The quantum-confined Stark effect in layered hybrid perovskites mediated by orientational polarizability of confined dipoles.

The quantum-confined Stark effect (QCSE) is an established optical modulation mechanism, yet top-performing modulators harnessing it rely on costly fabrication processes. Here, we present large modulation amplitudes for solution-processed layered hybrid perovskites and a modulation mechanism related to the orientational polarizability of dipolar cations confined within these self-assembled quantum wells. We report an anomalous (blue-shifting) QCSE for layers that contain methylammonium cations, in contrast with cesium-containing layers that show normal (red-shifting) behavior. We attribute the blue-shifts to an extraordinary diminution in the exciton binding energy that arises from an augmented separation of the electron and hole wavefunctions caused by the orientational response of the dipolar cations. The absorption coefficient changes, realized by either the red- or blue-shifts, are the strongest among solution-processed materials at room temperature and are comparable to those exhibited in the highest-performing epitaxial compound semiconductor heterostructures.

Reduced voltage losses yield 10% efficient fullerene free organic solar cells with >1 V open circuit voltages.

Optimization of the energy levels at the donor-acceptor interface of organic solar cells has driven their efficiencies to above 10%. However, further improvements towards efficiencies comparable with inorganic solar cells remain challenging because of high recombination losses, which empirically limit the open-circuit voltage (Voc) to typically less than 1 V. Here we show that this empirical limit can be overcome using non-fullerene acceptors blended with the low band gap polymer PffBT4T-2DT leading to efficiencies approaching 10% (9.95%). We achieve Voc up to 1.12 V, which corresponds to a loss of only Eg/q - Voc = 0.5 ± 0.01 V between the optical bandgap Eg of the polymer and Voc. This high Voc is shown to be associated with the achievement of remarkably low non-geminate and non-radiative recombination losses in these devices. Suppression of non-radiative recombination implies high external electroluminescence quantum efficiencies which are orders of magnitude higher than those of equivalent devices employing fullerene acceptors. Using the balance between reduced recombination losses and good photocurrent generation efficiencies achieved experimentally as a baseline for simulations of the efficiency potential of organic solar cells, we estimate that efficiencies of up to 20% are achievable if band gaps and fill factors are further optimized.

Coverage dependent adsorption dynamics in hyperthermal organic thin film growth.

We have examined the dynamics of adsorption of diindenoperylene (DIP) on SiO(2) and SiO(2) modified with an interfacial organic layer using in situ real time synchrotron x-ray scattering, focusing on the effects of coverage. On both surfaces we observe a substantial increase in the probability of adsorption with increasing coverage, which is most dramatic at the highest incident kinetic energies. On the initially uncovered surfaces, we observe a smooth decrease in the probability of adsorption with increasing incident kinetic energy, indicative of trapping-mediated adsorption. Once both surfaces are covered by DIP, the effects of incident kinetic energy are greatly reduced, and trapping is very efficient over the range of kinetic energies examined. Possible reasons for efficient trapping at high coverage and at high incident kinetic energy include more efficient momentum transfer due to mass matching, and possibly direct molecular insertion. Comparison to results on another small-molecule, pentacene, suggests that this behavior should be common to hyperthermal growth of a variety of other small-molecule thin films.