Thermally induced degradation of photovoltaic performance in bulk-heterojunction (BHJ) polymer solar cells as a result of changes either in the active layer morphology or at interfaces during operation at elevated temperature is a common phenomenon. In this work, we have studied the thermal stability of a high performance polymer:fullerene BHJ PSCcomprising a conjugated polymer poly{[4,8-bis-(2-ethyl-hexyl-thiophene-5-yl)-benzo[1,2-b:4,5-b0]dithiophene-2,6-diyl]-alt-[2-(20-ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl]} (PBDTTT-CT) and a fullerene derivative [6,6]-phenyl-C70-butyric acid methyl ester photoactive layer within a conventional device architecture of glass/ITO/PEDOT:PSS/active layer/Mg/Al. By varying the temperature exposure conditions, the degradation path has been identified as an interfacial change in the device rather than a bulk effect. Furthermore, charge carrier dynamics studied by open circuit corrected charge carrier extraction has shown that post-annealed devices suffer from charge extraction due to the development of interfacial changes as compared to the non-treated devices in both pristine and with 1,8-Diiodooctane added scenarios.
Small-molecule-based organic solar cells (OSCs) are a recurrent alternative to polymer-based OSCs. Due to the higher purity and definition of small molecules compared to polymers, the morphological requirements can be more relaxed. Here, we present a series of novel rhodanine-based small molecule electron donors and blend them with the standard acceptor PC70BM. By performing a target analysis on femtosecond spectroscopy data, we quantify the rates of geminate charge recombination. We are able to reproduce these rates by applying the Marcus-Levich-Jortner equation, using results from quantum chemical calculations. This shows that in a series of differently substituted compounds, one can correctly predict trends in geminate recombination rates by relying only on quantities that are easy to measure (cyclic voltammetry, optical spectra) or that can be calculated by relatively inexpensive methods such as (TD)DFT. Our method should thus accelerate the search for high-performance small-molecule photovoltaic blends.
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