In III-V nanowires the energetic barriers for nucleation in the zinc blende or wurtzite arrangement are typically of a similar order of magnitude. As a result, both arrangements can occur in a single wire. Here, we investigate the evolution of this polytypism in self-catalyzed GaAs nanowires on Si(111) grown by molecular beam epitaxy with time-resolved in situ x-ray diffraction. We interpret our data in the framework of a height dependent Markov model for the stacking in the nanowires. In this way, we extract the mean sizes of faultless wurtzite and zinc blende segments-a key parameter of polytypic nanowires-and their temporal evolution during growth. Thereby, we infer quantitative information on the differences of the nucleation barriers including their evolution without requiring a model of the nucleus.

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SummaryMagnetic nanocrystals with a narrow size distribution hold promise for many applications in different areas ranging from biomedicine to electronics and energy storage. Herein, the microwave-assisted sol–gel synthesis and thorough characterization of size-monodisperse zinc ferrite nanoparticles of spherical shape is reported. X-ray diffraction, 57Fe Mössbauer spectroscopy and X-ray photoelectron spectroscopy all show that the material is both chemically and phase-pure and adopts a partially inverted spinel structure with Fe3+ ions residing on tetrahedral and octahedral sites according to (Zn0.32Fe0.68)tet[Zn0.68Fe1.32]octO4±δ. Electron microscopy and direct-current magnetometry confirm the size uniformity of the nanocrystals, while frequency-dependent alternating-current magnetic susceptibility measurements indicate the presence of a superspin glass state with a freezing temperature of about 22 K. Furthermore, as demonstrated by galvanostatic charge–discharge tests and ex situ X-ray absorption near edge structure spectroscopy, the as-prepared zinc ferrite nanocrystals can be used as a high-capacity anode material for Li-ion batteries, showing little capacity fade – after activation – over hundreds of cycles. Overall, in addition to the good material characteristics, it is remarkable that the microwave-based synthetic route is simple, easily reproducible and scalable.

LiNi0.5Mn1.5O4 spinel cathode was studied during the first discharge cycle using combined full field Transmission X-ray Microscopy (TXM) and X-ray Absorption Near Edge Structure Spectroscopy (XANES) techniques to follow the chemical phase transformation as well as the microstructural evolution of cathode materials upon operation within an electrochemical cell. The spatial distribution and electrochemical process of the spinel material with spherical granules of 30 μm and 3 μm crystallite size was investigated. The spectroscopic imaging of the cathode within field of view of 40 × 32 μm(2) and spatial resolution of 40 nm has revealed an increase of the LiNi0.5Mn1.5O4 granule size during lithiation providing an insight into the effect of the particle size and morphology on the electrochemical process. The chemical elemental distribution and the content of the different oxidation states of the two absorbing elements (Ni and Mn) have been determined in operando from the XANES imaging. A gradual increase in the content of the oxidation state Mn(3+) from 8% up to 64% has been recorded during the discharge from 5 V to 2.7 V. The study of the local oxidation reduction behavior of Mn(3+) reveals a reversibility aspect in the local electrochemical reaction of Mn(4+) toward Mn(3+) in areas located in the center of the aggregate as well as in areas closed to the electrolyte. During the discharge process, a mixture of Mn(3+) and Mn(4+) has been detected while only single electron valence states have been found in the case of Ni. Probing the chemical changes during the discharge using two-dimensional XANES reveals spatial differences in the electrochemical activities of the two absorbing elements Ni and Mn.