ABSTRACT
Methylammonium lead tribromide perovskite (MAPbBr3) is an important material, for example, for light-emitting applications and tandem solar cells. The relevant photophysical properties are governed by a plethora of phenomena resulting from the complex and relatively poorly understood interplay of excitons and free charge carriers in the excited state. In this study, we combine transient spectroscopies in the visible and terahertz range to investigate the presence and evolution of excitons and free charge carriers at ultrafast times upon excitation at various photon energies and densities. For above- and resonant band-gap excitation, we find that free charges and excitons coexist and that both are mainly promptly generated within our 50-100 fs experimental time resolution. However, the exciton-to-free charge ratio increases upon decreasing the phonon energy toward resonant band gap excitation. The free charge signatures dominate the transient absorption response for above-band-gap excitation and low excitation densities, masking the excitonic features. With resonant band gap excitation and low excitation densities, we find that although the exciton density increases, free charges remain. We show evidence that the excitons localize into shallow trap and/or Urbach tail states to form localized excitons (within tens of picoseconds) that subsequently get detrapped. Using high excitation densities, we demonstrate that many-body interactions become pronounced and effects such as the Moss-Burstein shift, band gap renormalization, excitonic repulsion, and the formation of Mahan excitons are evident. The coexistence of excitons and free charges that we demonstrate here for photoexcited MAPbBr3 at ultrafast time scales confirms the high potential of the material for both light-emitting diode and tandem solar cell applications.
ABSTRACT
Organic-inorganic perovskites are one of the most promising photovoltaic materials for the design of next generation solar cells. The lead-based perovskite prepared with methylammonium and iodide was the first in demonstrating high power conversion efficiency, and it remains one of the most used materials today. However, perovskites prepared by mixing several halides and several cations systematically yield higher efficiencies than "pure" methylammonium lead iodide (MAPbI3) devices. In this work, we unravel the excited-state properties of a mixed-halide (iodide and bromide) and mixed-cation (methylammonium and formamidinium) perovskite. Combining time-resolved photoluminescence, transient absorption, and optical-pump-terahertz-probe experiments with density functional theory calculations, we show that the population of higher-lying excited states in the mixed material increases the lifetime of photogenerated charge carriers upon well above-bandgap excitation. We suggest that alloying different halides and different cations reduces the structural symmetry of the perovskite, which partly releases the selection rules to populate the higher-energy states upon light absorption. Our investigation thus shows that mixed halide perovskites should be considered as an electronically different material than MAPbI3, paving the way toward further materials optimization and improved power conversion efficiency of perovskite solar cells.
ABSTRACT
Future lightweight, flexible, and wearable electronics will employ visible-light-communication schemes to interact within indoor environments. Organic photodiodes are particularly well suited for such technologies as they enable chemically tailored optoelectronic performance and fabrication by printing techniques on thin and flexible substrates. However, previous methods have failed to address versatile functionality regarding wavelength selectivity without increasing fabrication complexity. This work introduces a general solution for printing wavelength-selective bulk-heterojunction photodetectors through engineering of the ink formulation. Nonfullerene acceptors are incorporated in a transparent polymer donor matrix to narrow and tune the response in the visible range without optical filters or light-management techniques. This approach effectively decouples the optical response from the viscoelastic ink properties, simplifying process development. A thorough morphological and spectroscopic investigation finds excellent charge-carrier dynamics enabling state-of-the-art responsivities >102 mA W-1 and cutoff frequencies >1.5 MHz. Finally, the color selectivity and high performance are demonstrated in a filterless visible-light-communication system capable of demultiplexing intermixed optical signals.
ABSTRACT
Methylammonium lead iodide (MAPI) has excellent properties for photovoltaic applications, although it typically shows low photoluminescence quantum yield. Here, we report on vacuum-deposited MAPI perovskites obtained by modifying the methylammonium iodide (MAI) to PbI2 ratio during vacuum deposition. By studying the excitation density dependence of the photoluminescence lifetime, a large concentration of trap states was deduced for the stoichiometric MAPI films. The use of excess MAI during vacuum processing is capable of passivating these traps, resulting in luminescent films which can be used to fabricate planar light-emitting diodes with quantum efficiency approaching 2%.
