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Abstract:

Metal-halide perovskite semiconductors have attracted intensive interest in the last decade, particularly for applications in photovoltaics. Low-energy optical phonons combined with significant crystal anharmonicity play an important role in charge-carrier cooling and scattering in these materials, strongly affecting their optoelectronic properties. We have observed optical phonons associated with Pb—I stretching in both MAPbI3 single crystals and polycrystalline thin films as a function of temperature by measuring their terahertz (THz) conductivity spectra with and without photoexcitation. An anomalous bond hardening was observed under above-bandgap illumination for both single-crystal and polycrystalline MAPbI3. First-principles calculations reproduced this photo-induced bond hardening and identified a related lattice contraction (photostriction), with the mechanism revealed as Pauli blocking. For single-crystal MAPbI3, phonon lifetimes were significantly longer and phonon frequencies shifted less with temperature, compared with polycrystalline MAPbI3. We attribute these differences to increased crystalline disorder, associated with grain boundaries and strain in the polycrystalline MAPbI3. Thus we provide fundamental insight into the photoexcitation and electron–phonon coupling in MAPbI3.

Abstract:

Semiconducting polycrystalline thin films are cheap to produce and can be deposited on flexible substrates, yet high-performance electronic devices usually utilize single-crystal semiconductors, owing to their superior charge-carrier mobilities and longer diffusion lengths. Here we show that the electrical performance of polycrystalline films of metal-halide perovskites (MHPs) approaches that of single crystals at room temperature. Combining temperature-dependent terahertz conductivity measurements and ab initio calculations we uncover a complete picture of the origins of charge-carrier scattering in single crystals and polycrystalline films of CH3NH3PbI3. We show that Fröhlich scattering of charge carriers with multiple phonon modes is the dominant mechanism limiting mobility, with grain-boundary scattering further reducing mobility in polycrystalline films. We reconcile the large discrepancy in charge-carrier diffusion lengths between single crystals and films by considering photon reabsorption. Thus, polycrystalline films of MHPs offer great promise for devices beyond solar cells, including light-emitting diodes and modulators.