CN1682362A - 处理光电活性层和有机基光电元件 - Google Patents

处理光电活性层和有机基光电元件 Download PDF

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CN1682362A
CN1682362A CN03821159.9A CN03821159A CN1682362A CN 1682362 A CN1682362 A CN 1682362A CN 03821159 A CN03821159 A CN 03821159A CN 1682362 A CN1682362 A CN 1682362A
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克里斯托夫·布拉贝克
帕维尔·希林斯基
克里斯托夫·瓦尔道夫
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Konarka Technologies Inc
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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    • H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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Abstract

本发明涉及有机基光电元件，特别是包括光电活性层的太阳能电池，其中活性层的最大吸收可移动到较长波的区域和/或可增加其效率。

Description

处理光电活性层和有机基光电元件
本发明涉及有机基光电元件，特别是包括在蓝色光区域吸收的光电活性层的太阳能电池。
已知有机基太阳能电池来自1994年的美国专利5,331,183和随后大量的出版物。
特别熟知的是以聚烷基噻吩(P3AT)为基础的有机太阳能电池。这种光电元件典型的电池结构包括如下的薄层：阳极，复合层，例如ITO(铟锡氧化物)，共聚物的空穴-导电层盖在上面，如PEDOT与作为阴离子的PSS的混合物。顶部是一层P3AT：PCBM[聚(3-己基噻吩)与苯基C61-丁氧基甲氧基的混合]，该层是光电活性层。在其之上是阴极层，例如，包含金属如铝或Ca/Ag合金。然而，单独层可以不同于这一方式；特别是电极和接受器(PCBM)均可以由另外的材料制造。例如，已经使用氰基取代的PPVs(CN PPVs)作为接受器；但是可预期聚噻吩中有任意的多种添加物。
需要将光电活性层的最大吸收转移到更长的波段，一则因为聚噻吩与富勒烯混合引起最大吸收的蓝色偏移。这增加了不匹配性，即，最大吸收和阳光的峰发射之间的差异。
本发明的目的是提供一种方法，按照这一方法光电活性层的最大吸收可被转移到更长的波段区域和/或改进它的效率(例如，通过增加短路电流)。特别地，本发明的目的是提供一种方法，由此方法含聚(烷基)噻吩与富勒烯的混合物的光电活性层的最大吸收可被转移到更长的波段。
本发明涉及一种用溶剂和/或通过退火来处理光电活性层的方法，其特征在于光电活性层与溶剂分子接触和/或对其加热。本发明还涉及一种光电活性元件，其包括在混合物中含聚烷基噻吩的光电活性层，且该光电活性元件在深红色区域吸收。
光电活性层优选聚烷基噻吩，其与添加剂以混合物的形式存在，所述添加剂如富勒烯，尤其是亚甲基富勒烯。例如，代替富勒烯的其它添加剂可为基于如下物质的无机纳米粒子：碲化镉(CdTe)；硫化镉(CdS)；具有高亲电子能力的聚合物，如，氰基取代的PPVs(CNPPVs)；或具有高亲电子能力的小分子，如，四氰基醌(TCNQ)或四氰基蒽醌二甲烷(TCAQ)。
在本发明的一实施例中，在室温下光电活性层暴露于溶剂蒸气。例如，这可通过使光电活性层经过(保持)含有溶剂的容器上部和/或将溶剂蒸气传导到光电活性层上来实现。
在一个实施例中，光电活性层仅短暂地暴露于溶剂蒸气，即，少于一分钟，或例如仅在秒或豪秒的范围内。
在本发明的一个实施例中，在至少70℃的温度下，优选约80℃或更高的温度下，使光电活性层退火。可用短路电流的增加来监测退火的进程。也可考虑其它温度和时间的组合；当光电参数一停止增加就可认为完成了这一过程。可通过将光电活性层放置在干燥炉中或放在热板上或类似物上进行退火。退火同时也可进行溶剂处理。
使用的溶剂例如可以是芳香族溶剂，如二甲苯、甲苯或类似物；或含卤素的溶剂如氯仿或类似物。根据形成光电活性层材料的混合物选择适当溶剂。溶剂的影响在于，例如，溶剂二甲苯、甲苯、丁酮和/或氯仿和/或其它溶剂或所述溶剂的任意混合物至少部分蚀刻和/或软化聚烷基噻吩。
用常规方式制备光电活性层；按照现有技术，例如，由P3AT[聚(3-烷基噻吩)]/PCBM(苯基C61-丁氧基甲氧基)溶液形成旋涂薄膜或由标准的印刷方法进行(丝网印刷法，苯胺印刷(术)等)。
在下面反映实验结果的三幅图的基础上，对这些图作更详细的描述。
图1表示在玻璃上有和没有富勒稀的条件下，溶剂蒸气对用氯仿旋涂的P3AT膜吸收的影响，三角形表示在玻璃上的纯P3AT膜，实心矩形表示P3AT/PCBM膜。图中清楚表明在P3AT的典型吸收约550nm波长范围，该薄膜缺少吸收贡献。一旦该膜暴露于氯仿蒸气(空心菱形)，其对P3AT的典型吸收特征再次明显。
图2表示短路电流Isc(实心矩形)和效率(实心圆圈)随该层退火温度的变化。每个样品(结构：ITO/PEDOT/P3HT：PCBM/Ca/Ag)退火20分钟，并室温时在70mW/cm2氙气灯白光的照射下测量其电学特征(Isc和效率)。可以看到，在温度大于80℃时短路电流开始增加，因而效率也开始增加。
图3表示在溶剂蒸气处理之前(实心圆圈)或之后(实线矩形)，经过一次温度处理后电池的电流/电压(I/V)特征。短路电流(Isc)和效率的增加反映了电池吸收性能的红移(见图1说明)。
P3ATs，尤其是聚己基噻吩与富勒烯混合引起P3AT的最大吸收偏移高于100nm进入蓝色光谱区域。这增加了太阳能电池和太阳光谱之间的光谱不匹配。该发明解决了如下问题：
a)通过溶剂退火，使P3AT/富勒烯薄膜吸收偏移回红色光谱区域，和
b)由温度退火增加太阳能电池的效率。
在本发明的上下文中，“退火”表示为了达到目的而进行的光电活性层处理，即引起该层最大吸收的红移。

Claims (8)

1、一种用溶剂和/或由退火处理光电活性层的方法，特征在于所说的光电活性层与溶剂分子接触和/或被加热。
2、按照权利要求1中的方法，其中所述的光电活性层是与添加剂以混合物形式存在的聚烷基噻吩，其中添加剂例如，富勒烯，尤其是亚甲基富勒烯。
3、按照权利要求1和2中任一项的方法，其中将所述的光电活性层置于溶剂蒸气中。
4、按照权利要求3中的方法，其中在室温下将所述光电活性层置于所述溶剂蒸气中。
5、按照上述任一项权利要求的方法，其中将所述的光电活性层置于所述溶剂蒸气中不超过一分钟。
6、按照上述任一项权利要求的方法，其中所述的溶剂是二甲苯、甲苯、丁酮和/或氯仿和/或另外的溶剂和/或所述溶剂的任意混合物，其至少部分蚀刻和/或软化所述的聚烷基噻吩。
7、按照上述任一项权利要求的方法，其中在温度至少70℃下退火处理所述的光电活性层。
8、一种包括光电活性层的光电元件，所说的光电活性层包括混合物中的聚烷基噻吩，其中该光电层在深红区有最大吸收。
CN03821159.9A 2002-09-05 2003-09-03 处理光电活性层和有机基光电元件 Pending CN1682362A (zh)

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CN102623642A (zh) * 2012-03-22 2012-08-01 中国科学院长春应用化学研究所 聚合物太阳能电池的制备方法
CN102939673A (zh) * 2010-04-08 2013-02-20 密歇根大学董事会 通过热和溶剂蒸汽退火法制备的增强的体异质结器件
CN110518120A (zh) * 2018-05-22 2019-11-29 中国科学院化学研究所 一种固体添加剂及其在有机太阳能电池中的应用

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CN102623642A (zh) * 2012-03-22 2012-08-01 中国科学院长春应用化学研究所 聚合物太阳能电池的制备方法
CN102623642B (zh) * 2012-03-22 2014-04-16 中国科学院长春应用化学研究所 聚合物太阳能电池的制备方法
CN110518120A (zh) * 2018-05-22 2019-11-29 中国科学院化学研究所 一种固体添加剂及其在有机太阳能电池中的应用
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DE50306270D1 (de) 2007-02-22
WO2004025746A3 (de) 2004-09-16
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