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Halide perovskites belong to an important family of semiconducting materials with electronic properties that enable a myriad of applications, especially in photovoltaics and optoelectronics. Their optical properties, including photoluminescence quantum yield, are affected and notably enhanced at crystal imperfections where the symmetry is broken and the density of states increases. These lattice distortions can be introduced through structural phase transitions, allowing charge gradients to appear near the interfaces between phase structures. In this work, we demonstrate controlled multiphase structuring in a single perovskite crystal. The concept uses cesium lead bromine (CsPbBr3) placed on a thermoplasmonic TiN/Si metasurface and enables single-, double-, and triple-phase structures to form on demand above room temperature. This approach promises application horizons of dynamically controlled heterostructures with distinctive electronic and enhanced optical properties.

Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

Manipulating the light polarization properties of gold nanoparticle aggregates can facilitate their applications in sensing and imaging. However, control of the intrinsic light polarization on demand at the nanoscale is hindered by the lack of a fundamental understanding of the structure-dependent plasmon coupling in the aggregates. Here, the polarization properties of intrinsic photoluminescence (PL) and scattering of gold nanoparticle dimers and trimers are studied experimentally and computationally at the single-aggregate level. We find that the PL excitation and emission polarization degrees of the aggregates are highly correlated to the shift of their PL and scattering spectra. The results suggest that the degree of PL polarization is dominated by the strength of the longitudinal plasmon resonance mode arising from the plasmon coupling between the two closest particles in the aggregate. While the PL direction is always along the two most strongly interacting particles in the trimers, changing the arrangement can modify the PL polarization degree. This work provides further insights into the mechanism of the plasmon coupling-induced polarized optical response of aggregated metal nanoparticles and suggests routes to achieve on-demand control of the PL light polarization. This paves the way to using the polarized optical response of plasmonic nanostructures for applications in photonics including sensing and imaging. [ABSTRACT FROM AUTHOR]

Defects in metal halide perovskites (MHP) are photosensitive, making the observer effect unavoidable when laser spectroscopy methods are applied. Photoluminescence (PL) bleaching and enhancement under light soaking and recovery in dark are examples of the transient phenomena that are consequent to the creation and healing of defects. Depending on the initial sample composition, environment, and other factors, the defect nature and evolution can strongly vary, making spectroscopic data analysis prone to misinterpretations. Herein, the use of an automatically acquired dependence of PL quantum yield (PLQY) on the laser pulse repetition rate and pulse fluence as a unique fingerprint of both charge carrier dynamics and defect evolution is demonstrated. A simple visual comparison of such fingerprints allows for assessment of similarities and differences between MHP samples. The study illustrates this by examining methylammonium lead triiodide (MAPbI3) films with altered stoichiometry that just after preparation showed very pronounced defect dynamics at time scale from milliseconds to seconds, clearly distorting the PLQY fingerprint. Upon weeks of storage, the sample fingerprints evolve toward the standard stoichiometric MAPbI3 in terms of both charge carrier dynamics and defect stability. Automatic PLQY mapping can be used as a universal method for assessment of perovskite sample quality. [ABSTRACT FROM AUTHOR]

Metal‐halide perovskites (MHPs) are promising as active optoelectronic materials for a diverse range of devices. Anion exchange is a post‐growth modification of MHP materials that allows tuning of the band gap and crystal structure by exposure to alternative halides, normally using solution methods. Here, low temperature gas‐phase anion exchange for the conversion of CsPbBr3 nanowires (NW) into CsPb(Br1−xClx) NWs using two media, fuming HCl and Cl2 gas, is systematically investigated. It is found that both methods can be used to tune the composition in the full range with excellent control. While fuming HCl is the simplest process, Cl2 gives similar results with no surface damage and better process control. Based on a simple solid diffusion model, an average diffusivity of 1.4 × 10−12 cm2s−1 is extracted for Cl‐anions inside CsPbBr3. By combining the Cl2 exchange process with electron‐beam lithography patterning, heterojunction NWs with varying halide compositions are produced, including complex barcode‐like NWs with segment lengths as short as 500 nm. Designed heterostructures provide an important basis for optoelectronic device applications of MHPs, and gas‐phase anion exchange should be suitable for any MHP morphology. [ABSTRACT FROM AUTHOR]

Two-dimensional polarization imaging (2D POLIM) is an experimental method where correlations between fluorescence excitation- and fluorescence emission-polarization properties are measured. One way to analyze 2D POLIM data is to apply a so-called single funnel approximation (SFA). The SFA allows for quantitative assessment of energy transfer between chromophores with identical spectra [homo-FRET (Förster resonance energy transfer)]. In this paper, we run a series of computer experiments to investigate the applicability of the analysis based on the SFA to various systems ranging from single multichromophoric systems to isotropic ensembles. By setting various scenarios of energy transfer between individual chromophores within a single object, we were able to define the borders of the practical application of SFA. It allowed us to reach a more comprehensive interpretation of the experimental data in terms of uncovering the internal arrangement of chromophores in the system and energy transfer between them. We also found that the SFA can always formally explain the data for isotropic ensembles and derived a formula connecting the energy funneling efficiency parameter and traditional fluorescence anisotropy. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: It has been a mystery that the detected fluorescence intensity of single MEH‐PPV molecules is much lower than expected based on their chain length. In this review, after re‐evaluating of the literature data in the light of new specially designed experiments, we present a comprehensive explanation of this issue: The actual size of MEH‐PPV molecules at single molecule level is much smaller than expected due to de‐aggregation and chain scission, while static quenching ("dark matter") also exists for large molecules, further reducing their brightness. [ABSTRACT FROM AUTHOR]

Photo‐ and charge‐carrier‐induced ion migration is a major challenge when utilizing metal halide perovskite semiconductors for optoelectronic applications. For mixed iodide/bromide perovskites, the compositional instability due to light‐ or electrical bias induced phase‐segregation restricts the exploitation of the entire bandgap range. Previous experimental and theoretical work suggests that excited states or charge carriers trigger the process, but the exact mechanism is still under debate. To identify the mechanism and cause of light‐induced phase‐segregation phenomena, the full compositional range of methylammonium lead bromide/iodide samples are investigated, MAPb(BrxI1‐x)3 with x = 0...1, by simultaneous in situ X‐ray diffraction (XRD) and photoluminescence (PL) spectroscopy during illumination. The quantitative comparison of composition‐dependent in situ XRD and PL shows that at excitation densities of 1 sun, only the initial stage of photo‐segregation is rationalized with the previously established thermodynamic models. However, a progression of the phase segregation is observed that is rationalized by considering long‐lived accumulative photo‐induced material alterations. It is suggested that (additional) photo‐induced defects, possibly halide vacancies and interstitials, need to be considered to fully rationalize light‐induced phase segregation and anticipate the findings to provide crucial insight for the development of more sophisticated models. [ABSTRACT FROM AUTHOR]

The photoluminescence (PL) of metal halide perovskites can recover after light or current‐induced degradation. This self‐healing ability is tested by acting mechanically on MAPbI3 polycrystalline microcrystals by an atomic force microscope tip (applying force, scratching, and cutting) while monitoring the PL. Although strain and crystal damage induce strong PL quenching, the initial balance between radiative and nonradiative processes in the microcrystals is restored within a few minutes. The stepwise quenching–recovery cycles induced by the mechanical action is interpreted as a modulation of the PL blinking behavior. This study proposes that the dynamic equilibrium between active and inactive states of the metastable nonradiative recombination centers causing blinking is perturbed by strain. Reversible stochastic transformation of several nonradiative centers per microcrystal under application/release of the local stress can lead to the observed PL quenching and recovery. Fitting the experimental PL trajectories by a phenomenological model based on viscoelasticity provides a characteristic time of strain relaxation in MAPbI3 on the order of 10–100 s. The key role of metastable defect states in nonradiative losses and in the self‐healing properties of perovskites is suggested. [ABSTRACT FROM AUTHOR]

Recently, research on the edge states of 2D lead halide perovskites (LHPs) has been attracting much attention. The lower‐energy edge state (LES) is believed to provide an efficient pathway for the dissociation of photoexcited excitons. However, the mechanism of the LES formation remains controversial, and studies that establish precisely the local electronic properties are lacking. Herein, the first study of spatially resolved electronic structures in 2D LHP single‐crystal flakes by X‐ray photoemission electron microscopy is presented, specifically identifying the contribution from the edge area. The results show that blueshifts occur in the Pb 5d core‐level peaks at the edge area compared to the interior area with much less difference in I 4d core‐level peaks. The shift becomes more pronounced as n varies from 1 to 3 (≈0.2–1.0 eV). This phenomenon is attributed to the surface restructuring of the edge area induced by the release of mechanical strain through lattice expansion. This work provides an important reference on the origin of the LES of 2D LHPs and is beneficial for future optoelectronic device applications. [ABSTRACT FROM AUTHOR]

Organo metal halide perovskites are solution processed semiconductors that recently attracted a great attention. They possess a rather “soft” and (photo) chemically active solid structure allowing for ion migration and other mass diffusion processes. This is a likely reason why non-radiative recombination centres in these materials are activated and deactivated on relatively slow time-scales. This dynamics reveals as photoluminescence (PL) fluctuations (blinking) of individual microcrystals and local areas of films and allows for application of a broad range of single molecule spectroscopy methods including optical super-resolution. Studying PL blinking resolves properties of individual non-radiative centres and helps to unravel their chemical nature.