One of distinguishing features of metal halide perovskites is their long (up to microseconds) photoluminescence (PL) lifetimes, which are regularly observed for this class of semiconductors in spite of their direct gap origin. It is difficult to explain this contradiction in the framework of usual two-level Jablonski photophysical diagram because the absorption coefficient (i.e., the oscillator strength of the direct optical transition) is too high in perovskites to hold such long PL lifetimes. In this paper, we describe practical steps how the PL decay kinetics of perovskites in the forms of (1) passivated nanocrystals and (2) thin multicrystalline films can be described. In case of nanocrystals, the three-level delayed luminescence model is described by including shallow non-quenching traps providing multiple trapping and de-trapping of carriers and thus essentially lengthening the observed PL lifetime. In the case of perovskite thin films limited by interfacial recombination, the PL decay kinetics is usually determined by the non-radiative recombination on the film surfaces and can be satisfactorily described in terms of one-dimensional diffusion equation. The limits of applicability of such approaches are discussed.
It is widely accepted that a long photoluminescence (PL) lifetime in metal halide perovskite films is a crucial and favorable factor, as it ensures a large charge diffusion length leading to a high power conversion efficiency (PCE) in solar cells. It has been recently found that vacuumevaporated CH3NH3PbI3 (eMAPI) films show very short PL lifetimes of several nanoseconds. The corresponding solar cells, however, have high photovoltage (>1.1 V) and PCEs (up to 20%). We rationalize this apparent contradiction and show that eMAPI films are characterized by a very high diffusion coefficient D, estimated from modeling the PL kinetics to exceed 1 cm2/s. Such high D values are favorable for long diffusion length as well as fast transport of carriers to film surfaces, where they recombine nonradiatively with surface recombination velocity S ∼ 104 cm/s. Possible physical origins leading to the high D values are also discussed
Anti-Stokes photoluminescence (ASPL), which is an up-conversion phonon-assisted process of the radiative recombination of photoexcited charge carriers, was investigated in methylammonium lead bromide (MALB) perovskite nanocrystals (NCs) with mean sizes that varied from about 6 to 120 nm. The structure properties of the MALB NCs were investigated by means of the scanning and transmission electron microscopy, X-ray diffraction and Raman spectroscopy. ASPL spectra of MALB NCs were measured under near-resonant laser excitation with a photon energy of 2.33 eV and they were compared with the results of the photoluminescence (PL) measurements under non-resonant excitation at 3.06 eV to reveal a contribution of phonon-assisted processes in ASPL. MALB NCs with a mean size of about 6 nm were found to demonstrate the most efficient ASPL, which is explained by an enhanced contribution of the phonon absorption process during the photoexcitation of small NCs. The obtained results can be useful for the application of nanocrystalline organometal perovskites in optoelectronic and all-optical solid-state cooling devices.
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