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Inorganic halide perovskites have become attractive for many optoelectronic applications due to their outstanding properties. While chemical synthesis techniques have been successful in producing high-quality perovskite crystals, scaling up to wafer-scale thin films remains challenging. Vapor deposition methods, particularly physical vapor deposition and chemical vapor deposition, have emerged as potential solutions for large-scale thin film fabrication. However, the control of phase purity during deposition remains problematic. Here, we investigate single-source (CsPbBr3) and dual-source (CsBr and PbBr2) vapor deposition techniques to achieve phase-pure CsPbBr3 thin films. Utilizing Knudsen Effusion Mass Spectrometry, we demonstrate that while the single-source CsPbBr3 evaporation is partially congruent, it leads to compositional changes in the evaporant over time. The dual-source evaporation, with a precise control of the PbBr2/CsBr flux ratio, can improve phase purity, particularly at elevated substrate temperatures at excess PbBr2 conditions. Our results give direct evidence that the growth is CsBr-limited. Overall, our findings provide critical insights into the vapor phase deposition processes, highlighting the importance of evaporation conditions in achieving the desired inorganic perovskite stoichiometry and morphology., Comment: 33 pages, 5 figures, 8 figures in Supporting Information

Blue phosphorene -- two-dimensional, hexagonal-structured, semiconducting phosphorus -- has gained attention as it is considered easier to synthesize on metal surfaces than its allotrope, black phosphorene. Recent studies report different structures of phosphorene, for example, on Cu(111), but the underlying mechanisms of their formation are not known. Here, using a combination of in situ ultrahigh vacuum low-energy electron microscopy and in vacuo scanning tunneling microscopy, we determine the time-evolution of the surface structure and morphology during the deposition of phosphorus on single-crystalline Cu(111). We find that during early stages of deposition, phosphorus intermixes with Cu, resulting in copper phosphide structures. With increasing surface concentration of phosphorus, the phosphide phase disappears and a blue phosphorene layer forms, followed by self-assembly of highly ordered phosphorus clusters that eventually grow into multilayer islands. We attribute the unexpected transformation of stable phosphide to a phosphorene layer, and the previously unreported multilayer growth, to the presence of a large concentration of P2 dimers on the surface. Our results constitute direct evidence for a new growth mode leading to a phosphorene layer via an intermediary phase, which could underpin the growth of other 2D materials on strongly interacting substrates., Comment: 25 pages, 5 figures

We report on the optical properties of CsPbBr3 polycrystalline thin film on a single grain level. A sample comprised of isolated nanocrystals (NCs) mimicking the properties of the polycrystalline thin film grains that can be individually probed by photoluminescence spectroscopy was prepared. These NCs were analyzed using correlative microscopy allowing the examination of structural, chemical, and optical properties from identical sites. Our results show that the stoichiometry of the CsPbBr3 NCs is uniform and independent of the NCs' morphology. The photoluminescence (PL) peak emission wavelength is slightly dependent on the dimensions of NCs, with the blue shift up to 9 nm for the smallest analyzed NCs. The magnitude of the blueshift is smaller than the emission linewidth, thus detectable only by high-resolution PL mapping. By comparing the emission wavelengths obtained from the experiment and a rigorous effective mass model we can fully attribute the observed variations to the size-dependent quantum confinement effect., Comment: 25 pages, 3 figures

Fabrication of chiral assemblies of plasmonic nanoparticles is a highly attractive and challenging task with promising applications in light emission, detection, and sensing. So far, primarily organic chiral templates have been used for chirality inscription. However, this significantly limits the variety of nanoparticle preparation techniques to an in-pot approach at very low synthesis temperatures. Here, we demonstrate utilization of seemingly achiral inorganic nanotubes as templates for the chiral assembly of nanoparticles. We show that both metallic and dielectric nanoparticles can be attached to scroll-like chiral edges propagating on the surfaces of WS2 nanotubes. Due to relatively high temperature stability of these nanotubes, such assembly can be performed at temperatures as high as 550 {\deg}C. This large temperature range significantly widens the portfolio of usable nanoparticle fabrication techniques, allowing us to demonstrate a variety of chiral nanoparticle assemblies, ranging from metals (Au, Ga) and semiconductors (Ge) to oxides (WO3)., Comment: 20 pages, 3 figures

Direct growth of large-area vertically stacked two-dimensional (2D) van der Waal (vdW) materials is a prerequisite for their high-end applications in integrated electronics, optoelectronics and photovoltaics. Currently, centimetre- to even metre-scale monolayers of single-crystal graphene (MLG) and hexagonal boron nitride (h-BN) have been achieved by epitaxial growth on various single-crystalline substrates. However, in principle, this success in monolayer epitaxy seems extremely difficult to be replicated to bi- or few-layer growth, as the full coverage of the first layer was believed to terminate the reactivity of those adopting catalytic metal surfaces. Here, we report an exceptional layer-by-layer chemical vapour deposition (CVD) growth of large size bi-layer graphene single-crystals, enabled by self-transmitting catalytic activity from platinum (Pt) surfaces to the outermost graphene layers. In-situ growth and real-time surveillance experiments, under well-controlled environments, unambiguously verify that the growth does follow the layer-by-layer mode on open surfaces of MLG/Pt(111). First-principles calculations indicate that the transmittal of catalytic activity is allowed by an appreciable electronic hybridisation between graphene overlayers and Pt surfaces, enabling catalytic dissociation of hydrocarbons and subsequently direct graphitisation of their radicals on the outermost sp2 carbon surface. This self-transmitting catalytic activity is also proven to be robust for tube-furnace CVD in fabricating single-crystalline graphene bi-, tri- and tetra-layers, as well as h-BN few-layers. Our findings offer an exceptional strategy for potential controllable, layer-by-layer and wafer-scale growth of vertically stacked few-layered 2D single crystals., Comment: 5 figures and 9 extended figures