In this paper, we address the phase stability and the relationship between optical gap and structural perturbations in cesium lead halide nanocrystals. We report photoluminescence (PL) spectra for cesium lead iodide (CsPbI3) perovskite nanocrystals under hydrostatic pressures up to 2.5 GPa. The peak position of the CsPbI3 PL shifts as a function of pressure. Initially, the PL shifts to lower energies, until a reversal occurs near 0.33 GPa. At higher pressures, the PL peak position shifts to the blue until PL vanishes above 2.5 GPa. We explain the pressure response with different modes of deformation of the perovskite crystal structure.

Solid-state chemical transformations at the nanoscale can be a powerful tool for achieving compositional complexity in nanomaterials. It is desirable to understand the mechanisms of such reactions and characterize the local-level composition of the resulting materials. Here, we examine how reaction temperature controls the elemental distribution in (GaZn)(NO) nanocrystals (NCs) synthesized via the solid-state nitridation of a mixture of nanoscale ZnO and ZnGaO NCs. (GaZn)(NO) is a visible-light absorbing semiconductor that is of interest for applications in solar photochemistry. We couple elemental mapping using energy-dispersive X-ray spectroscopy in a scanning transmission electron microscope (STEM-EDS) with colocation analysis to study the elemental distribution and the degree of homogeneity in the (GaZn)(NO) samples synthesized at temperatures ranging from 650 to 900 °C with varying ensemble compositions (i.e., x values). Over this range of temperatures, the elemental distribution ranges from highly heterogeneous at 650 °C, consisting of a mixture of larger particles with Ga and N enrichment near the surface and very small NCs, to uniform particles with evenly distributed constituent elements for most compositions at 800 °C and above. We propose a mechanism for the formation of the (GaZn)(NO) NCs in the solid state that involves phase transformation of cubic spinel ZnGaO to wurtzite (GaZn)(NO) and diffusion of the elements along with nitrogen incorporation. The temperature-dependence of nitrogen incorporation, bulk diffusion, and vacancy-assisted diffusion processes determines the elemental distribution at each synthesis temperature. Finally, we discuss how the visible band gap of (GaZn)(NO) NCs varies with composition and elemental distribution.

The performance and solvation characteristics of two novel latex nanoparticle (NP) pseudo-stationary phases (PSPs) for EKC are determined and compared to those of previously reported micellar, polymeric, and NP materials. The new NPs have shells composed of strongly acidic poly(AMPS) as opposed to the poly(acrylic acid) shell of the prior NP, and have varied hydrophobic core chemistry of either poly(butyl acrylate) or poly(ethyl acrylate). The NPs poly(AMPS) shell shows only minor changes in mobility and selectivity between pH 4.9 and 9.4, allowing adjustment of pH to influence and optimize separation performance. All of the NP phases have significantly different solvation characteristics and selectivity relative to SDS micelles. The selectivity and solvent character are similar for NPs with poly(butyl acrylate) cores and different shells, but vary significantly between NPs with poly(butyl acrylate) versus poly(ethyl acrylate) cores. NPs with poly(butyl acrylate) cores are among the least cohesive PSPs reported to date, while the NP with poly(ethyl acrylate) core is among the most cohesive. The results demonstrate that PSPs with unique selectivity can be generated by altering the chemistry of the hydrophobic core.

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Many ternary and quaternary semiconductors have been made in nanocrystalline forms for a variety of applications, but we have little understanding of how well their ensemble properties reflect the properties of individual nanocrystals. We examine electronic structure heterogeneities in nanocrystals of (Ga1–x Zn x )(N1–x O x ), a semiconductor that splits water under visible illumination. We use valence electron energy loss spectroscopy (VEELS) in a scanning transmission electron microscope to map out electronic spectra of (Ga1–x Zn x )(N1–x O x ) nanocrystals with a spatial resolution of 8 nm. We examine three samples with varying degrees of intraparticle and interparticle compositional heterogeneity and ensemble optical spectra that range from a single band gap in the visible to two band gaps, one in the visible and one in the UV. The VEELS spectra resemble the ensemble absorption spectra for a sample with a homogeneous elemental distribution and a single band gap and, more interestingly, one with intraparticle compositional heterogeneity and two band gaps. We observe spatial variation in VEELS spectra only with significant interparticle compositional heterogeneity. Hence, we reveal the conditions under which the ensemble spectra reveal the optical properties of individual (Ga1–x Zn x )(N1–x O x ) particles. More broadly, we illustrate how VEELS can be used to probe electronic heterogeneities in compositionally complex nanoscale semiconductors.