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.
Colloidal lead halide perovskite nanocrystals and nanoplatelets have emerged as promising semiconductor nanomaterials because of their spectral tunability, facile processability, and bright emission with high color purity. In particular, strong quantum and dielectric confinement make atomically thin colloidal lead bromide perovskite nanoplatelets a favorable candidate for next-generation deep-blue-emitting (λmax = 437 nm) materials. However, poor photostability poses a critical challenge; colloidal nanoplatelets suffer from photobleaching or transformation into thicker, less-confined nanostructures with red-shifted emission upon UV irradiation. In this study, we synthesize deep-blue-emitting organic–inorganic hybrid perovskite nanoplatelets (formula: L2[ABX3]BX4, L: butylammonium and octylammonium, A: methylammonium or formamidinium, B: lead, and X: bromide or iodide) with large lateral dimension (∼1 μm) by ligand-assisted reprecipitation and systematically investigate the factors that affect the photostability of those nanoplatelets. We find that freshness of the prepared precursor solutions for ligand-assisted reprecipitation is critical to obtain better stability with high photoluminescence quantum yield of perovskite nanoplatelets. Photobleaching is found to result from intrinsic instability of the perovskite lattice against UV irradiation in nanoplatelets, whereas transformation into thicker nanostructures results from extrinsic factorsmoisture, primarily. Furthermore, we observe that substitution of the organic cation from formamidinium to methylammonium and addition of excess alkylammonium bromide ligands significantly enhance both the ambient and photostability. Lastly, we demonstrate that the dropcast film of methylammonium lead bromide nanoplatelets with excess alkylammonium bromide ligands shows dramatically improved stability both under UV irradiation and under ambient conditions. This study expands our understanding of the factors that affect perovskite nanoplatelet photostability and opens up new possibilities for the fabrication of stable perovskite nanoplatelet-based optoelectronic devices.
Cesium lead halide perovskite nanocrystals are promising emissive materials for a variety of optoelectronic applications. To fully realize the potential of these materials, we must understand the energetics and dynamics of multiexciton states which are populated under device relevant excitation conditions. We utilized time-resolved and spectrally-resolved photoluminescence studies to investigate the biexciton binding energy as well as a red-shifted emission feature previously reported under high-flux excitation conditions. We determine that this red-shifted emission feature can be ascribed to sample sintering induced by air-exposure and high-flux irradiation. Furthermore, we determine that the biexciton binding energy at room temperature is at most ±20 meV, providing a key insight toward understanding many-body interactions in the lead halide perovskite lattice.
Silver phenylselenolate (AgSePh) is a hybrid organic–inorganic two-dimensional (2D) semiconductor exhibiting narrow blue emission, in-plane anisotropy, and large exciton binding energy. Here, we show that the addition of carefully chosen solvent vapors during the chemical transformation of metallic silver to AgSePh allows for control over the size and orientation of AgSePh crystals. By testing 28 solvent vapors (with different polarities, boiling points, and functional groups), we controlled the resulting crystal size from <200 nm up to a few μm. Furthermore, choice of solvent vapor can substantially improve the orientational homogeneity of 2D crystals with respect to the substrate. In particular, solvents known to form complexes with silver ions, such as dimethyl sulfoxide (DMSO), led to the largest lateral crystal dimensions and parallel crystal orientation. We perform systematic optical and electrical characterizations on DMSO vapor-grown AgSePh films demonstrating improved crystalline quality, lower defect densities, higher photoconductivity, lower dark conductivity, suppression of ionic migration, and reduced midgap photoluminescence at low temperature. Overall, this work provides a strategy for realizing AgSePh films with improved optical properties and reveals the roles of solvent vapors on the chemical transformation of metallic silver.
Substitutional metal doping is a powerful strategy for manipulating the emission spectra and excited state dynamics of semiconductor nanomaterials. Here, we demonstrate the synthesis of colloidal manganese (Mn2+)-doped organic–inorganic hybrid perovskite nanoplatelets (chemical formula: L2[APb1–x Mn x Br3] n−1Pb1–x Mn x Br4; L, butylammonium; A, methylammonium or formamidinium; n (= 1 or 2), number of Pb1–x Mn x Br6 4– octahedral layers in thickness) via a ligand-assisted reprecipitation method. Substitutional doping of manganese for lead introduces bright (approaching 100% efficiency) and long-lived (>500 μs) midgap Mn2+ atomic states, and the doped nanoplatelets exhibit dual emission from both the band edge and the dopant state. Photoluminescence quantum yields and band-edge-to-Mn intensity ratios exhibit strong excitation power dependence, even at a very low incident intensity (<100 μW/cm2). Surprisingly, we find that the saturation of long-lived Mn2+ dopant sites cannot explain our observation. Instead, we propose an alternative mechanism involving the cross-relaxation of long-lived Mn-site excitations by freely diffusing band-edge excitons. We formulate a kinetic model based on this cross-relaxation mechanism that quantitatively reproduces all of the experimental observations and validate the model using time-resolved absorption and emission spectroscopy. Finally, we extract a concentration-normalized microscopic rate constant for band edge-to-dopant excitation transfer that is ∼10× faster in methylammonium-containing nanoplatelets than in formamidinium-containing nanoplatelets. This work provides fundamental insight into the interaction of mobile band edge excitons with localized dopant sites in 2D semiconductors and expands the toolbox for manipulating light emission in perovskite nanomaterials.
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