Room-Temperature Halide Perovskite Field-Effect Transistors by Ion Transport Mitigation.

Solution-processed halide perovskites have emerged as excellent optoelectronic materials for applications in photovoltaic solar cells and light-emitting diodes. However, the presence of mobile ions in the material hinders the development of perovskite field-effect transistors (FETs) due to screening of the gate potential in the nearby perovskite channel, and the resulting impediment to achieving gate modulation of an electronic current at room temperature. Here, room-temperature operation is demonstrated in cesium lead tribromide (CsPbBr3 ) perovskite-based FETs using an auxiliary ferroelectric gate of poly(vinylidenefluoride-co-trifluoroethylene) [P(VDF-TrFE)], to electrostatically fixate the mobile ions. The large interfacial polarization of the ferroelectric gate attracts the mobile ions away from the main nonferroelectric gate interface, thereby enabling modulation of the electronic current through the channel by the main gate. This strategy allows for realization of the p-type CsPbBr3 channel and revealing the thermally activated nature of the hole charge transport. The proposed strategy is generic and can be applied for regulating ions in a variety of ionic-electronic mixed semiconductors.

3D-to-2D Transition of Anion Vacancy Mobility in CsPbBr3 under Hydrostatic Pressure.

Anion vacancy migration in the orthorhombic Pnma phase of the lead-halide perovskite CsPbBr3 under hydrostatic pressure is studied computationally. Density functional theory calculations are used to determine transition states, activation enthalpies, and attempt frequencies for vacancies to hop between nearby lattice sites, under pressure in the range 0.0-2.0 GPa. The resulting data are used to parametrize a kinetic model of vacancy migration under the influence of an electric field, which is solved in the steady state to determine the anion vacancy mobility tensor as a function of pressure. It is found that the mobility tensor becomes increasingly anisotropic with increasing pressure, such that at 2.0 GPa, the mobility within the (010) lattice plane is 3 orders of magnitude greater than the mobility normal to it. The results demonstrate the potentially significant influence of pressure, and by extension, other forms of stress, on defect migration in lead-halide perovskites.

Delocalised kinetic Monte Carlo for simulating delocalisation-enhanced charge and exciton transport in disordered materials.

Charge transport is well understood in both highly ordered materials (band conduction) or highly disordered ones (hopping conduction). In moderately disordered materials-including many organic semiconductors-the approximations valid in either extreme break down, making it difficult to accurately model the conduction. In particular, describing wavefunction delocalisation requires a quantum treatment, which is difficult in disordered materials that lack periodicity. Here, we present the first three-dimensional model of partially delocalised charge and exciton transport in materials in the intermediate disorder regime. Our approach is based on polaron-transformed Redfield theory, but overcomes several computational roadblocks by mapping the quantum-mechanical techniques onto kinetic Monte Carlo. Our theory, delocalised kinetic Monte Carlo (dKMC), shows that the fundamental physics of transport in moderately disordered materials is that of charges hopping between partially delocalised electronic states. Our results reveal why standard kinetic Monte Carlo can dramatically underestimate mobilities even in disordered organic semiconductors, where even a little delocalisation can substantially enhance mobilities, as well as showing that three-dimensional calculations capture important delocalisation effects neglected in lower-dimensional approximations.