The mechanism of rapid and selective heating of magnetic metal oxides under the magnetic field of microwaves which continues beyond the Curie temperature $ T_{c} $ is identified by using the Heisenberg model. Monte Carlo calculations based on the energy principle show that such heating is caused by non-resonant response of electron spins in the unfilled 3d shell to the wave magnetic field. Small spin reorientation thus generated leads to a large internal energy change through the exchange interactions between spins, which becomes maximal around $ T_{c} $ for magnetite $ {\rm Fe}_{3}{\rm O}_{4} $. The dissipative spin dynamics simulation yields the imaginary part of the magnetic susceptibility, which becomes largest around $ T_{c} $ and for the microwave frequency around 2 GHz. Hematite $ {\rm Fe}_{2}{\rm O}_{3} $ with weak spontaneous magnetization responds much less to microwaves as observed in experiments. The heating of titanium oxide by microwave magnetic field only when oxygen defects are present is also explained by our theory in terms of the absence of spontaneous magnetization.
Zirconia (ZrO2) has emerged as a promising technical ceramic, both as high temperature structural material and thermal barrier coating material, etc. The traditional synthesis of ZrO2 with spark plasma sintering (SPS) usually requires a sintering temperature as high as 1200C. General interest in lowering the sintering temperature to reduce energy consumption and thermal stresses has led to research on two promising routes, cold sintering via temperature-dependent chemical reactivity and sintering aids, which facilitates mass transport and improves densification. Here we combine both by develop…
The manufacture of solid oxide fuel cells (SOFCs) involves fabrication of a multilayer ceramic structure, for which constrained sintering is a key processing step in many cases. Defects are often observed in the sintered structure, but their formation during sintering is not well understood. In this work, various ceramic films were fabricated by screen printing and a variety of defects observed. Some films showed mud-cracking defects, whereas others presented distributed large pores. Mud cracking defects were found to originate from a network of fine cracks present in the green film and formed…
The Sn substituted Ni-Zn ferrites were synthesized by the standard double sintering technique using nano powders of nickel oxide (NiO), zinc oxide (ZnO), iron oxide (Fe2O3) and tin oxide (SnO2). The structural and electrical properties have been investigated by the X-ray diffraction, scanning electron microscopy, DC resistivity and dielectric measurements. Extra intermediate phase has been detected along with the inverse cubic spinel phase of Ni-Zn ferrite. Enhancement of grain size is observed in Sn substituted Ni-Zn ferrites. DC resistivity as a function of temperature has been investigated …
Interdiffusion between the yttria stabilized zirconia (YSZ) electrolyte and the gadolinia doped ceria (CGO) barrier layer is one of the major causes to the degradation of solid oxide fuel cells (SOFCs). We present in this work experimental investigations on CGO-YSZ bi-layer electrolyte sintered at 1250 C or 1315 C and element transport as a function of sintering temperature and dwelling time. In order to quantitatively simulate the experimental observations, the CALPHAD-type thermodynamic assessment of the CGO-YSZ system is performed by simplifying the system to a CeO2-ZrO2 quasi-binary system…
Recent investigations have shown that highly oxygen defective cerium oxides generate non-classical electrostriction that is superior to lead-based ferroelectrics. In this work, we report the effect of field-assisted spark plasma sintering (SPS) on electro-chemo-mechanical properties on Ca-doped ceria (CDC). Nanometric powders of ca. 10 nm are rapidly consolidated to form polycrystalline nanostructures with a high degree of crystalline disorder. Remarkably, the resultant material demonstrates a large electromechanical strain without a frequency-related relaxation effect. We conclude that electr…
The metastability of supported metal nanoparticles limits their application in heterogeneous catalysis at elevated temperatures due to their tendency to sinter. One strategy to overcome these thermodynamic limits on reducible oxide supports is encapsulation via strong metal-support interaction (SMSI). While annealing-induced encapsulation is a well-explored phenomenon for extended nanoparticles, it is as yet unknown whether the same mechanisms hold for sub-nanometer clusters, where concomitant sintering and alloying might play a significant role. In this article, we explore the encapsulation a…
Room-temperature ferromagnetism has been observed in the nanoparticles (7 - 30 nm dia) of nonmagnetic oxides such as CeO2, Al2O3, ZnO, In2O3 and SnO2. The saturated magnetic moments in CeO_2 and Al_2O_3 nanoparticles are comparable to those observed in transition metal doped wide band semiconducting oxides. The other oxide nanoparticles show somewhat lower values of magnetization but with a clear hysteretic behavior. Conversely, the bulk samples obtained by sintering the nanoparticles at high temperatures in air or oxygen became diamagnetic. As there were no magnetic impurities present, we ass…
Ultra-high-temperature ceramics (UHTCs) are optimal structural materials for applications that require extreme temperature resilience, resistance to chemically aggressive environments, wear, and mechanical stress. Processing UHTCs with laser-based additive manufacturing (AM) has not been fully realized due to a variety of obstacles. In this work, selective laser reaction sintering (SLRS) techniques were investigated for the production of near net-shape UHTC ceramics such as HfC, ZrC, TiC, HfN, ZrN, and TiN. Group IV transition metal and metal oxide precursor materials were chemically converted…
Selective laser reaction sintering techniques (SLRS) techniques were investigated for the production of near net-shape non-oxide ceramics including SiC, Si$_3$N$_4$, and HfC/SiC composites that might be compatible with prevailing powder bed fusion additive manufacturing processes. Reaction bonded layers of covalent ceramics were produced using in-situ reactions that occur during selective laser processing and layer formation. During SLRS, precursor materials composed of metal and/or metal oxide powders were fashioned into powder beds for conversion to non-oxide ceramic layers. Laser-processing…
The application of modern layer-by-layer growth techniques to transition-metal oxide materials raises the possibility of creating new classes of materials with rationally designed correlated electron properties. An important step toward this goal is the demonstration that electronic structure can be controlled by atomic composition. In compounds with partially occupied transition-metal d shells, one important aspect of the electronic structure is the relative occupancy of different d orbitals. Previous work has established that strain and quantum confinement can be used to influence orbital oc…
A high reversible capacity is a key feature for any rechargeable battery. In the lithium-ion battery technology, tin-oxide anodes do fulfill this requirement, but a fast loss of capacity hinders a full commercialization. Using first-principles calculations, we propose a microscopic model that sheds light on the reversible lithiation/delithiation of SnO and reveals that a sintering of Sn causes a strong degradation of SnO-based anodes. When the initial irreversible transformation ends, active anode grains consist of Li-oxide layers separated by Sn bilayers. During the following reversible lithi…
High-Tc Cu oxides consist of the alternating stack of the superconductive CuO2 layer and the block layer, such as Bi2Sr2O4 or La2-xSrxO2. By changing the block layer, we can change their physical properties, such as transition temperature Tc. The thermoelectric Co oxides have a similar layered structure composed of the conductive CoO2 layer and the blocking layer. Thus, we propose that their thremoelectric properties can be finely tuned by modifying the block layer.
We have investigated the magnetic ordering in the ultrathin c(10$\times$2) CoO(111) film supported on Ir(100) on the basis of ab-initio calculations. We find a close relationship between the local structural properties of the oxide film and the induced magnetic order, leading to alternating ferromagnetically and anti-ferromagnetically ordered segments. While the local magnetic order is directly related to the geometric position of the Co atoms, the mismatch between the CoO film and the Ir substrate leads to a complex long-range order of the oxide.
Electric fields can transform materials with respect to their structure and properties, enabling various applications ranging from batteries to spintronics. Recently electrolytic gating, which can generate large electric fields and voltage-driven ion transfer, has been identified as a powerful means to achieve electric-field-controlled phase transformations. The class of transition metal oxides (TMOs) provide many potential candidates that present a strong response under electrolytic gating. However, very few show a reversible structural transformation at room-temperature. Here, we report the …
We report on the development and application of an atomic layer etching (ALE) procedure based on alternating exposures of trimethylaluminum and anhydrous hydrogen fluoride (HF) implemented to controllably etch aluminum oxide. Our ALE process utilizes the same chemistry previously demonstrated in the atomic layer deposition of aluminum fluoride thin films, and can therefore be exploited to remove the surface oxide from metallic aluminum and replace it with thin fluoride layers in order to improve the performance of ultraviolet aluminum mirrors. This ALE process is modified relative to existing …
ZnO is a promising candidate as an environment friendly thermoelectric (TE) material. However, the poor TE figure of merit (zT) needs to be addressed to achieve significant TE efficiency for commercial applications. Here we demonstrate that selective enhancement in phonon scattering leads to increase in zT of RGO encapsulated Al-doped ZnO core shell nanohybrids, synthesized via a facile and scalable method. The incorporation of 1 at% Al with 1.5 wt% RGO into ZnO (AGZO) has been found to show significant enhancement in zT (=0.52 at 1100 K) which is an order of magnitude larger compared to that …
Atomically sharp domain walls (DWs) in ferroelectrics are considered as an ideal platform to realize easy-to-reconfigure nanoelectronic building blocks, created, manipulated and erased by external fields. However, conductive DWs have been exclusively observed in oxides, where DW mobility and conductivity is largely influenced by stoichiometry and defects. In contrast, we here report on conductive DWs in the non-oxide ferroelectric GaV$_4$S$_8$, where charge carriers are provided intrinsically by multivalent V$_4$ molecular clusters. We show that this new mechanism gives rise to DWs composed of…
A novel metallic and magnetic transition metal oxide Ag2NiO2 is studied by means of resistivity, magnetic susceptibility, specific heat and X-ray diffraction. The crystal structure is characterized by alternating stacking of a Ni3+O2 layer and a (Ag2)+ layer, the former realizing a spin-1/2 triangular lattice with eg orbital degeneracy and the latter providing itinerant electrons. It is found that the NiO2 layer exhibits orbital ordering at Ts = 260 K and antiferromagnetic spin ordering at TN = 56 K. Moreover, a moderately large mass enhancement is found for the itinerant electrons, suggesting…
We perform density functional theory plus dynamical mean field theory calculations to investi- gate internal charge transfer in an artificial superlattice composed of alternating layers of vanadate and manganite perovskite and Ruddlesden-Popper structure materials. We show that the elec- tronegativity difference between vanadium and manganese causes moderate charge transfer from VO2 to MnO2 layers in both perovskite and Ruddlesden-Popper based superlattices, leading to hole doping of the VO2 layer and electron doping of the MnO2 layer. Comparison of the perovskite and Ruddlesden-Popper based h…
The structure and dehydration mechanism of the proton conducting oxide Ba$_{2}$In$_{2}$O$_{5}$(H$_{2}$O)$_{x}$ are investigated by means of variable temperature Raman spectroscopy together with inelastic neutron scattering. At room temperature, Ba$_{2}$In$_{2}$O$_{5}$(H$_{2}$O)$_{x}$ is found to be fully hydrated ($x=1$) and to have a perovskite-like structure, which dehydrates gradually with increasing temperature and at around 600 $^{\circ}$C the material is essentially completely dehydrated ($x=0$). The dehydrated material exhibits a brownmillerite structure, which is featured by alternatin…
The misfit oxide, Bi$_{2}$Ba$_{1.3}$K$_{0.6}$Co$_{2.1}$O$_{y}$, made of alternating rocksalt-structured [BiO/BaO] layers and hexagonal CoO$_{2}$ layers, was studied by angle-resolved photoemission spectroscopy. Detailed electronic structure of such a highly strained oxide interfaces is revealed for the first time. We found that under the two incommensurate crystal fields, electrons are confined within individual sides of the interface, and scattered by umklapp scattering of the crystal field from the other side. In addition, the high strain on the rocksalt layer raises its chemical potential a…
Some oxygen defective metal oxides, such as cerium and bismuth oxides, have recently shown exceptional electrostrictive properties that are even superior to the best performing lead-based electrostrictors, e.g. lead-magnesium-niobates (PMN). Compared to piezoelectric ceramics, electromechanical mechanisms of such materials do not depend on crystalline symmetry, but on the concentration of oxygen vacancy in the lattice. In this work, we investigate for the first time the role of oxygen defect configuration on the electro-chemo-mechanical properties. This is achieved by tuning the oxygen defects…
Domain-wall-to-domain interconversion in a polar conducting oxide
University of Groningen（格罗宁根大学）；Zernike Institute for Advanced Materials, University of Groningen（格罗宁根大学泽尔尼克先进材料研究所）；Groningen Cognitive Systems and Materials Center (CogniGron), University of Groningen（格罗宁根认知系统与材料中心）；Faculty of Physics, University of Duisburg-Essen（杜伊斯堡-埃森大学物理学院）；Research Center Future Energy Materials and Systems (RC FEMS), Research Alliance Ruhr（鲁尔研究联盟未来能源材料与系统研究中心）；Institut des Molécules et Matériaux du Mans, UMR 6283 CNRS, Le Mans Université（勒芒大学CNRS 6283分子与材料研究所）；The European Synchrotron Radiation Facility (ESRF)（欧洲同步辐射装置）；Theoretical Materials Physics, Q-MAT, University of Liège（列日大学Q-MAT理论物质物理）
Metal oxide thin-film transistors are fast becoming a ubiquitous technology for application in driving backplanes of organic light-emitting diode displays. Currently all commercial products rely on metal oxides processed via physical vapor deposition methods. Transition to simpler, higher throughput manufacturing methods such as solution-based processes, are currently been explored as cost-effective alternatives. However, developing printable oxide transistors with high carrier mobility and bias-stable operation has proved challenging. Here we show that hybrid multilayer channels composed of a…
A unique type of frustrated lattice is found in two A-site ordered spinel oxides, LiGaCr4O8 and LiInCr4O8. Because of the large size mismatch between Li+ and Ga3+/In3+ ions at the A site, the pyrochlore lattice, made up of Cr3+ ions carrying spin 3/2, becomes an alternating array of small and large tetrahedra, i.e., a "breathing" pyrochlore lattice. We introduce a parameter, the breathing factor Bf, which quantifies the degree of frustration in the pyrochlore lattice: Bf is defined as J'/J, where J' and J are nearest-neighbor magnetic interactions in the large and small tetrahedra, respectivel…
Rashba-like spin-orbit interaction at oxide heterostructures emerges as a much sought-after feature in the context of oxide spintronics and spin-orbitronics. KTaO$_3$ (KTO) is one of the best substrates available for the purpose, owing to its strong spin-orbit interaction and alternating $+1|-1$ charged layers along the (001) direction. Employing first-principles calculations within density functional theory (DFT) and proposing a possible electrostatic model for charge transfer to the surfaces of KTO slabs, we comprehensively analyze Rashba-like spin-orbit interaction with the help of three-di…
Current approaches for electric power generation from nanoscale conducting or semi-conducting layers in contact with moving aqueous droplets are promising as they show efficiencies of around 30 percent, yet, even the most successful ones pose challenges regarding fabrication and scaling. Here, we report stable, all-inorganic single-element structures synthesized in a single step that generate electrical current when alternating salinity gradients flow along its surface in a liquid flow cell. 10 nm to 30 nm thin nanolayers of iron, vanadium, or nickel produce several tens of mV and several micr…
Among the strategies to fight cancer, multi-therapeutic approaches are considered as a wise choice to put in place multiple weapons to suppress tumors. In this work, to combine chemotherapeutic effects to magnetic hyperthermia when using biocompatible scaffolds, we have established an electrospinning method to produce nanofibers of polycaprolactone loaded with magnetic nanoparticles as heat mediators to be selectively activated under alternating magnetic field and doxorubicin as a chemotherapeutic drug. Production of the fibers was investigated with iron oxide nanoparticles of peculiar cubic s…
The concept of spin-orbital entanglement on superexchange bonds in transition metal oxides is introduced and explained on several examples. It is shown that spin-orbital entanglement in superexchange models destabilizes the long-range (spin and orbital) order and may lead either to a disordered spin-liquid state or to novel phases at low temperature which arise from strongly frustrated interactions. Such novel ground states cannot be described within the conventionally used mean field theory which separates spin and orbital degrees of freedom. Even in cases where the ground states are disentan…
We report dynamical magnetotransport in a ferromagnetic metallic oxide, La0.7Sr0.3MnO3 using the ac impedance technique. The temperature dependence of the ac resistance(R) and the inductive reactance (X) of the complex impedance (Z = R+jX) under different dc bias magnetic fields (Hdc = 0-1 kOe) were studied for different frequencies f = 0.1 to 5 MHz of alternating current. The zero field R, which decreases smoothly around the Curie temperature TC for f = 100 kHz, transforms into a peak for f = 0.5-5 MHz. The peak decreases in amplitude, broadens and shifts downward in temperature as the bias f…
Polycrystalline samples of Sr2Mn2CuAs2O2, Sr2Mn3As2O2, and Sr2Zn2MnAs2O2 were synthesized. Their temperature- and applied magnetic field-dependent structural, transport, thermal, and magnetic properties were characterized by means of x-ray and neutron diffraction, electrical resistivity rho, heat capacity, magnetization and magnetic susceptibility measurements. These compounds have a body-centered-tetragonal crystal structure (space group I4/mmm) that consists of MO2 (M = Zn and/or Mn) oxide layers similar to the CuO2 layers in high superconducting transition temperature Tc cuprate superconduc…
In this work, the capability of primary, monocyte-derived dendritic cells (DCs) to uptake iron oxide magnetic nanoparticles (MNPs) is assessed and a strategy to induce selective cell death in these MNP-loaded DCs using external alternating magnetic fields (AMFs) is reported. No significant decrease in the cell viability of MNP-loaded DCs, compared to the control samples, was observed after five days of culture. The amount of MNPs incorporated into the cytoplasm was measured by magnetometry, which confirmed that 1 to 5 pg of the particles were uploaded per cell. The intracellular distribution o…
Magnetic particle hyperthermia, in which colloidal nanostructures are exposed to an alternating magnetic field, is a promising approach to cancer therapy. Unfortunately, the clinical efficacy of hyperthermia has not yet been optimized. Consequently, routes to improve magnetic particle hyperthermia such as designing hybrid structures comprised from different phase materials are actively pursued. Here we demonstrate enhanced hyperthermia efficiency in relative large spherical Fe/Fe-oxide core/shell nanoparticles through the manipulation of interactions between the core and shell phases. Experime…
The spinel oxides LiGaCr4O8 and LiInCr4O8 contain size-alternating pyrochlore lattices of spin-3/2 Cr3+ tetrahedra with different magnitudes of alternation. We show here that the solid solutions LiGa1-xInxCr4O8 between these two 'breathing' pyrochlore compounds display (i) rapid suppression of magnetic and structural transitions upon doping the end members, (ii) spin-glass-like freezing above 2 K in the range 0.1 $\lesssim$ x $\lesssim$ 0.6, and (iii) apparent spin-gap behavior for x $\gtrsim$ 0.7. Furthermore, no transitions are observed above 2 K at x ~ 0.9, where magnetic susceptibility rem…
Magnetic mineral inclusions, as iron oxides or sulfides, occur quite rarely in natural diamonds. Nonetheless, they represent a key tool not only to unveil the conditions of formation of host diamonds, but also to get hints about the paleointensity of the geomagnetic field present at times of the Earth's history otherwise not accessible. This possibility is related to their capability to carry a remanent magnetization dependent on their magnetic history. However, comprehensive experimental studies on magnetic inclusions in diamonds have been rarely reported so far. Here we exploit X-ray diffrac…
Alternating layers of granular Iron (Fe) and Titanium dioxide (TiO$_{2-δ}$) were deposited on (100) Lanthanum aluminate (LaAlO$_3$) substrates in low oxygen chamber pressure using a controlled pulsed laser ablation deposition technique. The total thickness of the film was about 200 nm. The films show ferromagnetic behavior for temperatures ranging from 4 to $400 ^oK$. The layered film structure was characterized as p-type magnetic semiconductor at $300 ^oK$ with a carrier density of the order of $10^{20} /cm^3$. The undoped pure TiO$_{2-δ}$ film was characterized as an n-type magnetic semicond…
