Splay-bend nematic phases of bent colloidal silica rods induced by polydispersity.

Liquid crystal (LC) phases are in between solids and liquids with properties of both. Nematic LCs composed of rod-like molecules or particles exhibit long-range orientational order, yielding characteristic birefringence, but they lack positional order, allowing them to flow like a liquid. This combination of properties as well as their sensitivity to external fields make nematic LCs fundamental for optical applications e.g. liquid crystal displays (LCDs). When rod-like particles become bent, spontaneous bend deformations arise in the LC, leading to geometric frustration which can be resolved by complementary twist or splay deformations forming intriguing twist-bend (NTB) and splay-bend (NSB) nematic phases. Here, we show experimentally that the elusive NSB phases can be stabilized in systems of polydisperse micron-sized bent silica rods. Our results open avenues for the realization of NTB and NSB phases of colloidal and molecular LCs.

In Situ Study of the Wet Chemical Etching of SiO2 and Nanoparticle@SiO2 Core-Shell Nanospheres.

The recent development of liquid cell (scanning) transmission electron microscopy (LC-(S)TEM) has opened the unique possibility of studying the chemical behavior of nanomaterials down to the nanoscale in a liquid environment. Here, we show that the chemically induced etching of three different types of silica-based silica nanoparticles can be reliably studied at the single particle level using LC-(S)TEM with a negligible effect of the electron beam, and we demonstrate this method by successfully monitoring the formation of silica-based heterogeneous yolk-shell nanostructures. By scrutinizing the influence of electron beam irradiation, we show that the cumulative electron dose on the imaging area plays a crucial role in the observed damage and needs to be considered during experimental design. Monte-Carlo simulations of the electron trajectories during LC-(S)TEM experiments allowed us to relate the cumulative electron dose to the deposited energy on the particles, which was found to significantly alter the silica network under imaging conditions of nanoparticles. We used these optimized LC-(S)TEM imaging conditions to systematically characterize the wet etching of silica and metal(oxide)-silica core-shell nanoparticles with cores of gold and iron oxide, which are representative of many other core-silica-shell systems. The LC-(S)TEM method reliably reproduced the etching patterns of Stöber, water-in-oil reverse microemulsion (WORM), and amino acid-catalyzed silica particles that were reported before in the literature. Furthermore, we directly visualized the formation of yolk-shell structures from the wet etching of Au@Stöber silica and Fe3O4@WORM silica core-shell nanospheres.

Interplay between spherical confinement and particle shape on the self-assembly of rounded cubes.

Self-assembly of nanoparticles (NPs) inside drying emulsion droplets provides a general strategy for hierarchical structuring of matter at different length scales. The local orientation of neighboring crystalline NPs can be crucial to optimize for instance the optical and electronic properties of the self-assembled superstructures. By integrating experiments and computer simulations, we demonstrate that the orientational correlations of cubic NPs inside drying emulsion droplets are significantly determined by their flat faces. We analyze the rich interplay of positional and orientational order as the particle shape changes from a sharp cube to a rounded cube. Sharp cubes strongly align to form simple-cubic superstructures whereas rounded cubes assemble into icosahedral clusters with additionally strong local orientational correlations. This demonstrates that the interplay between packing, confinement and shape can be utilized to develop new materials with novel properties.