X-ray diffraction with synchrotron radiation has been used for the first time to study chemical interaction in the FeO-ZnO system at 4.8 GPa and temperatures up to 1300 K. Above 750 K, the chemical reaction between FeO and ZnO has been observed that resulted in the formation of rock salt (rs) Fe1-xZnxO solid solutions (0.3 \leq x \leq 0.85). The lattice parameters of these solid solutions have been in situ measured as a function of temperature under pressure, and corresponding thermal expansion coefficients have been calculated.
Low-temperature heat capacities (Cp) of nanostructured rock salt (rs-ZnO) and wurtzite (w-ZnO) polymorphs of zinc oxide were measured in the 2-315 K temperature range. No significant influence of nanostructuring on Cp of w-ZnO has been observed. The measured Cp of rock salt ZnO is lower than that of wurtzite ZnO below 100 K and is higher above this temperature. Using available thermodynamic data, we established that the equilibrium pressure between nanocrystalline w-ZnO and rs-ZnO is close to 4.6 GPa at 300 K (half as much as the onset pressure of direct phase transformation) and slightly chan…
Metastable LiMeO2-ZnO (Me = Fe3+, Ti3+) solid solutions with rock salt crystal structure have been synthesized by solid state reaction of ZnO with LiMeO2 complex oxides at 7.7 GPa and 1350-1450 K. Structure, phase composition, thermal stability and thermal expansion of the recovered samples have been studied by X-ray diffraction with synchrotron radiation. At ambient pressure rock salt LiMeO2-ZnO solid solutions are kinetically stable up to 670-800 K depending on the composition.
The enthalpies of dissolution of metastable rock salt and thermodynamically stable wurtzite polymorphs of zinc oxide in aqueous H2SO4 have been measured in direct calorimetric experiments at 303 K and 0.1 MPa and the obtained results enabled determination of the standard enthalpy of the rock salt-to-wurtzite phase transition in ZnO, ΔtrH = -11.7+/-0.3 kJ/mol.
Lattice parameter of metastable high-pressure phase of zinc oxide, rock-salt ZnO was measured in the 10-300 K temperature range using synchrotron X-ray powder diffraction. No phase transition was observed down to 10 K. The lattice parameter of rock-salt ZnO was found to increase from 4.266 Å in the 10-80 K range up to 4.2752(3) Å at 298 K, while the volume thermal expansion coefficient increases from slight negative values below 40 K up to 4.77\times10^-5 K^-1 at 298 K.
Electrical conductivity of FeO was measured up to 141 GPa and 2480 K in a laserheated diamond-anvil cell. The results show that rock-salt (B1) type structured FeO metallizes at around 70 GPa and 1900 K without any structural phase transition. We computed fully self-consistently the electronic structure and the electrical conductivity of B1 FeO as a function of pressure and temperature, and found that although insulating as expected at ambient condition, B1 FeO metallizes at high temperatures, consistent with experiments. The observed metallization is related to spin crossover.
X-ray diffraction with synchrotron radiation has been used for the first time to study chemical interaction in the MnO-ZnO system at 4.8 GPa and temperatures up to 1600 K. Above 750 K, the chemical reaction between MnO and ZnO has been observed that resulted in the formation of rock salt (rs) Mn1-xZnxO solid solutions (0.3 \leq x \leq 0.7). The lattice parameters of these solid solutions have been in situ measured at high pressure as a function of temperature, and corresponding thermal expansion coefficients have been calculated.
Very recently Leitner et al. [Thermochimica Acta 572 (2013) 1-5] have tried to extract the thermodynamic data of rock-salt ZnO from ab initio and experimental data available in the literature. In this Comment we show that neglecting (i) the strongly pronounced kinetic features of the pressure-induced phase transition in ZnO at room temperature and (ii) results of calorimetric measurements available in the literature [Russ. Chem. Bull. 59 (2010) 325-328] makes the proposed set of thermodynamic functions completely incorrect.
Series of metastable Me1-xZnxO solid solutions (Me = Ni2+, Co2+, Fe2+, Mn2+) with the rocksalt (rs) crystal structure have been synthesized from the binary oxides by quenching from 7.7 GPa and 1450-1650 K. Phase composition of the samples, as well as structural properties and stoichiometry of synthesized solid solutions have been studied by X-ray powder diffraction, both conventional and with synchrotron radiation. The widest (0.3 \leq x \leq 0.8) composition range of the existence of individual rock-salt solid solution has been established for the NiO-ZnO system. The bulk rs-Co1-xZnxO, rs-Fe1…
Despite decades of efforts, achieving $p$-type conductivity in the wide band gap ZnO in its ground-state wurtzite structure continues to be a challenge. Here we detail how $p$-type ZnO can be realized in the metastable, high-pressure rocksalt phase (also wide-gap) with Li as an external dopant. Using modern first-principles defect theory, we predict Li to dope the rocksalt phase $p$-type by preferentially substituting for Zn and introducing shallow acceptor levels. Formation of compensating donors like interstitial Li and/or hydrogen, ubiqutous in the wurtzite phase, is inhibited by the close-…
We fabricate fully epitaxial Fe/ZnO/MgO/Fe magnetic tunnel junctions (MTJs) with a bilayer tunnel barrier, in which ZnO has a metastable rock-salt crystal structure. We observe a high magnetoresistance ratio up to 96% at room temperature (RT) and find that these MTJs have asymmetric current-voltage characteristics, and their rectifying performances are largely dependent on the magnetization alignments of the Fe electrodes. Diode responsibilities at a zero-bias voltage ($β_{0}$), which is an important performance index for harvesting applications, are observed up to 1.3 A/W at RT in the antipar…
Preliminary results on the properties of transition-metal (Ti, V, Cr, Mn, Fe, Co, Ni) $δ$-doped ZnO are reported. Using \emph{ab-initio} electronic structure calculations the magnetic order is studied assuming both the cubic rock-salt and zinc-blende structures for ZnO. The ground state magnetic order is found to depend strongly on the transition-metal atom.
An ab initio pseudopotential method based on density functional theory, generalized gradient corrections to exchange and correlation, and projector-augmented waves is used to investigate structural, energetical, electronic and optical properties of MgO, ZnO, and CdO in rocksalt, cesium chloride, zinc blende, and wurtzite structure. In the case of MgO we also examine the nickel arsenide structure and a graphitic phase. The stability of the ground-state phases rocksalt (MgO, CdO) and wurtzite (ZnO) against hydrostatic pressure and biaxial strain is studied. We also present the band structures of…
We determine the equation of state of stoichiometric FeO employing the diffusion Monte Carlo method. The fermionic nodes are fixed to those of a wave function having the form of a single Slater determinant. The calculated ambient pressure properties (lattice constant, bulk modulus and cohesive energy) agree very well with available experimental data. At approximately 65 GPa, the lattice structure is found to change from rocksalt type (B1) to NiAs based (inverse B8).
By means of full-potential all-electron density-functional theory and many-body perturbation theory, we compute the band alignment at a prototypical hybrid inorganic/organic interface. The electronic properties of a model system built of poly(\emph{para}-phenylene) and \emph{rs}-ZnO are studied in two different geometries, employing several approaches of increasing sophistication. To this extent, we explore models for predicting the level alignment, which are based on the knowledge of the electronic structure of the individual constituents and are commonly used for semiconductor interfaces. Fo…
We present results of a density functional theory study of MnO in the wurtzite structure. Our motivation is provided by recent experiments reporting ferromagnetism in Mn-doped wurtzite structure ZnO. We find that wurtzite MnO a) is not strongly energetically disfavored as compared with the ground state rocksalt MnO, b) shows strong magnetostructural coupling and c) has a piezoelectric response that is larger than that of ZnO. These predictions augur well for the creation of ferromagnetic piezoelectric semiconductor based on Mn-doped ZnO.
We have studied the pressure-induced structural transition of ZnO nanocrystals using constant pressure molecular dynamics simulations for finite system. We have observed the transition from the fourfold coordination wurtzite to the sixfold coordination rocksalt structure, and the process of transition is strongly dependent on the morphology of the nanocrystals. It is found that the perfect faceted ZnO nanocrystals undergo wurtzite to rocksalt transition with a perfect fivefold h-MgO structure as the intermediate status. But for the faceted ones without perfect surface structure, as the number …
We study the ferromagnetism in the compound (Zn,Mn)O within the Haldane-Anderson impurity model by using the quantum Monte Carlo technique and the tight-binding approximation for determining the host band-structure and the impurity-host hybridization. This computational approach allows us to determine how the host crystal structure influences the impurity bound state, which plays an important role in the development of the ferromagnetic (FM) correlations between the impurities. We find that the FM correlations are strongly influenced by the crystal structure. In particular, in p-type (Zn,Mn)O,…
Using the hybrid exchange-correlation functional within the density-functional theory, we have systematically investigated the structural and electronic properties of MO (M = Be, Mg, Ca, Sr, Ba, Zn, Cd) in binary rocksalt (B1), zincblende (B3) and wurtzite (B4) phases, including the structural parameters, bulk moduli, band gaps and deformation potentials. Our results agree well with the experimental data and other theoretical results, and give a better understanding of the relationship between the geometric and electronic structure. After calculating the band alignment, we find that in both th…
Volume Collapse Without a Structural Transition in Shock-Compressed FeO
University of Oxford（牛津大学）；European XFEL（欧洲XFEL）；Technische Universität Dortmund（多特蒙德工业大学）；AWE（英国原子武器研究所）；Queen’s University Belfast（贝尔法斯特女王大学）；The University of Osaka（大阪大学）；University of Rochester（罗切斯特大学）
The electrical and structural characteristics of 50 nm zinc oxide (ZnO) metal-semiconductor-metal (MSM) ultraviolet (UV) photodetectors subjected to proton irradiation at different temperatures are reported and compared. We irradiated the devices with 200 keV protons to a fluence of 1016 cm-2. Examination of the X-ray diffraction (XRD) rocking curves indicates a strongly preferred (100) orientation for the grains of the as-deposited film, with decreases in crystal quality for all irradiated samples. In addition, peak shifts in XRD and Raman spectra of the control sample relative to well-known …
