Advanced Functional Materials and Devices (AFMD) Group

Abstract:

Here we present a comprehensive study on the photophysics of QDs–fullerene blends, aiming to elucidate the impact of ligands on the extraction of carriers from QDs. We investigated how three different ligands (oleylamine, octadecanethiol and propanethiol) influence the dynamics of charge generation, separation, and recombination in blends of CdSe/CdS core/shell QDs and PCBM. We accessed each relevant process directly by combining the results from both optical and magnetic spectroscopies. Transient absorption measurements revealed a faster interaction dynamics in thiol-capped ligands. Through phenomenological modeling of the interaction processes, i.e., energy transfer and electron transfer, we estimated the suppression of exciton migration and the enhancement of electron transfer processes when alkyl–thiols are employed as ligands. Contextually, we report the profound impact of the ligands’ alkyl chain length, leading to strengthened interactions with PCBM acceptors. Quantitatively, we measured a 10-fold increase in the electron transfer rate when oleylamine ligands were exchanged with propanethiol ligands. EPR spectroscopy gave access to subtle details regarding both the enhanced charge generation and lower binding energy of charge-transfer states in blends compared to PCBM alone. Moreover, through pulsed EPR techniques, we inferred the localization of deep electron traps in localized sites close to QDs in the blends. Therefore, our thorough characterization evidenced the essential role of ligands in determining QD interactions. We believe that these discoveries will contribute to the efficient incorporation of QDs in existing organic PV technologies.

Abstract:

© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. 2017 saw the publication of several new material systems that challenge the long-held notion that a driving force is necessary for efficient exciton dissociation in organic photovoltaics (OPVs) and that a loss of ≈0.6 eV between the energy of the charge transfer state E ct and the energy corresponding to open circuit is general. In light of these developments, the authors combine insights from device physics and spectroscopy to review the two key tradeoffs limiting OPV performances. These are the tradeoff between the charge carrier generation efficiency and the achievable open circuit voltage (V oc ) and the tradeoff between device thickness (light absorption) and fill factor. The emergence of several competitive nonfullerene acceptors (NFAs) is exciting for both of these. The authors analyze what makes these materials compare favorably to fullerenes, including the potential role of molecular vibrations, and discuss both design criteria for new molecules and the achievable power conversion efficiencies.

Abstract:

The well-known organic semiconductor C60 is attracting renewed attention due to its centimetre-long electron diffusion length and high performance of solar cells containing 95% fullerene. Yet, its photophysical properties remain poorly understood. Here, we elucidate the dynamics of Frenkel and intermolecular (inter- C60) charge transfer (CT) excitons in neat and diluted C60 films from high quality femtosecond transient absorption (TA) measurements, performed at low fluences and free from oxygen or pump-induced photo-dimerization. We find from preferential excitation of either species that the CT excitons give rise to a strong electro-absorption signal but are extremely short-lived. The Frenkel exciton relaxation and triplet yield depend strongly on the C60 aggregation. Finally, TA measurements on full devices with applied electric field allow us to optically monitor the dissociation of CT excitons into free charges for the first time and to demonstrate the influence of cluster size on the spectral signature of the C60 anion.