Absorption Tails of Donor:C60 Blends Provide Insight into Thermally Activated Charge-Transfer Processes and Polaron Relaxation.

In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D-A complexes occur at photon energies below the optical gaps of both the donors and the C60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D-A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes.

Author Correction: Molecular vibrations reduce the maximum achievable photovoltage in organic solar cells.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Molecular vibrations reduce the maximum achievable photovoltage in organic solar cells.

The low-energy edge of optical absorption spectra is critical for the performance of solar cells, but is not well understood in the case of organic solar cells (OSCs). We study the microscopic origin of exciton bands in molecular blends and investigate their role in OSCs. We simulate the temperature dependence of the excitonic density of states and low-energy absorption features, including low-frequency molecular vibrations and multi-exciton hybridisation. For model donor-acceptor blends featuring charge-transfer excitons, our simulations agree very well with temperature-dependent experimental absorption spectra. We unveil that the quantum effect of zero-point vibrations, mediated by electron-phonon interaction, causes a substantial exciton bandwidth and reduces the open-circuit voltage, which is predicted from electronic and vibronic molecular parameters. This effect is surprisingly strong at room temperature and can substantially limit the OSC's efficiency. Strategies to reduce these vibration-induced voltage losses are discussed for a larger set of systems and different heterojunction geometries.

Oxygen-Induced Degradation in C60-Based Organic Solar Cells: Relation Between Film Properties and Device Performance.

Fullerene-based molecules are the archetypical electron-accepting materials for organic photovoltaic devices. A detailed knowledge of the degradation mechanisms that occur in C60 layers will aid in the development of more stable organic solar cells. Here, the impact of storage in air on the optical and electrical properties of C60 is studied in thin films and in devices. Atmospheric exposure induces oxygen-trap states that are 0.19 eV below the LUMO of the fullerene C60. Moreover, oxygen causes a 4-fold decrease of the exciton lifetime in C60 layers, resulting in a 40% drop of short-circuit current from optimized planar heterojunction solar cells. The presence of oxygen-trap states increases the saturation current of the device, resulting in a 20% loss of open-circuit voltage. Design guidelines are outlined to improve air stability for fullerene-containing devices.