在真空中保持1小时,之后向其中加入7ml甲苯并且将混合物搅拌30分钟之外,从而获得220mg聚合物[Mw=12,233g/mol(PDI=2.6)]。
对比例4:聚合物-7的合成
重复实施例1的程序,除了将0.3g(0.429mmol)2,7-二(4′,4′,5′,5′-四甲基-1′,3′,2′-二氧杂环戊硼烷-2′-基)-9,9-二癸基芴、0.098g(0.215mmol)4,7-二-2′-(5′-溴)-噻吩基-2,1,3-苯并噻二唑、和0.106g(0.215mmol)N-十二烷基-2,7-二溴咔唑加入到反应烧瓶中并且在真空中保持1小时之外,之后向其中加入7ml甲苯并且将混合物搅拌30分钟之外,从而获得270mg聚合物[Mw=9,342g/mol(PDI=2.4)]。
实施例4:有机光伏器件1的制造
将通过Suzuki方法合成的实施例1~3和对比例1~4的含有咔唑的导电聚合物各自用作电子给体,并且使用C70-PCBM作为电子受体。将所述电子给体和所述电子受体以1∶3的重量比彼此混合以制备光电转换层材料,然后将其以1.5重量%的含量溶解在氯苯溶剂中。然后,在氩气气氛中将该溶液旋涂于其上形成有PEDOT层的ITO玻璃基底上,从而形成具有70-120nm厚度的光电转换层。然后,将所得结构在热板上在120℃热处理5分钟。
接着,在具有10-7托或更低的真空度的真空室中,在光电转换层上顺序地热沉积0.6nm LiF和100-200nm铝,从而制造有机光伏器件。
测试例1:有机光伏器件的电光性质
将如以下反应方案1中所示制备的实施例1~3和对比例1~4的聚合物各自与C70-PCBM以1∶3的重量比混合以制备光电转换层材料,和测量包括所制备的光电转换层材料的有机光伏器件的电光性质。测量结果示于下表1中。
图2是显示包括光电转换层材料的有机光伏器件的电流密度-电压(J-V)的测量结果的图,所述光电转换层材料通过将实施例1~3和对比例1~4的导电聚合物各自与C70-PCBM以1∶3的重量比混合而制备。
在所述电光性质中,填充因子和能量转换效率分别使用以下方程1和2计算。
[方程1]
填充因子=(Vmp×Imp)/(Voc×Isc)
其中Vmp是在最大功率点处的电压值,Imp是电流密度,Voc是开路电压,和Isc是短路电流。
[方程2]
能量转换效率(%)=填充因子×(Jsc×Voc)/100
其中Jsc是短路电流密度,和Voc是开路电压。
[反应方案1]
[表1]
有机光伏器件的电光性质
如可从表1和图1中的结果看出的,与对比例1的聚合物(聚合物-1)相比,各自在芴和二噻吩基苯并噻二唑的共聚物中含有少量咔唑的实施例1~3的聚合物(聚合物-2至聚合物-4)分别显示出31%、23%和19%的在能量转换效率方面的提高。
而且,在通过将超过30重量%的单体加入到芴中制备的对比例2~4的聚合物(聚合物-5至聚合物-7)的情况下,能量转换效率降低约50%,而不是增加。
实施例5:聚合物-9的合成
将0.300g(0.436mmol)2,6-二(三丁基锡烷基)-4,4′-二己基二噻吩并噻咯、0.122g(0.414mmol)4,7-溴-2,1,3-苯并噻二唑、0.0107g(0.0218mmol)N-十二烷基-2,7-二溴咔唑和2ml甲苯加入到反应烧瓶中并且用氮气鼓泡10分钟以除去溶解在溶剂中的氧气。在氮气气氛中向其中加入2.9mg(0.0129mmol)Pd(OAc)2和10.8mg(0.0386mmol)三环己基膦,并且将混合物再次用氮气鼓泡5分钟。然后,在将外部油浴的温度保持为120℃的同时,使该混合物在氮气气氛中回流2天。
将0.05g三丁基苯基锡加入其中并且反应以反应3小时,然后加入0.12g溴苯并且反应4小时。将反应溶液滴入300ml甲醇中,并且将所得粗制固体聚合物在索氏装置中用甲醇洗涤24小时。将溶剂用氯仿替代以溶解该聚合物,然后蒸发溶剂以留下仅最少量的溶剂,并且将残留物在300ml甲醇中沉淀。然后,滤出固体,之后除去溶剂,并且将残留物溶解在最少量的氯仿中,再次在300ml甲醇中沉淀,过滤并且在真空下干燥,从而获得130mg聚合物[Mw=9,764g/mol(PDI=3.7)]。
实施例6:聚合物-10的合成
将0.300g(0.436mmol)2,6-(三丁基锡烷基)-4,4′-己基二噻吩并噻咯、0.102g(0.349mmol)4,7-溴-2,1,3-苯并噻二唑、0.043g(0.087mmol)N-十二烷基-2,7-二溴咔唑和1.5ml甲苯加入到反应烧瓶中并且用氮气鼓泡10分钟以除去溶解在溶剂中的氧气。
在氮气气氛中向其中加入4.3mg(0.0190mmol)Pd(OAc)2和15.8mg(0.0563mmol)三环己基膦,并且将混合物再次用氮气鼓泡5分钟。然后,在将外部油浴的温度保持为120℃的同时,使该混合物在氮气气氛中回流2天。后续程序以与实施例5相同的方式进行,从而获得180mg聚合物[Mw=6,583g/mol(PDI=3.8)]。
对比例5:聚合物-8的合成
将0.40g(0.58mmol)2,6-(三丁基锡烷基)-4,4′-己基二噻吩并噻咯、0.17g(0.58mmol)4,7-溴-2,1,3-苯并噻二唑和2ml甲苯加入到反应烧瓶中并且用氮气鼓泡10分钟以除去溶解在溶剂中的氧气。
在氮气气氛中向其中加入4.0mg(0.017mmol)Pd(OAc)2和15.0mg(0.052mmol)三环己基膦,并且将混合物再次用氮气鼓泡5分钟。然后,在将外部油浴的温度保持为120℃的同时,使该混合物在氮气气氛中回流2天。后续程序以与实施例5相同的方式进行,从而获得200mg聚合物[Mw=8,452g/mol(PDI=3.1)]。
对比例6:聚合物-11的合成
将0.300g(0.436mmol)2,6-二(三丁基锡烷基)-4,4′-二己基二噻吩并噻咯、0.064g(0.218mmol)4,7-溴-2,1,3-苯并噻二唑、0.107g(0.218mmol)N-十二烷基-2,7-二溴咔唑和1.5ml甲苯加入到反应烧瓶中并且用氮气鼓泡10分钟以除去溶解在溶剂中的氧气。在氮气气氛中向其中加入2.0mg(0.013mmol)Pd(OAc)2和11.0mg(0.039mmol)三环己基膦,并且将混合物再次用氮气鼓泡5分钟。然后,在将外部油浴的温度保持为120℃的同时,使该混合物在氮气气氛中回流2天。后续程序以与实施例5相同的方式进行,从而获得150mg聚合物[Mw=11,154g/mol(PDI=3.8)]。
实施例7:有机光伏器件2的制造
将通过Stille方法合成的实施例5和6以及对比例5和6的含有咔唑的导电聚合物各自用作电子给体,和使用C70-PCBM作为电子受体。所述电子给体和所述电子受体以1∶3的重量比彼此混合以制备光电转换层材料,然后将其以1.5重量%的含量溶解在氯苯溶剂中。然后,使用该溶液,以与实施例4相同的方式制造有机光伏器件。
测试例2:有机光伏器件的电光性质
将如以下反应方案2中所示制备的实施例5和6以及对比例5和6的聚合物各自与C70-PCBM以1∶3的重量比混合以制备光电转换层材料,和测量包括所制备的光电转换层材料的有机光伏器件的电光性质。测量结果示于下表2中。
图3是显示包括光电转换层材料的有机光伏器件的电流密度-电压(J-V)的测量结果的图,所述光电转换层材料通过将实施例5和6以及对比例5和6的导电聚合物各自与C70-PCBM以1∶3的重量比混合而制备。
[反应方案2]
[表2]
有机光伏器件的电光性质
如可从上表2和图3中的结果看出的,与不含有咔唑的对比例5的聚合物(聚合物-8)相比,各自在二噻吩并噻咯和苯并噻二唑的共聚物中含有少量咔唑的实施例5和6的聚合物(聚合物-9和聚合物-10)分别显示出46%和258%的在能量转换效率方面的提高。
而且,在含有提高量的咔唑的对比例6的聚合物(聚合物-11)的情况下,能量转换效率降低而不是增加。
如上所述,本发明提供包括引入仅由给体官能团构成、包含一种或多种芳族单体的聚合物中、或者引入包含引入给体官能团中的重复的受体基团的给体-受体型聚合物中的特定量的咔唑的导电聚合物。所述导电聚合物具有提高的电荷迁移率,并且因此当其用作有机薄膜太阳能电池中的电子给体时,其可改善有机薄膜太阳能电池的能量转换效率。
此外,本发明的含有咔唑的导电聚合物可用作有机光伏器件中的电子给体并且还可有利地用于各种领域,包括有机薄膜晶体管(OTFT)和有机发光二极管(OLED)。
此外,本发明提供包括含有咔唑的导电聚合物作为电子给体的有机光伏器件,并且因此在有机薄膜太阳能电池中可实现高的光电转换效率。
虽然已经出于说明的目的描述了本发明的优选实施方式,然而本领域技术人员将理解,在不脱离如所附权利要求中公开的本发明的范围和精神的情况下,各种改进、添加和替代是可能的。
Claims (11)
3.权利要求1的含有咔唑的导电聚合物,其中X和Y之一为给体单体结构,和另一个为受体单体结构。
6.用于有机光伏器件、有机发光二极管或有机薄膜晶体管的光电转换材料,其包括根据权利要求1的由式1表示的含有2,7-咔唑的导电聚合物:
[式1]
其中l、m、n、X、Y和R1如权利要求1中定义的。
9.权利要求8的有机光伏器件,其中n为
10.权利要求8的有机光伏器件,其中所述光电转换层由光电转换材料制成,所述光电转换材料为作为电子给体的式1的含有2,7-咔唑的导电聚合物和作为电子受体的C60富勒烯衍生物或C70富勒烯衍生物的混合物,其中所述电子给体和所述电子受体以1:0.5-1:4的重量比彼此混合。
11.权利要求8的有机光伏器件,其中所述光电转换材料是通过将其溶解在选自氯苯、1,2-二氯苯和氯仿的任意一种溶剂中以达到1.0-3.0重量%的固含量作为溶液制备的。
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WO2010117158A2 (ko) | 2010-10-14 |
WO2010117158A3 (ko) | 2010-12-23 |
JP2012522067A (ja) | 2012-09-20 |
US20120018715A1 (en) | 2012-01-26 |
US8519068B2 (en) | 2013-08-27 |
JP5085805B2 (ja) | 2012-11-28 |
DE112010001554T5 (de) | 2012-08-23 |
CN102405247A (zh) | 2012-04-04 |
KR101102079B1 (ko) | 2012-01-04 |
KR20100111767A (ko) | 2010-10-18 |
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