On the Location of Boron in SiO2‐embedded Si Nanocrystals – An X‐ray Absorption Spectroscopy and Density Functional Theory Study

Doping of silicon nanostructures is crucial to understand their properties and to enhance their potential in various fields of application. Herein, SiO2-embedded Si nanocrystals (quantum dots) ≈3–6 nm in diameter are used as a model system to study the incorporation of B dopants by X-ray absorption near-edge spectroscopy (XANES). Such samples represent a model system for ultimately scaled, 3D-confined Si nanovolumes. The analysis is complemented by real-space density functional theory to calculate the 1s (K shell) electron binding energies of B in 11 different, thermodynamically stable configurations of the Si/SiOx/SiO2 system. Although no indications for a substitutional B-acceptor configuration are found, the predominant O coordination of B indicates the preferred B incorporation into the SiO2 matrix and near the Si-nanocrystal/SiO2 interface, which is inherently incompatible with charge carrier generation by dopants. It is concluded that B doping of ultrasmall Si nanostructures fails due to a lack of B incorporation onto Si lattice sites that cannot be overcome by increasing the B concentration. The inability to efficiently insert B into Si nanovolumes appears to be a boron-specific fundamental obstacle for electronic doping (e.g., not observed for phosphorus) that adds to the established nanosize effects, namely, increased dopant activation and ionization energies

On the Origin of Reversible and Irreversible Reactions in LiNix_{x}Co(1−x)/2_{(1-x)/2}Mn(1−x)/2_{(1-x)/2}O2_{2}

Bond formation and breakage is crucial upon energy storage in lithium transition metal oxides (LiMeO$_{2}$, Me = Ni, Co, Mn), i.e., the conventional cathode materials in Li ion batteries. Near-edge X-ray absorption finestructure spectroscopy (NEXAFS) of the Me L and O K edge performed upon the first discharge of LiNi$_{x}$Co$_{(1-x)/2}$Mn$_{(1-x)/2}$O$_{2}$ (x = 0.33: NCM111, x = 0.6: NCM622, x = 0.8: NCM811) in combination with charge transfer multiplet (CTM) calculations provide unambiguous evidence that redox reactions in NCMs proceed via a reversible oxidation of Ni associated with the formation of covalent bonds to O neighbors, and not, as widely assumed, via pure cationic or more recently discussed, pure anionic redox processes. Correlating these electronic changes with crystallographic data using operando synchrotron X-ray powder diffraction (SXPD) shows that the amount of ionic Ni limits the reversible capacity— at states of charge where all ionic Ni is oxidized (above 155 mAh g$^{-1}$), the lattice parameters collapse, and irreversible reactions are observed. Yet the covalence of the Ni–O bonds also triggers the electronic structure and thus the operation potential of the cathodes

Observation of Exchange Interaction in Iron(II) Spin Crossover Molecules in Contact with Passivated Ferromagnetic Surface of Co/Au(111)

Spin crossover (SCO) complexes sensitively react on changes of the environment by a change in the spin of the central metallic ion making them ideal candidates for molecular spintronics. In particular, the composite of SCO complexes and ferromagnetic (FM) surfaces would allow spin-state switching of the molecules in combination with the magnetic exchange interaction to the magnetic substrate. Unfortunately, when depositing SCO complexes on ferromagnetic surfaces, spin-state switching is blocked by the relatively strong interaction between the adsorbed molecules and the surface. Here, the Fe(II) SCO complex [FeII(Pyrz)2] (Pyrz = 3,5-dimethylpyrazolylborate) with sub-monolayer thickness in contact with a passivated FM film of Co on Au(111) is studied. In this case, the molecules preserve thermal spin crossover and at the same time the high-spin species show a sizable exchange interaction of > 0.9 T with the FM Co substrate. These observations provide a feasible design strategy in fabricating SCO-FM hybrid devices

First-time synthesis of a magnetoelectric core-shell composite via conventional solid-state reaction

In recent years, multiferroics and magnetoelectrics have demonstrated their potential for a variety of applications. However, no magnetoelectric material has been translated to a real application yet. Here, we report for the first time that a magnetoelectric core–shell ceramic, is synthesized via a conventional solid-state reaction, where core–shell grains form during a single sintering step. The core consists of ferrimagnetic $CoFe_{2}O_{4}$, which is surrounded by a ferroelectric shell consisting of $(BiFeO_{3})_{x}–(Bi_{1/2}K_{1/2}TiO_{3})_{1−x}$. We establish the core–shell nature of these grains by transmission-electron microscopy (TEM) and find an epitaxial crystallographic relation between core and shell, with a lattice mismatch of 6 ± 0.7%. The core–shell grains exhibit exceptional magnetoelectric coupling effects that we attribute to the epitaxial connection between the magnetic and ferroelectric phase, which also leads to magnetic exchange coupling as demonstrated by neutron diffraction. Apparently, ferrimagnetic $CoFe_{2}O_{4}$ cores undergo a non-centrosymmetric distortion of the crystal structure upon epitaxial strain from the shell, which leads to simultaneous ferrimagnetism and piezoelectricity. We conclude that in situ core–shell ceramics offer a number of advantages over other magnetoelectric composites, such as lower leakage current, higher density and absence of substrate clamping effects. At the same time, the material is predestined for application, since its preparation is cost-effective and only requires a single sintering step. This discovery adds a promising new perspective for the application of magnetoelectric materials

From LiNiO₂ to Li₂NiO₃ : Synthesis, Structures and Electrochemical Mechanisms in Li-Rich Nickel Oxides

The Li−Ni−O phase diagram contains a variety of compounds, most of which are electrochemically active in Li-ion batteries. Other than the well-known LiNiO2, here we report a facile solid-state method to prepare Li2NiO3 and other Li-rich Ni oxides of composition Li1+xNi1−xO2 (0 ≤ x ≤ 0.33). We characterize their crystal and electronic structure, exhibiting a highly oxidized Ni state and defects of various nature (Li−Ni disorder, stacking faults, oxygen vacancies). We then investigate the use of Li2NiO3 as a cathode active material and show its remarkably high specific capacity, which however fades quickly. While we demonstrate that the initial capacity is due to irreversible O2 release, such process stops quickly in favor of more classical reversible redox mechanisms that allow cycling the material for >100 cycles. After the severe oxygen loss (∼15−20%) and prolonged cycling, the Bragg reflections of Li2NiO3 disappear. Analysis of the diffracted intensities suggests the resulting phase is a disordered rock salt-type material with high Li content, close to Li0.5Ni0.5O, never reported to date and capable of Li diffusion. Our findings demonstrate that the Li−Ni−O phase diagram has not been fully investigated yet, especially concerning the preparation of new promising materials by out-of-equilibrium methods