Max Planck Research Group for Organic Optoelectronics, Max Planck Institute for Polymer Research, Ackermannweg 10, Mainz D-55128, Germany.
J Am Chem Soc. 2011 Jun 22;133(24):9469-79. doi: 10.1021/ja201837e. Epub 2011 May 26.
The precise mechanism and dynamics of charge generation and recombination in bulk heterojunction polymer:fullerene blend films typically used in organic photovoltaic devices have been intensively studied by many research groups, but nonetheless remain debated. In particular the role of interfacial charge-transfer (CT) states in the generation of free charge carriers, an important step for the understanding of device function, is still under active discussion. In this article we present direct optical probes of the exciton dynamics in pristine films of a prototypic polycarbazole-based photovoltaic donor polymer, namely poly[N-11''-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), as well as the charge generation and recombination dynamics in as-cast and annealed photovoltaic blend films using methanofullerene (PC(61)BM) as electron acceptor. In contrast to earlier studies we use broadband (500-1100 nm) transient absorption spectroscopy including the previously unobserved but very important time range between 2 ns and 1 ms, which allows us not only to observe the entire charge carrier recombination dynamics but also to quantify the existing decay channels. We determine that ultrafast exciton dissociation occurs in blends and leads to two separate pools of products, namely Coulombically bound charge-transfer (CT) states and unbound (free) charge carriers. The recombination dynamics are analyzed within the framework of a previously reported model for poly(3-hexylthiophene):PCBM (Howard, I. A. J. Am. Chem. Soc. 2010, 132, 14866) based on concomitant geminate recombination of CT states and nongeminate recombination of free charge carriers. The results reveal that only ~11% of the initial photoexcitations generate interfacial CT states that recombine exclusively by fast nanosecond geminate recombination and thus do not contribute to the photocurrent, whereas ~89% of excitons create free charge carriers on an ultrafast time scale that then contribute to the extracted photocurrent. Despite the high yield of free charges the power conversion efficiency of devices remains moderate at about 3.0%. This is largely a consequence of the low fill factor of devices. We relate the low fill factor to significant energetic disorder present in the pristine polymer and in the polymer:fullerene blends. In the former we observed a significant spectral relaxation of exciton emission (fluorescence) and in the latter of the polaron-induced ground-state bleaching, implying that the density of states (DOS) for both excitons and charge carriers is significantly broadened by energetic disorder in pristine PCDTBT and in its blend with PCBM. This disorder leads to charge trapping in solar cells, which in turn causes higher carrier concentrations and more significant nongeminate recombination. The nongeminate recombination has a significant impact on the IV curves of devices, namely its competition with charge carrier extraction causes a stronger bias dependence of the photocurrent of devices, in turn leading to the poor device fill factor. In addition our results demonstrate the importance of ultrafast free carrier generation and suppression of interfacial CT-state formation and question the applicability of the often used Braun-Onsager model to describe the bias dependence of the photocurrent in polymer:fullerene organic photovoltaic devices.
富勒烯共混膜中电荷产生和复合的精确机制和动力学一直是许多研究小组深入研究的课题,但仍存在争议。特别是界面电荷转移(CT)态在产生自由电荷载流子中的作用,这是理解器件功能的重要步骤,仍然是一个活跃的讨论话题。在本文中,我们介绍了对原初聚芴基光电给体聚合物(即聚[N-11''-二十二烷基-2,7-咔唑-alt-5,5-(4',7'-二噻吩基-2',1',3'-苯并噻二唑)]](PCDTBT))的纯膜中激子动力学的直接光学探针,以及使用甲氧基富勒烯(PC(61)BM)作为电子受体的铸膜和退火光伏共混膜中的电荷产生和复合动力学。与早期的研究不同,我们使用宽带(500-1100nm)瞬态吸收光谱学,包括以前未观察到但非常重要的 2ns 到 1ms 时间范围,这不仅使我们能够观察整个电荷载流子复合动力学,还能够量化现有的衰减通道。我们确定超快激子离解发生在共混物中,并导致两个单独的产物池,即库仑束缚 CT 态和无束缚(自由)电荷载流子。复合动力学是在先前报道的聚(3-己基噻吩):PCBM(霍华德,IAJ。美国化学学会 2010,132,14866)的基础上进行分析的,该模型基于 CT 态的同时复合复合和自由电荷载流子的非复合复合。结果表明,只有约 11%的初始光激发产生界面 CT 态,它们通过快速纳秒级的复合复合进行排他性复合,因此不会对光电流做出贡献,而约 89%的激子在超快时间尺度上产生自由电荷载流子,然后对提取的光电流做出贡献。尽管自由电荷的产率很高,但器件的功率转换效率仍然适中,约为 3.0%。这主要是器件填充因子低的结果。我们将低填充因子与原始聚合物和聚合物:富勒烯共混物中存在的显著的能量无序联系起来。在前者中,我们观察到激子发射(荧光)的显著光谱弛豫,而在后者中,我们观察到极化子诱导的基态漂白,这意味着激子和电荷载流子的态密度(DOS)都被原始 PCDTBT 和其与 PCBM 的共混物中的能量无序显著拓宽。这种无序导致了太阳能电池中的电荷俘获,这反过来又导致了更高的载流子浓度和更显著的非复合复合。非复合复合对器件的 IV 曲线有显著的影响,即它与电荷载流子提取的竞争导致了器件光电流的更强的偏压依赖性,进而导致了较差的器件填充因子。此外,我们的结果表明了超快自由载流子产生的重要性以及界面 CT 态形成的抑制,并对经常使用的 Braun-Onsager 模型在描述聚合物:富勒烯有机光伏器件中光电流的偏压依赖性的适用性提出了质疑。