Structure and Stability of the Iodide Elpasolite, Cs2AgBiI6

Iodide elpasolites (or double perovskites, A2B'B"I6, B' = M+, B" = M3+) are predicted to be promising alternatives to lead-based perovskite semiconductors for photovoltaic and optoelectronic applications, but no iodide elpasolite has ever been definitively prepared or structurally characterized. Iodide elpasolites are widely predicted to be unstable due to favorable decomposition to the competing A3B2I9 (B = M3+) phase. Here, we report the results of synchrotron XRD and X-ray total scattering measurements on putative Cs2AgBiI6 nanocrystals made via anion exchange from parent Cs2AgBiBr6 nanocrystals. Rietveld refinement of XRD and PDF data shows that these nanocrystals indeed exhibit a tetragonal (I4-m) elpasolite structure, making them the first example of a structurally characterized iodide elpasolite. A series of experiments probing structural relaxation and the effects of surface ligation or grain size all point to the critical role of surface free energy in stabilizing the iodide elpasolite phase in these nanocrystals.Comment: 7 figures, 1 scheme, plus supporting information fil

Fluctuations and Gibbs-Thomson Law - the Simple Physics.

Crystals of slightly soluble materials should be subject of relatively weak attachment/detachment fluctuations on their faces so that steps on that faces have low kink density. These steps are parallel to the most close packed lattice rows and form polygons on a crystal surface. The process responsible for implementation of the classical Gibbs-Thomson law (GTL) for the polygonal step (in two dimensions, 2D) is kink exchange between the step corners. For the 3D crystallites, this mechanism includes step exchange. If these mechanisms do not operate because of slow fluctuations the GTL is not applicable. Physics of these processes and conditions for the GTL applicability are discussed on a simple qualitative level

Microscopic evidence for liquid-liquid separation in supersaturated CaCO3 solutions

Recent experimental observations of the onset of calcium carbonate (CaCO3) mineralization suggest the emergence of a population of clusters that are stable rather than unstable as predicted by classical nucleation theory. This study uses molecular dynamics simulations to probe the structure, dynamics, and energetics of hydrated CaCO3 clusters and lattice gas simulations to explore the behavior of cluster populations before nucleation. Our results predict formation of a dense liquid phase through liquid-liquid separation within the concentration range in which clusters are observed. Coalescence and solidification of nanoscale droplets results in formation of a solid phase, the structure of which is consistent with amorphous CaCO3. The presence of a liquid-liquid binodal enables a diverse set of experimental observations to be reconciled within the context of established phase-separation mechanisms

A classical view on nonclassical nucleation

Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO_{3}) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO_{3} nucleation is still a topic of intense discussion, with new pathways for its growth from ions in solution proposed in recent years. These new pathways include the so-called nonclassical nucleation mechanism via the assembly of thermodynamically stable prenucleation clusters, as well as the formation of a dense liquid precursor phase via liquid–liquid phase separation. Here, we present results from a combined experimental and computational investigation on the precipitation of CaCO_{3} in dilute aqueous solutions. We propose that a dense liquid phase (containing 4–7 H_{2}O per CaCO_{3} unit) forms in supersaturated solutions through the association of ions and ion pairs without significant participation of larger ion clusters. This liquid acts as the precursor for the formation of solid CaCO_{3} in the form of vaterite, which grows via a net transfer of ions from solution according to z Ca^{2+} + zCO_{3}^{2−} → z CaCO_{3}. The results show that all steps in this process can be explained according to classical concepts of crystal nucleation and growth, and that long-standing physical concepts of nucleation can describe multistep, multiphase growth mechanisms

The Effect of Ring Substitution Position on the Structural Conformation of Mercaptobenzoic Acid Self-Assembled Monolayers on Au(111)

Near edge X-ray absorption fine structure (NEX-AFS) spectroscopy, photoemission spectroscopy (PES) and contact angle measurements have been used to examine the structure and bonding of self-assembled monolayers (SAMs) prepared on Au(111) from the positional isomers of mercaptobenzoic acid (MBA). The isomer of MBA and solvent chosen in SAM preparation has considerable bearing upon film morphology. Carbon K-edge NEXAFS measurements indicate that the monomers of 2-, 3- and 4-MBA have well-defined orientations within their respective SAMs. Monomers of 3- and 4-MBA assume an upright orientation on the Au substrates in monolayers prepared using an acetic acid in ethanol solvent. The aryl ring and carboxyl group of these molecules are tilted from the surface normal by a colatitudal angle of {approx} 30{sup o}. Preparation of 4-MBA SAMs using pure ethanol solvent, a more traditional means of synthesis, had no appreciable effect upon the monomer orientation. Nonetheless, S(2p) PES measurements illustrate that it results in extensive bilayer formation via carboxyl group hydrogen-bonding between 4-MBA monomers. In 2-MBA monolayers prepared using acetic acid/ethanol solvent, the monomers adopt a more prostrate orientation on the Au substrates, in which the aryl ring and carboxyl group of the molecules are tilted {approx} 50{sup o} from the surface normal. This configuration is consistent with an interaction between both the mercaptan sulfur and carboxyl group of 2-MBA with the underlying substrate. S(2p) and C(1s) PES experiments provide supporting evidence for a bidentate interaction between 2-MBA and Au(111)