Coherent piezoelectric strain transfer to thick epitaxial ferromagnetic films with large lattice mismatch

Strain control of epitaxial films using piezoelectric substrates has recently attracted significant scientific interest. Despite its potential as a powerful test bed for strain-related physical phenomena and strain-driven electronic, magnetic, and optical technologies, detailed studies on the efficiency and uniformity of piezoelectric strain transfer are scarce. Here, we demonstrate that full and uniform piezoelectric strain transfer to epitaxial films is not limited to systems with small lattice mismatch or limited film thickness. Detailed transmission electron microscopy (TEM) and x-ray diffraction (XRD) measurements of 100 nm thick CoFe2O4 and La2/3Sr1/3MnO3 epitaxial films on piezoelectric 0.72Pb(Mg1/3Nb2/3)O3–0.28PbTiO3 substrates (+4.3% and -3.8% lattice mismatch) indicate that misfit dislocations near the interface do not hamper the transfer of piezoelectric strain. Instead, the epitaxial magnetic oxide films and PMN-PT substrates are strained coherently and their lattice parameters change linearly as a function of applied electric field when their remnant growth-induced strain state is negligible. As a result, ferromagnetic properties such as the coercive field, saturation magnetization, and Curie temperature can be reversibly tuned by electrical means. The observation of efficient piezoelectric strain transfer in large-mismatch heteroepitaxial structures opens up new possibilities for the engineering of strain-controlled physical properties in a broad class of hybrid material systems.Peer reviewe

Thin film growth by pulsed laser deposition and properties of 122-type iron-based superconductor AE(Fe1--xCox)2As2 (AE = alkaline earth)

This paper reports comprehensive results on thin-film growth of 122-type iron-pnictide superconductors, AE(Fe1-xCox)2As2 (AE = Ca, Sr, and Ba, AEFe2As2:Co) by a pulsed laser deposition method using a neodymium-doped yttrium aluminum garnet laser as an excitation source. The most critical parameter to produce the SrFe2As2:Co and BaFe2As2:Co phases is the substrate temperature (Ts). It is difficult to produce highly-pure CaFe2As2:Co phase thin film at any Ts. For BaFe2As2:Co epitaxial films, controlling Ts at 800-850 {\deg}C and growth rate to 2.8-3.3 {\AA}/s produced high-quality films with good crystallinity, flat surfaces, and high critical current densities > 1 MA/cm2, which were obtained for film thicknesses from 100 to 500 nm. The doping concentration x was optimized for Ba(Fe1-xCox)2As2 epitaxial films, leading to the highest critical temperature of 25.5 K in the epitaxial films with the nominal x = 0.075.Comment: will be published in the special issue of Superconductor Science and Technology, `Iron12

Alternating domains with uniaxial and biaxial magnetic anisotropy in epitaxial Fe films on BaTiO[sub 3]

We report on domain formation and magnetization reversal in epitaxial Fe films on ferroelectric BaTiO3 substrates with ferroelastica–c stripe domains. The Fe films exhibit biaxial magnetic anisotropy on top of c domains with out-of-plane polarization, whereas the in-plane lattice elongation of a domains induces uniaxial magnetoelasticanisotropy via inverse magnetostriction. The strong modulation of magnetic anisotropy symmetry results in full imprinting of the a–c domain pattern in the Fe films. Exchange and magnetostaticinteractions between neighboring magnetic stripes further influence magnetization reversal and pattern formation within the a and c domains.Peer reviewe

Magneto-ionic control of interfacial magnetism

In metal/oxide heterostructures, rich chemical electronic magnetic and mechanical properties can emerge from interfacial chemistry and structure. The possibility to dynamically control interface characteristics with an electric field paves the way towards voltage control of these properties in solid-state devices. Here, we show that electrical switching of the interfacial oxidation state allows for voltage control of magnetic properties to an extent never before achieved through conventional magneto-electric coupling mechanisms. We directly observe in situ voltage-driven O{superscript 2−] migration in a ​Co/metal-oxide bilayer, which we use to toggle the interfacial magnetic anisotropy energy by >0.75 erg cm[superscript −2] at just 2 V. We exploit the thermally activated nature of ion migration to markedly increase the switching efficiency and to demonstrate reversible patterning of magnetic properties through local activation of ionic migration. These results suggest a path towards voltage-programmable materials based on solid-state switching of interface oxygen chemistry.National Science Foundation (U.S.) (NSF-ECCS-1128439)National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (DMR-0819762)Samsung (Firm) (Samsung Global MRAM Innovation program

Understanding the Stabilizing Effects of Nanoscale Metal Oxide and Li–Metal Oxide Coatings on Lithium-Ion Battery Positive Electrode Materials

Nickel-rich layered oxides, such as LiNi0.6Co0.2Mn0.2O2 (NMC622), are high-capacity electrode materials for lithium-ion batteries. However, this material faces issues, such as poor durability at high cut-off voltages (>4.4 V vs Li/Li+), which mainly originate from an unstable electrode-electrolyte interface. To reduce the side reactions at the interfacial zone and increase the structural stability of the NMC622 materials, nanoscale (Peer reviewe

Long term cycling behavior of Mg-doped LiCoO2 materials investigated with the help of laboratory scale X-ray absorption near-edge spectroscopy

The use of Li-ion batteries is increasing rapidly. Understanding the processes behind active material aging helps to enhance the materials, and therefore, development of new in situ methods for structural studies is important. In addition, understanding the effect of different synthesis methods on the active material properties is necessary to optimize the material cycle life. In this work, the performance of LiCoO2 doped with Mg during the lithiation step is compared to LiCoO2 prepared using an Mg-doped Co3O4 precursor. In situ laboratory-scale X-ray absorption near-edge spectroscopy is used to analyze the Co valence changes in LiCoO2 to understand the electrochemical behavior of the investigated materials. The maximum reachable Co valence state is found to decrease upon aging, a small decrease indicating a good cycle-life, and this is attributed to the enhanced stacking order, better Mg distribution in the lattice, and fine primary particle size in the material. In the synthesis conditions used in this study, Mg doping during the lithiation step is shown to perform better compared to the precursor doping. Overlithiation is shown to reduce the electrochemical performance of nondoped and precursor-doped LiCoO2 materials but not to affect the cyclability of lithiation-doped LiCoO2. (c) 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).Peer reviewe

An integrated approach to Deacon chemistry on RuO2-based catalysts

AbstractRationally designed RuO2-based Deacon catalysts can contribute to massive energy saving compared to the current electrolysis process in chemically recycling HCl to produce molecular chlorine. Here, we report on our integrated approach between state-of-the-art experiments and calculations. The aim is to understand industrial Deacon catalyst in its realistic surface state and to derive mechanistic insights into this sustainable reaction. We show that the practically relevant RuO2/SnO2 consists of two major RuO2 morphologies, namely 2–4 nm-sized particles and 1–3-ML-thick epitaxial RuO2 films attached to the SnO2 support particles. A large fraction of the small nanoparticles expose {110} and {101} facets, whereas the film grows with the same orientations, due to the preferential surface orientation of the rutile-type support. Steady-state Deacon kinetics indicate a medium-to-strong positive effect of the partial pressures of reactants and deep inhibition by both water and chlorine products. Temporal Analysis of Products and in situ Prompt Gamma Activation Analysis strongly suggest a Langmuir–Hinshelwood mechanism and that adsorbed Cl poisons the surface. Under relevant operation conditions, the reactivity is proportional to the coverage of a specific atomic oxygen species. On the extensively chlorinated surface that can be described as surface oxy-chloride, oxygen activation is the rate-determining step. DFT-based micro-kinetic modeling reproduced all experimental observations and additionally suggested that the reaction is structure sensitive. Out of the investigated models, the 2ML RuO2 film-covered SnO2 gives rise to significantly higher reactivity than the (101) surface, whereas the 1ML film seems to be inactive