Charge-Carrier Recombination in Halide Perovskites.

The success of halide perovskites in a host of optoelectronic applications is often attributed to their long photoexcited carrier lifetimes, which has led to charge-carrier recombination processes being described as unique compared to other semiconductors. Here, we integrate recent literature findings to provide a critical assessment of the factors we believe are most likely controlling recombination in the most widely studied halide perovskite systems. We focus on four mechanisms that have been proposed to affect measured charge carrier recombination lifetimes, namely: (1) recombination via trap states, (2) polaron formation, (3) the indirect nature of the bandgap (e.g., Rashba effect), and (4) photon recycling. We scrutinize the evidence for each case and the implications of each process on carrier recombination dynamics. Although they have attracted considerable speculation, we conclude that multiple trapping or hopping in shallow trap states, and the possible indirect nature of the bandgap (e.g., Rashba effect), seem to be less likely given the combined evidence, at least in high-quality samples most relevant to solar cells and light-emitting diodes. On the other hand, photon recycling appears to play a clear role in increasing apparent lifetime for samples with high photoluminescence quantum yields. We conclude that polaron dynamics are intriguing and deserving of further study. We highlight potential interdependencies of these processes and suggest future experiments to better decouple their relative contributions. A more complete understanding of the recombination processes could allow us to rationally tailor the properties of these fascinating semiconductors and will aid the discovery of other materials exhibiting similarly exceptional optoelectronic properties.EPSRC DTP Studentshi

Excitonic Properties of Low-Band-Gap Lead-Tin Halide Perovskites

The MAPb1–xSnxI3 (x = 0–1) (MA = methylammonium) perovskite family comprises a range of ideal absorber band gaps for single- and multijunction perovskite solar cells. Here, we use spectroscopic measurements to reveal a range of hitherto unknown fundamental properties of this materials family. Temperature-dependent transmission results show that the temperature of the tetragonal to orthorhombic structural transition decreases with increasing tin content. Through low-temperature magnetospectroscopy, we show that the exciton binding energy is lower than 16 meV, revealing that the dominant photogenerated species at typical operational conditions of optoelectronic devices are free charges rather than excitons. The reduced mass increases approximately proportionally to the band gap, and the mass values (0.075–0.090me) can be described with a two-band k·p perturbation model extended across the broad band gap range of 1.2–2.4 eV. Our findings can be generalized to predict values for the effective mass and binding energy for other members of this family of materials

Visualizing Buried Local Carrier Diffusion in Halide Perovskite Crystals via Two-Photon Microscopy.

Halide perovskites have shown great potential for light emission and photovoltaic applications due to their remarkable electronic properties. Although the device performances are promising, they are still limited by microscale heterogeneities in their photophysical properties. Here, we study the impact of these heterogeneities on the diffusion of charge carriers, which are processes crucial for efficient collection of charges in light-harvesting devices. A photoluminescence tomography technique is developed in a confocal microscope using one- and two-photon excitation to distinguish between local surface and bulk diffusion of charge carriers in methylammonium lead bromide single crystals. We observe a large dispersion of local diffusion coefficients with values between 0.3 and 2 cm2·s-1 depending on the trap density and the morphological environment-a distribution that would be missed from analogous macroscopic or surface measurements. This work reveals a new framework to understand diffusion pathways, which are extremely sensitive to local properties and buried defects

Influence of Grain Size on Phase Transitions in Halide Perovskite Films

Grain size in polycrystalline halide perovskite films is known to have an impact on the optoelectronic properties of the films, but its influence on their soft structural properties and phase transitions is unclear. Here, we use temperature-dependent X-ray diffraction, absorption, and macro- and micro-photoluminescence measurements to investigate the tetragonal to orthorhombic phase transition in thin methylammonium lead iodide films with grain sizes ranging from the micron scale down to the tens of nanometre scale. We show that the phase transition nominally at ~150 K is increasingly suppressed with decreasing grain size and, in the smallest grains, we only see the first evidence of a phase transition at temperatures as low as ~80 K. With decreasing grain size, we also see an increasing magnitude of the hysteresis in the structural and optoelectronic properties when cooling to, and then upon heating from, 100K. Our work reveals the remarkable sensitivity of the optoelectronic, physical and phase properties to the local environment of the perovskite structure, which will have large ramifications for phase and defect engineering in operating devices.EPSRC NanoDTC Royal Society ERC Starting Gran

Static and Dynamic Disorder in Triple-Cation Hybrid Perovskites

A detailed understanding of the carrier dynamics and emission characteristics of organic-inorganic lead halide perovskites is critical for their optoelectronic and energy harvesting applications. In this work, we reveal the impact of the crystal lattice disorder on the photo-generated electron-hole pairs through low-temperature photoluminescence measurements. We provide strong evidence that the intrinsic disorder forms a sub-bandgap tail density of states, which determines the emission properties at low temperature. The PL spectra indicate that the disorder evolves with increasing temperature, changing its character from static to dynamic. This change is accompanied by a rapid drop of the PL efficiency, originating from the increased mobility of excitons/polarons, which enables them to reach deep non-radiative recombination centers more easily

Graphene-perovskite fibre photodetectors

The integration of optoelectronic devices, such as transistors and photodetectors (PDs), into wearables and textiles is of great interest for applications such as healthcare and physiological monitoring. These require flexible/wearable systems adaptable to body motions, thus materials conformable to non-planar surfaces, and able to maintain performance under mechanical distortions. Here, we prepare fibre PDs combining rolled graphene layers and photoactive perovskites. Conductive fibres ($\sim$500$\Omega$/cm) are made by rolling single layer graphene (SLG) around silica fibres, followed by deposition of a dielectric layer (Al$_{2}$O$_{3}$ and parylene C), another rolled SLG as channel, and perovskite as photoactive component. The resulting gate-tunable PDs have response time$\sim$5ms, with an external responsivity$\sim$22kA/W at 488nm for 1V bias. The external responsivity is two orders of magnitude higher and the response time one order of magnitude faster than state-of-the-art wearable fibre based PDs. Under bending at 4mm radius, up to$\sim$80\% photocurrent is maintained. Washability tests show$\sim$72\% of initial photocurrent after 30 cycles, promising for wearable applications

Photo-induced halide redistribution in organic-inorganic perovskite films.

Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance

Imaging Light-Induced Migration of Dislocations in Halide Perovskites with 3d Nanoscale Strain Mapping

In recent years, halide perovskite materials have been used to make high-performance solar cells and light-emitting devices. However, material defects still limit device performance and stability. Here, synchrotron-based Bragg coherent diffraction imaging is used to visualize nanoscale strain fields, such as those local to defects, in halide perovskite microcrystals. Significant strain heterogeneity within MAPbBr3 (MA = CH3NH3+) crystals is found in spite of their high optoelectronic quality, and both 〈100〉 and 〈110〉 edge dislocations are identified through analysis of their local strain fields. By imaging these defects and strain fields in situ under continuous illumination, dramatic light-induced dislocation migration across hundreds of nanometers is uncovered. Further, by selectively studying crystals that are damaged by the X-ray beam, large dislocation densities and increased nanoscale strains are correlated with material degradation and substantially altered optoelectronic properties assessed using photoluminescence microscopy measurements. These results demonstrate the dynamic nature of extended defects and strain in halide perovskites, which will have important consequences for device performance and operational stability