First-principles study on the magnetism in ZnS-based diluted magnetic semiconductors

The electronic and magnetic properties of wurtzite ZnS semiconductor doped with transition metal (Cr, Mn, Fe, Co, and Ni) atoms are studied by using the first-principle’s method in this paper. The ZnS bulk materials doped with Cr, Fe, and Ni are determined to be half-metallic, while those doped with Mn and Co impurities are found to be semiconducting. These doped transition metal ions have long range interactions mediated through the induced magnetic moments in anions and cations of host semiconductors. These doped ZnS-based diluted magnetic semiconductors seem to be good candidates for the future spintronic applications.     

Spin glass behavior in the new amorphous alloys M2SnTe4 (M=Cr,Mn, Fe)

The amorphous alloys M₂SnTe₄ (M=Cr, Mn, Fe) are prepared by a new method involving the oxidation of main group polyanions (Zintl anions) by transition metal cations in solution at or below room temperature. The M₂SnTe₄ materials undergo a transition to a spin glass state at 12 K ? T_f ? 20 K and were characterized by dc magnetization, ⁵⁷Fe and ¹¹⁹Sn Mossbauer and x-ray diffraction measurements as well as the behavior of the remanent magnetization.     

Surface cation ratios of binary oxide solid solutions

The cation ratios in the (100) surface of cubic oxides of bulk composition A_0.99B_0.01O, in which A and B are divalent cations were calculated using a monolayer model. Divalent cations including Ni, Co, Mn, Fe and Mg were studied. The cations were represented by a shell model, and the surface compositions were calculated by minimizing the total Gibbs free energy of the solid. The bulk energy change on surface segregation was evaluated by minimizing the energy change on substituting one bulk cation by another in an infinitely dilute solid solution and the surface energy was evaluated by a statistical method to accommodate the possibility that both cations can exist at non-negligible densities at the surface. The bulk energy change on surface segregation was found to be dominant in most cases. The surface energy change, the entropy change, and the change in crystal field stabilization energy were all secondary. Thus, except when the difference in ionic radii is very small, the larger cation is always more preferred at the surface. This conclusion appears to be in agreement with available experimental data.     

Synthesis of nanoporous TiO2 materials using a doubly surfactant system and applying them as useful adsorbents

Hydrothermal and non-hydrothermal nanoporous TiO₂ materials were synthesized via a doubly surfactant route by using cationic cetyltrimethylammonium bromide and anionic sodium dodecyl sulfate surfactants as the molecular template/structure directing agent. Hydrothermal treatment was performed for comparison. The bulk chemical and phase compositions, crystalline structures, particle morphologies, thermal stabilities and surface texturing were determined by means of X-ray powder analysis, SEM and N₂ sorptiometry. The nanoporous TiO₂ materials were found to have a spherical morphology with a diameter range of 50–200 nm and a high surface area (390 m² g^?1). Hydrothermal and non-hydrothermal nanoporous TiO₂ materials were applied for adsorption of heavy metal cations and the toxic organic compound, copper phthalocyanine, from water for evaluation of their adsorption properties. Both nanoporous TiO₂ materials were found to have similar adsorption capacities toward heavy metal cations and CuPc. Both hydrothermal and non-hydrothermal TiO₂ nanoporous materials were found to have very good potential for application as a new adsorbent especially for adsorbing heavy metal cations from wastewaters.     

Organometal Halide Perovskites: Bulk Low‐Dimension Materials and Nanoparticles

Organometal halide perovskites (hybrid perovskites) contain an anionic metal–halogen‐semiconducting framework and charge‐compensating organic cations. As hybrid materials, they combine useful properties of both organic and inorganic materials, such as plastic mechanical properties and good electronic mobility related to organic and inorganic material, respectively. They are prepared from abundant and low cost starting compounds. The perovskite stoichiometry is associated with the dimensionality of its inorganic framework, which can vary from three to zero, 3D consisting of corner‐sharing MX₆ octahedra, and 0D consisting of isolated octahedra. Small‐sized organic cations can fit into the MX₆ octahedra of the 3D framework and in all dimensions organic cations surround the inorganic framework. Regarding the low dimensionality in the material, this refers to at least one of its dimensions being shorter than approximately 100 nanometers. These materials should be considered as genuine nanomaterials or as bulk materials depending on whether they have three or less than three dimensions on the nanoscale, respectively. In principle, hybrid perovskite nanoparticles can be prepared with different shapes and with inorganic framework dimensionalities varying from 0D to 3D, and this also applies to the bulk material. This report is mainly focused on the unique properties of organometal halide perovskite nanoparticles.     

软 X射线共振非弹性光散射及其应用

软 X射线共振非弹性光散射是近年来随着高亮度第三代同步辐射出现而发展起来的光散射光谱技术 ,可以用于对多原子构成的分子、凝聚态物质进行位置选择的价电子态结构的研究。与 X射线光电子能谱 ( XPS)或紫外光电子能谱 ( UPS)相比 ,这一光谱方法由于测量样品激发后产生的散射 X射线 ,因而不仅可以获得表面的原子分子信息 ,而且可以用于研究样品体内或掩埋薄层的原子分子。同时这一方法的共振特性使得其可以进行灵敏的元素选择测量。本文将介绍这一光散射光谱技术及其在原子分子物理、表面物理及凝聚态物理中的应用     

First study of manganese diffusion in Cr2O3 polycrystals and thin films by SIMS

Chromia layers are formed on many industrial alloys and act as a protective barrier against the corrosion of the materials by limiting the diffusion of oxygen and cations. Most of these alloys contain manganese as an impurity, and manganese oxides are often found at the outer surface of the oxide films. In order to clarify the oxidation mechanism and to check if chromia acts as a barrier, manganese diffusion in chromia was studied in both polycrystals and oxide films formed by oxidation of Ni–30Cr alloy in the temperature range 700–1100°C at an oxygen pressure of 10^?4?atm. After deposition of Mn on the chromia surface and a diffusing treatment, the manganese penetration profiles were established by secondary ion mass spectrometry. In all cases, the diffusion profiles showed two domains. For the first domain, using the solution of Fick's law for diffusion from a thick film into a semi-infinite medium, bulk diffusion coefficients were determined. For the second domain, the Le Claire model allowed the grain boundary diffusion parameter (αD _gbδ) to be obtained. Manganese diffusion does not vary significantly according to the nature and microstructure of chromia. The activation energy of grain boundary diffusion is not far from that obtained for bulk diffusion, probably on account of segregation phenomena. Manganese diffusion was compared to cationic self-diffusion and iron diffusion, and related to the protective character of chromia.     

Levels of mineral nutrients in fresh- and frozen bulk hydrated biological specimens: A comparison of EDS data collected in the environmental SEM and a conventional cryo-SEM

Energy-dispersive X-ray microanalysis (EDS) was compared in fresh- and frozen bulk hydrated tissues using the Environmental SEM (ESEM) and conventional cryo-SEM, respectively. Analyses of globoid inclusions of Eucalyptus calophylla seed from two soil types demontsrated that higher levels of cations (K, Ca, Mg, Al, Fe, Mn, Cu, Zn) occurred in seeds from soils containing higher levels of Al, while EDS-detectable levels of S and P were dependent upon the techniques utilised. Cumulative changes in ESEM-EDS-detectable levels of S and P were characterised by collecting cumulative spectra from nutrient standards and compared with those for K. Progressive increases in K occurred and were consistent with an enriching effect. Levels of S and P increased during early analysis (40–60 sec live time) and decreased thereafter. The semi-conductive nature of biological samples, the loss of anions and gain of cations from the net negatively-charged electron interaction volume contributed to an electrochemical bias. These local modifications in fluid chemistry were reversible. Dehydration effects also occurred in stable, “wet‘ samples. These differences indicated that EDS in ESEM may be limited to cations rather than anions, and that changes in fluid electrochemistry and dehydration may affect the level and distribution of elements.     

Growth of Bi-Sb alloy thin films and their characterization by TEM, PIXE and RBS

Polycrystalline bulk materials of Bi₉₃Sb₇ Bi₈₈Sb₁₂, Bi₈₅Sb₁₅ and Bi₈₀Sb₂₀ were synthesized by melt-quench technique starting from the stoichiometric mixture of constituent elements. The phase purity and compositional uniformity of bulk materials were investigated using powder X-ray diffraction (XRD) and proton induced X-ray emission (PIXE) experiments. The single phase formation and the compositional analysis of thin films were confirmed by transmission electron microscopy (TEM) and Rutherford backscattering spectroscopy (RBS). X-ray diffraction studies confirmed the phase homogeneity of the materials. Atomic concentration ratio of constituent elements (Bi and Sb) determined by PIXE and RBS revealed that near-stoichiometric composition is nearly the same in the bulk as well as in thin film forms.     

Antiferromagnetic coupling driven by bond length contraction near the Ga1-xMnxN film surface

Using first principles calculations based on gradient corrected density functional theory we show that Mn atoms, which couple ferromagnetically in bulk Ga1-xMnxN, couple antiferromagnetically on its surface. This change in magnetic behavior is brought about by a contraction of the Mn-Mn and Mn-N bond lengths, which is significantly greater on the surface than in the bulk. The present study provides new insight to the numerous conflicting experimental observations in Mn doped GaN systems.     

Luminescence of Mn ions in Tb3Al5O12 garnet

The paper is dedicated to investigation of the Mn²⁺ luminescence in Tb₃Al₅O₁₂ (TbAG) garnet, as well as the processes of excitation energy transfer between host cations (Tb³⁺ ions) and activators (Mn²⁺ and Mn²⁺-Ce³⁺ pair ions) in single crystalline films of TbAG:Mn and TbAG:Mn,Ce garnets which can be considered as promising luminescent materials for conversion of LED's radiation. Due to the effective energy transfer between TbAG host and activator, Mn²⁺ ions in TbAG possess the bright orange luminescence in the bands peaked at 595 nm with a lifetime of 0.64 ms which are caused by the ⁴T₁→⁶A₁ radiative transitions. The simultaneous process of energy transfer is realized in TbAG:Mn,Ce: (i) from Tb³⁺ to Mn²⁺ ions; (ii) from Tb³⁺ cations to Ce³⁺ ions and then partly to Mn²⁺ ions through Tb³⁺ ion sublattice and Ce-Mn dipole-dipole interaction.     

Investigating lanthanide dopant distributions in Yttrium Aluminum Garnet (YAG) using solid state paramagnetic NMR

This paper demonstrates the approach of using paramagnetic effects observed in NMR spectra to investigate the distribution of lanthanide dopant cations in YAG (yttrium aluminum garnet, Y₃Al₅O₁₂) optical materials, as a complimentary technique to optical spectroscopy and other standard methods of characterization. We investigate the effects of Ce³⁺, Nd³⁺, Yb³⁺, Tm³⁺, and Tm³⁺-Cr³⁺ on ²⁷Al and ⁸⁹Y NMR spectra. We note shifted resonances for both AlO₄ and AlO₆ sites. In some cases, multiple shifted peaks are observable, and some of these can be empirically assigned to dopant cations in known configurations to the observed nuclides. In many cases, AlO₆ peaks shifted by more than one magnetic neighbor can be detected. In general, we observe that the measured intensities of shifted resonances, when spinning sidebands are included, are consistent with predictions from models with dopant cations that are randomly distributed throughout the lattice. In at least one set of ²⁷Al spectra, we identify two sub-peaks possibly resulting from two paramagnetic cations with magnetically coupled spin states neighboring the observed nucleus. We identify systematic changes in the spectra related to known parameters describing the magnetic effects of lanthanide cations, such as larger shift distances when the expectation value of electron spins is greater. We lastly comment on the promise of this technique in future analyses of laser and other crystalline oxide materials.     

Spectral Properties and Thermal Quenching of Mn4+ Luminescence in Silicate Garnet Hosts CaY2MgMAlSi2O12 (M = Al,Ga, Sc)

Physics of the Solid State - Multi-component silicate garnet ceramics CaY2MgMAlSi2O12 comprising different cations M = Al, Ga or Sc in octahedral sites doped with Mn4+ ions have been synthesized...     

Growth and properties of self‐catalyzed (In,Mn)As nanowires

Mn‐assisted molecular beam epitaxy is used for the growth of (In,Mn)As nanowires (NWs) on GaAs(111)B. The transmission electron microscopy measurements revealed that despite the relatively high growth temperature regime this technique can be used to obtain (In,Mn)As NWs with high crystalline quality without any crystal defects, such as dislocations, stacking faults or precipitates inside the investigated NWs or on their side‐walls, although the growth processes of NWs were accompanied by the formation of MnAs precipitates between the NWs at the interface of the wetting layer. The results obtained are of importance for the realization of new spintronic nanostructured materials. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Synthesis of novel transition metal nitrides IrN2 and OsN2

Two new transition metal nitrides, IrN2 and OsN2, were synthesized at high pressures and temperatures using laser-heated diamond-anvil cell techniques. Synchrotron x-ray diffraction was used to determine the structures of novel nitrides and the equations of states of both the parent metals as well as the newly synthesized materials. The compounds have bulk moduli comparable with those of the traditional superhard materials. For IrN2, the measured bulk modulus [K0 = 428(12) GPa] is second only to that of diamond (K0 = 440 GPa). Ab initio calculations indicate that both compounds have a metal:nitrogen stoichiometry of 1:2 and that nitrogen intercalates in the lattice of the parent metal in the form of single-bonded N-N units.     

Non-Destructive Characterization of Engineering Materials Using High-Energy X-rays at the Advanced Photon Source

Engineering materials are typically made from transition metals and exist in polycrystalline form. The ability to characterize this class of materials, both ex situ and in situ, is particularly important as the demand for efficient, environment-friendly machines rises and the need to understand the material response at a smaller length scale increases. In the past decade, the use of high-energy synchrotron X-rays to characterize bulk engineering materials has increased significantly, with several high-energy beamlines and new characterization techniques coming online around the world.     

Two-dimensional triple-quantum Na MAS NMR spectroscopy of sodium cations in dehydrated zeolites

Two-dimensional triple-quantum (2D-3Q) ²³Na MAS NMR spectroscopy has been applied for the investigation of sodium cations in dehydrated zeolites NaY, NaEMT, NaZSM-5 and NaMOR. The experiments have shown that the new 2D-3Q technique allows the determination of the isotropic chemical shifts and quadrupolar couplings of sodium cations with SOQE (second-order quadrupolar effect) parameters of up to ca. 4 MHz. In the present work, SOQE parameters of 1.0–1.2 MHz were found for sodium cations located at positions SI in the hexagonal prisms of dehydrated zeolites NaY and NaEMT. The sodium cations located in the 10-ring and 12-ring channels of dehydrated zeolites NaZSM-5 and NaMOR, respectively, are characterized by a SOQE parameter of 2.0 MHz while a value of 3.1 MHz was determined for sodium cations in the sidepockets of the channels in dehydrated NaMOR.     

Identification of different electron screening behavior between the bulk and surface of (Ga,Mn)As

We report x-ray photoemission spectroscopy results on (Ga,Mn)As films as a function of both temperature and Mn doping. Analysis of Mn 2p core level spectra reveals the presence of a distinct electronic screening channel in the bulk, hitherto undetected in more surface sensitive analysis. Comparison with model calculations identifies the character of the Mn 3d electronic states and clarifies the role, and the difference between surface and bulk, of hybridization in mediating the ferromagnetic coupling in (Ga,Mn)As.     

Study of magnetic and optical properties of Zn_(1-x)TM_xTe(TM = Mn,Fe,Co,Ni) diluted magnetic semiconductors:First principle approach

We present structural,magnetic and optical characteristics of Zn_(1-x)TM_xTe(TM = Mn,Fe,Co,Ni and x = 6.25%),calculated through Wien2 k code,by using full potential linearized augmented plane wave(FP-LAPW) technique.The optimization of the crystal structures have been done to compare the ferromagnetic(FM) and antiferromagnetic(AFM) ground state energies,to elucidate the ferromagnetic phase stability,which further has been verified through the formation and cohesive energies.Moreover,the estimated Curie temperatures T_c have demonstrated above room temperature ferromagnetism(RTFM) in Zn_(1-x)TM_xTe(TM =Mn,Fe,Co,Ni and x= 6.25%).The calculated electronic properties have depicted that Mn- and Co-doped ZnTe behave as ferromagnetic semiconductors,while half-metallic ferromagnetic behaviors are observed in Fe- and Ni-doped ZnTe.The presence of ferromagnetism is also demonstrated to be due to both the p-d and s-d hybridizations between the host lattice cations and TM impurities.The calculated band gaps and static real dielectric constants have been observed to vary according to Penn's model.The evaluated band gaps lie in near visible and ultraviolet regions,which make these materials suitable for various important device applications in optoelectronic and spintronic.     

EELS analysis of cation valence states and oxygen vacancies in magnetic oxides

Transition metal oxides are a class of materials that are vitally important for developing new materials with functionality and smartness. The unique properties of these materials are related to the presence of elements with mixed valences of transition elements. Electron energy-loss spectroscopy (EELS) in the transmission electron microscope is a powerful technique for measuring the valences of some transition metal elements of practical importance. This paper reports our current progress in applying EELS for quantitative determination of Mn and Co valences in magnetic oxides, including valence state transition, quantification of oxygen vacancies, refinement of crystal structures, and identification of the structure of nanoparticles.