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Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light-emitting applications. Recent studies have focused on nanoplatelets that are able to self-assemble and transform on solid substrates. However, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present a detailed analysis of the transformation of self-assembled stacks of CsPbBr3 nanoplatelets in solution over a period of a few months by using ex situ transmission electron microscopy and surface analysis. We demonstrate that the transformation mechanism can be understood as oriented attachment, proceeding through the following steps: (i) desorption of the ligands from the surfaces of the particles, causing the seamless atomic merging of nanoplatelet stacks into nanobelts; (ii) merging of neighboring nanobelts that form more extended nanoplates; and (iii) attachment of nanobelts and nanoplates, forming objects with an atomic structure that resembles a mosaic made of broken nanotiles. We reveal that aged nanobelts and nanoplates, which are mainly stabilized by amine/ammonium ions, link through a bilayer of CsBr, with the atomic columns of neighboring perovskite lattices shifted by a half-unit-cell, forming Ruddlesden-Popper planar faults. We also show, via in situ monitoring of the nanocrystal photoluminescence combined with transmission electron microscopy analysis, that the transformation is temperature driven and that it can take place within tens of minutes in solution and in spin-coated films. Understanding this process gives crucial information for the design and fabrication of perovskite materials, where control over the type and density of defects is desired, stimulating the development of perovskite nanocrystal structures with tailored electronic properties.

Metal‐halide perovskites (PSKs) are emergent materials for a large range of applications, and the layered double PSK architectures vastly enrich the opportunities to design their composition, structural properties, and optoelectronic behavior. The stability, crystal phase, and electronic bandgap depend strongly on the bonds and distortions of the octahedra lattice that are at the origin of the vibrational spectrum of these materials. This work investigates the structural dynamics of flakes of exfoliated layered Ag‐Bi bromide double PSKs by angle‐dependent polarized Raman spectroscopy and density functional theory modeling. The well‐defined orientation of the inorganic octahedra lattice with respect to the light polarization allows to correlate the angle‐dependent intensity of the Raman signal to the directionality and symmetry of the phonon modes. Low‐frequency vibrations are revealed for which a detailed microscopic and group theory assignment of the Raman modes is provided. The temperature‐dependent measurements across the phase transitions show marked changes in the phonon frequencies, reveal soft modes, and help to distinguish first from second‐order transitions as well as to determine their transition temperature. This provides highly valuable insights to improve the properties of this class of Pb‐free PSKs for applications in energy harvesting and optoelectronics. [ABSTRACT FROM AUTHOR]

Perovskite-based optoelectronic devices have shown remarkable performances, especially in the field of photovoltaics. Still, a rapid solution-processing approach able to produce localized stable perovskite crystals remains a general challenge, and is a key step toward the miniaturization of such materials in on-chip components. This study presents the confined growth of methylammonium (MA) lead halide perovskite crystals that is thermally induced through localized laser irradiation. Importantly, such structures remain stable over time; that is, they neither dissolve back into the surrounding liquid nor detach from the substrate. This is attributed to a chemical reaction locally triggered by the induced heat on the substrate surface that is transferred to the perovskite precursors (liquid) layer, thus generating 'on-demand' MA ions from the N-methylformamide solvent. By tuning the laser parameters, such as power density or irradiation time, variations in shape and size of the crystals, from microcrystals of ≈50 µm to nanocuboids of ≈500 nm, are observed. This study also demonstrates that with an optimized distance between the irradiated regions and by controlling the relative laser displacement speed, luminescent and photoconductive MAPbBr3 wires and microplates can be generated. [ABSTRACT FROM AUTHOR]

Layered architectures for light-emitting diodes (LEDs) are the standard approach for solution-processable materials such as metal-halide perovskites. Upon designing the composition and thicknesses of the layers forming the LED, the primary focus is typically on the optimization of charge injection and balance. However, this approach only considers the process until electrons and holes recombine to generate photons, while for achieving optimized LED performance, the generated light must also be efficiently outcoupled. Our work focuses on the latter aspect. We assume efficient photon generation and analyze the effects of the geometrical configuration together with the dipole orientation, mimicking the light emission, on the main characteristics defining the LED, such as the Purcell effect and the outcoupling efficiency. We find that in-plane dipoles result in significantly increased outcoupling efficiency. Furthermore, the mismatch in refractive index among the layers and their different thicknesses can be tuned to maximize the Purcell effect and minimize internal losses. The combined optimization of dipole orientation and layer thicknesses can improve the efficiency of the LED up to a factor 10, hence highlighting the importance of considering also the photonic properties of the LED structures if the objective is to maximize the LED performance. [ABSTRACT FROM AUTHOR]

In article number 1701613, Milena P. Arciniegas, Liberato Manna, and co‐workers combine state‐of‐the‐art laser writing with a novel procedure allowing the in situ formation of methylammonium ions (the building blocks of perovskites) to localize stable MAPbBr3 crystals. By the laser‐induced heating of the liquid precursors, this approach produces luminescent and electrically conductive perovskite crystals following pre‐designed patterns. [ABSTRACT FROM AUTHOR]