Routes to cubic ice through heterogeneous nucleation

The freezing of water into ice is one of the most important processes in the physical sciences. However, it is still not understood at the molecular level. In particular, the crystallization of cubic ice (Ic)—rather than the traditional hexagonal polytype (Ih)—has become an increasingly debated topic. Although evidence for Ic is thought to date back almost 400 y, it is only in the last year that pure Ic has been made in the laboratory, and these processes involved high-pressure ice phases. Since this demonstrates that pure Ic can form, the question naturally arises if Ic can be made from liquid water. With this in mind, we have performed a high-throughput computational screening study involving molecular dynamics simulations of nucleation on over 1,100 model substrates. From these simulations, we find that 1) many different substrates can promote the formation of pristine Ic; 2) Ic can be selectively nucleated for even the mildest supercooling; 3) the water contact layer’s resemblance to a face of ice is the key factor determining the polytype selectivity and nucleation temperature, independent of which polytype is promoted; and 4) substrate lattice match to ice is not indicative of the polytype obtained. Through this study, we have deepened understanding of the interplay of heterogeneous nucleation and ice I polytypism and suggest routes to Ic. More broadly, the substrate design methodology presented here combined with the insight gained can be used to understand and control polymorphism and stacking disorder in materials in general.

Nanoscale mapping of chemical composition in organic-inorganic hybrid perovskite films

Lead-based organic-inorganic hybrid perovskite (OIHP) solar cells can attain efficiencies over 20%. However, the impact of ion mobility and/or organic depletion, structural changes, and segregation under operating conditions urge for decisive and more accurate investigations. Hence, the development of analytical tools for accessing the grain-to-grain OIHP chemistry is of great relevance. Here, we used synchrotron infrared nanospectroscopy (nano-FTIR) to map individual nanograins in OIHP films. Our results reveal a spatial heterogeneity of the vibrational activity associated to the nanoscale chemical diversity of isolated grains. It was possible to map the chemistry of individual grains in CsFAMA [Cs0.05FA0.79MA0.16Pb(I0.83Br0.17)3] and FAMA [FA0.83MA0.17Pb(I0.83Br0.17)3] films, with information on their local composition. Nanograins with stronger nano-FTIR activity in CsFAMA and FAMA films can be assigned to PbI2 and hexagonal polytype phases, respectively. The analysis herein can be extended to any OIHP films where organic cation depletion/accumulation can be used as a chemical label to study composition.

Photo-induced cubic-to-hexagonal polytype transition in silicon nanowires

Crystalline phase transformation in silicon nanowires from cubic diamond to hexagonal diamond under strong laser excitation, caused by inhomogeneous heating-induced mechanical stresses.

Stabilization of 4H hexagonal phase in gold nanoribbons

Gold, silver, platinum and palladium typically crystallize with the face-centred cubic structure. Here we report the high-yield solution synthesis of gold nanoribbons in the 4H hexagonal polytype, a previously unreported metastable phase of gold. These gold nanoribbons undergo a phase transition from the original 4H hexagonal to face-centred cubic structure on ligand exchange under ambient conditions. Using monochromated electron energy-loss spectroscopy, the strong infrared plasmon absorption of single 4H gold nanoribbons is observed. Furthermore, the 4H hexagonal phases of silver, palladium and platinum can be readily stabilized through direct epitaxial growth of these metals on the 4H gold nanoribbon surface. Our findings may open up new strategies for the crystal phase-controlled synthesis of advanced noble metal nanomaterials.

3C-SiC Heteroepitaxy on Hexagonal SiC Substrates

The growth of 3C-SiC on hexagonal polytype is addressed and a brief review is given for various growth techniques. The Chemical Vapor Deposition is shown as a suitable technique to grow single domain 3C epilayers on 4H-SiC substrate and a 12.5 µm thick layer is demonstrated; even thicker layers have been obtained. Various characterization techniques including optical microscopy, X-ray techniques and photoluminescence are compared for the evaluation of the crystal quality and purity of the layers.

Quality Investigation of 3C-SiC Crystals Grown by CF-PVT Technique

This work presents the crystalline quality investigation of 3C-SiC unseeded crystals grown from vapor phase. Samples were polished after different crystallographic planes from crystals grown with or without nitrogen flow. The structural and optical investigation showed that the central part of the samples exhibited a very good crystalline quality. The best samples proved to be the {100} growth sectors where the only defects found were stacking faults with a defect density under 103 cm-1. At the edges, i.e. between two adjacent growth sectors, structural investigation by transmission electron microscopy revealed stacking faults and hexagonal polytype inclusions. The nitrogen doping was found not to have an influence on the crystalline quality.