Local chemical distribution and electronic structure of Ge1−xTx DMS single crystals (T=Cr,Mn, Fe)

The spatial concentration distribution and local electronic structure of ferromagnetic Ge_1−xT_x (T=Cr, Mn, Fe) DMS single crystals have been investigated by using scanning photoelectron microscopy (SPEM), X-ray absorption spectroscopy (XAS), and photoemission spectroscopy (PES). It is found that doped T ions in Ge_1−xT_x crystals are chemically phase-separated, suggesting that the observed ferromagnetism arises from the phase-separated T-rich phases in Ge_1−xT_x.     

Manganese silicide single crystal and films deposited on Si(1 1 1): A comparative spectroscopic study

A comparative experimental study is presented of the electronic properties of MnSi films grown on Si(1 1 1) and of MnSi single crystals, using X-ray absorption spectroscopy (XAS), and core level and valence band photoemission spectroscopy (PES). No significant differences in the electronic structure of the two systems can be found.Absorption measurements on the Mn 2p threshold show a mixed valence ground state, where the multiplet structure is washed out by the hybridisation of the Mn 3d states with the Si sp states. These results are also confirmed by photoemission (PE) spectra from the valence band and the Mn 3s, 3p and 2p core levels.Strong attention has been paid to the effect of contamination. The occurrence of multiplet effects in the absorption spectra indicates unambiguously the localisation of the Mn 3d electrons in Mn-O bonds, which strongly influences the electronic properties of these systems.     

The Electronic Properties of Nanomaterials Elucidated by Synchrotron Radiation–Based Spectroscopy

The use of synchrotron radiation–based spectroscopy to investigate electronic and bonding structures of nanostructured materials is reviewed with focuses on the X-ray absorption spectroscopy (XAS), valence-band photoemission spectroscopy (VB-PES), and scanning photoelectron microscopy (SPEM) measurements. This review addresses the current status of synchrotron radiation–based nanoscale characterization of carbon-based and ZnO nanomaterials. Current research works that are relevant to this rapidly evolving experimental area and implications in nanoscience and nanotechnology are emphasized.     

X ray absorption spectroscopy investigation of phase transition in Ge,GaAs and GaP

Abstract

The phase transitions of GaAs, GaP and Ge under pressure have been investigated by x-ray absorption spectroscopy (XAS). At the onset of the transition the Debye-Waller factor increases and the x-ray absorption near edge structure (XANES) is progressively modified. A mixing of the low and high pressure phase can be determined by XAS as well as amorphization of the sample on pressure release.     

基于XPS与XAS的稀磁半导体GaMnN电子结构研究

采用基于同步辐射技术的X射线光电子能谱(XPS)与X射线吸收谱(XAS)测试由金属有机化学气相沉积(MOCVD)技术制备的不同Mn掺杂浓度的稀磁半导体GaMnN薄膜的电子结构,探究Mn掺杂浓度对磁性原子Mn周围的局域环境和电子态等方面的影响,并阐述材料铁磁性变化的机理. XPS和XAS图谱分析表明：Mn²⁺和Mn³⁺共存于薄膜样品内,样品D中Mn²⁺占比高达70%-80%,N空位随Mn掺杂浓度增加而增多且N空位能够使空穴浓度降低,导致Mn 3d和N 2p轨道间的相互交换作用减小,从而减弱体系铁磁性.此外,Mn不同的掺杂浓度会影响GaMnN薄膜p-d耦合杂化能力的强弱,当掺Mn 1.8%时具有较强的p-d耦合杂化能力.     

Nature of the well screened state in hard X-ray Mn 2p core-level photoemission measurements of La1-xSrxMnO3 films

Using hard x-ray (HX; hnu=5.95 keV) synchrotron photoemission spectroscopy (PES), we study the intrinsic electronic structure of La(1-x)Sr(x)MnO(3) (LSMO) thin films. Comparison of Mn 2p core-levels with soft x-ray (SX; hnu approximately 1000 eV) PES shows a clear additional well-screened feature only in HX PES. Takeoff-angle dependent data indicate its bulk (> or =20 A) character. The doping and temperature dependence track the ferromagnetism and metallicity of the LSMO series. Cluster model calculations including charge transfer from doping-induced states show good agreement, confirming this picture of bulk properties reflected in Mn 2p core-levels using HX PES.     

Growth of manganese silicide films by co-deposition of Mn and Si on Si(1 1 1): A spectroscopic and morphological investigation

MnSi is a ferromagnetic compound with a Curie temperature of 29 K. Recent theoretical studies predict that 2 ML of MnSi epitaxially grown on Si show a ferromagnetic metallic ground state with spin polarization of about 50%. This would allow the development of spintronic devices based on the injection of spin-polarized current from a ferromagnetic metal into a semiconductor.In this context the possibility of growing in situ MnSi on the Si(1 1 1) surface has been explored. Thermal reaction, crystalline structure and electronic properties of the grown films have been studied in situ by photoemission spectroscopy (PES), X-ray absorption spectroscopy (XAS), and low energy electron diffraction (LEED). Depositing a thin film of Mn on Si(1 1 1) the formation of ordered islands (with dimensions dependent on the amount of deposited Mn) is driven by annealing at selected temperatures, as already observed. Our preliminary studies show that by simultaneously depositing Mn and Si in 1:1 stoichiometry on Si(1 1 1) a large improvement in the homogeneity of the MnSi films is achieved.     

Thermal phase transition of RbMnFe(CN)6 observed by X-ray emission and absorption spectroscopy

The thermal phase transition of RbMnFe(CN)₆ has been observed by Mn and Fe 3p-1s X-ray emission spectroscopy (XES) and 1s X-ray absorption spectroscopy (XAS). The thermal variations of the spin states and the valences of Mn and Fe were determined to be Mn²⁺(S=5/2)-NC-Fe³⁺(S=1/2) for the high-temperature (HT) phase and Mn³⁺(S=2)-NC-Fe²⁺(S=0) for the low-temperature (LT) phase. These transitions are thus caused by charge transfer between Mn and Fe. The temperature dependences of Mn and Fe 3p-1s XES and 1s XAS were observed as the composition of the spectra of the HT and LT phases. The ratios of the HT component in each spectrum show good agreement with the thermal transition curves observed with magnetic susceptibility measurements.     

In situ photoemission study of the room temperature ferromagnet ZnGeP2:Mn

The chemical states of the ZnGeP(2):Mn interface which shows ferromagnetism above room temperature have been studied by photoemission spectroscopy. Mn deposition on the ZnGeP2 substrate heated to 400 degrees C induced Mn substitution for Zn and then the formation of metallic Mn-Ge-P compounds. Depth profile studies have shown that Mn 3d electrons changed their character from itinerant to localized along the depth, and in the deep region, dilute divalent Mn species (<5% Mn) was observed with a coexisting metallic Fermi edge of non-Mn 3d character. The possibility of hole doping through Mn substitution for Ge and/or Zn vacancy is discussed.     

Cd3Al2Ge3O12:Mn2+锗酸盐石榴石光谱性质

本文报道室温下Cd₃Al₂Ge₃O₁₂:Mn²⁺(简称CAGG:Mn²⁺)锗酸盐石榴石的漫反射光谱、激发和发射光谱.在UV光激发下,在CAGG中Mn²⁺离子发射强黄光,这是基质到Mn²⁺离子无辐射能量传递的结果.Mn²⁺的黄发射带是由一个弱的红带和一个强的绿带所组成.讨论了这两个Mn²⁺发射带的起因.     

金属间化合物DyMn_2Ge_2的自发磁相变和场诱导的磁相变

在 10— 80 0K的温度范围内用X射线衍射方法测量了DyMn2 Ge2 化合物的晶格常数与温度的变化关系 ,观察到高温时DyMn2 Ge2 由顺磁状态到反铁磁状态的自发磁相变伴随着晶格常数a的负的磁弹性异常现象 .在4 2K— 2 0 0K的温度范围内测量了DyMn2 Ge2 的交流磁化率 .在交换相互作用的分子场模型近似下 ,从理论上分析讨论了DyMn2 Ge2 的低温自发磁相变和场诱导的磁相变 .计算了DyMn2 Ge2 单晶的磁化强度与温度的变化关系以及不同温度下外磁场沿晶轴c方向时的磁化曲线 .理论分析和计算结果表明 ,温度低于 33K时在DyMn2 Ge2 中观察到的场诱导的一级磁相变为由亚铁磁状态 (Fi)到中间态 (IS)相变 .     

Ultrathin ZrO2 films on Si-rich SiC(0 0 0 1)-(3 × 3): Growth and thermal stability

The growth and thermal stability of ultrathin ZrO₂ films on the Si-rich SiC(0 0 0 1)-(3 × 3) surface have been explored using photoelectron spectroscopy (PES) and X-ray absorption spectroscopy (XAS). The films were grown in situ by chemical vapor deposition using the zirconium tetra tert-butoxide (ZTB) precursor. The O 1s XAS results show that growth at 400 °C yields tetragonal ZrO₂. An interface is formed between the ZrO₂ film and the SiC substrate. The interface contains Si in several chemically different states. This gives evidence for an interface that is much more complex than that formed upon oxidation with O₂. Si in a 4+ oxidation state is detected in the near surface region. This shows that intermixing of SiO₂ and ZrO₂ occurs, possibly under the formation of silicate. The alignment of the ZrO₂ and SiC band edges is discussed based on core level and valence PES spectra. Subsequent annealing of a deposited film was performed in order to study the thermal stability of the system. Annealing to 800 °C does not lead to decomposition of the tetragonal ZrO₂ (t-ZrO₂) but changes are observed within the interface region. After annealing to 1000 °C a laterally heterogeneous layer has formed. The decomposition of the film leads to regions with t-ZrO₂ remnants, metallic Zr silicide and Si aggregates.     

X-ray photoelectron and auger spectroscopy analysis of Ge:Mn-based magnetic semiconductor layers

Thin (～60 nm) germanium layers supersaturated with a manganese impurity of 10–16 at % have been studied by x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The layers have been fabricated by pulsed laser deposition onto a semi-insulating single-crystal GaAs substrate. The results of XPS analysis of the Ge:Mn layers reveal a change in the line shape of germanium and manganese (2p) in the surface region compared to deeper layers, which indicates a transition from the oxidized form of the base material (Ge²⁺ and Ge¹⁺) and impurity (Mn²⁺) near the surface to the unoxidized state of germanium (Ge ⁰) and manganese (Mn⁰) in the interior of the layer. The XPS spectra of the valence electrons of the Ge:Mn structure indicate that the density of states in the valence band of the ferromagnetic Ge:Mn structures is caused not only by mechanical mixing of germanium and manganese. The composition of heterogeneous inclusions in Ge:Mn films has been studied using scanning Auger microscopy.     

Cs adsorption on a polar NbC(111) surface: photoemission and auger electron spectroscopy studies

The Cs adsorption process on a NbC(111) surface has been studied with core-level photoemission spectroscopy (PES) and Auger electron spectroscopy (AES). Coverage-dependent Cs 4d core-level PES shows that the polarization-depolarization transition of the Cs overlayer occurs in the coverage region of 0.5 ≤ θ ≤ 0.8 ML where the work function shows a minimum value. The charge transfer in the initial stage of adsorption is investigated using valence-related AES, and it is found that the transfer of the Cs 6s charge to the substrate occurs in the polarized phase.     

Coordination changes in crystalline and vitreous GeO2

Abstract

High pressure x ray absorption spectroscopy (XAS) has been performed up to 29 GPa on crystalline and amorphous GeO₂. The modification of the x ray absorption near edge structure (XANES) as well as the variation of the Ge-O distance, indicate that the coordination of Ge changes from 4 to 6 above 6.5 GPa. The transition is confirmed by Raman spectroscopy.     

Electronic Structure And Magnetism of Novel Diluted Magnetic Semiconductors CdGeP 2 : Mn and ZnGeP 2 : Mn

Chalcopyrite II-IV-V 2 semiconductors CdGeP 2 : Mn and ZnGeP 2 : Mn are new types of diluted magnetic semiconductors (DMSs). Since their ferromagnetic Curie temperatures are much higher than room temperature, these DMSs are good candidates for materials to be used in spintronics devices. Their electronic and magnetic structures have been investigated using the first-principles calculations based on the Korringa-Kohn-Rostoker coherent-potential-approximation and local-density-approximation (KKR-CPA-LDA) methods. When Cd or Zn atoms are substituted by Mn atoms, the ground state magnetic structure is spinglass-like. On the other hand, if Mn atoms substitute Ge atoms, the system becomes ferromagnetic through the double-exchange mechanism. However, the calculation of the formation energies shows that this system is not energetically favorable. Instead, the system with vacancies (Cd, Vc, Mn)GeP 2 or a non-stoichiometric (Cd, Ge, Mn)GeP 2 are also ferromagnetic and, moreover, energetically stable. We conclude that either of these variants possess a ferromagnetic phase of the kind CdGeP 2 : Mn. Similar conclusions are obtained for ZnGeP 2 : Mn.     

Oxidation of Pt(111) under near-ambient conditions

The oxidation of Pt(111) at near-ambient O2 pressures has been followed in situ using x-ray photoelectron spectroscopy (XPS) and ex situ using x-ray absorption spectroscopy (XAS). Polarization-dependent XAS signatures at the O K edge reveal significant temperature- and pressure-dependent changes of the Pt-O interaction. Oxide growth commences via a PtO-like surface oxide that coexists with chemisorbed oxygen, while an ultrathin α-PtO2 trilayer is identified as the precursor to bulk oxidation. These results have important implications for understanding the chemical state of Pt in catalysis.     

Resonant photoemission at the L3 absorption edge of Mn and Ti and the electronic structure of 1T-Mn0.2TiSe2

Resonant valence band x-ray photoelectron spectra (ResPES) excited near the 2p(3/2) core level energies, 2p x-ray photoelectron spectra (XPS) and L(3,2) x-ray absorption spectra (XAS) of Ti and Mn in single crystals of 1T-Mn(0.2)TiSe(2) were studied for the first time. The ionic-covalent character of the bonds formed by the Mn atoms with the neighboring Se atoms in the octahedral coordination is established. From the XPS and XAS measurements compared with the results of atomic multiplet calculations of Ti and Mn L(3,2) XAS, it is found that the Ti atoms are in the ionic state of 4 + and the Mn atoms are in the state of 2 +. In ResPES of Mn(0.2)TiSe(2) excited near the Ti 2p(3/2) and Mn 2p(3/2) absorption edges the Ti 3d and Mn 3d bands at binding energies just below the Fermi level are observed. According to theoretical calculations of E(k) the Ti 3d states are localized in the vicinity of the Γ point and the Mn 3d states are localized along the direction K-Γ-M in the Brillouin zone of the crystal.     

Chemical states of GeTe thin-film during structural phase-change by annealing in ultra-high vacuum

The chemical states of GeTe thin film are investigated using high-resolution X-ray photoelectron spectroscopy (HRXPS) with synchrotron radiation, during amorphous to crystalline structural phase transition. As the temperature increases from 250 to 400 °C, we observe the rock-salt crystalline structure and phase with X-ray diffraction (XRD) and transmission electron microscopy (TEM). Spin-orbit splitting of the Ge 3d core-level spectrum clearly appears after annealing at 400 °C for 5 min. However, the binding energy of the Ge 3d_5/2 core-level peak of 29.8 eV does not change in the amorphous to crystalline structural phase transition. In the case of the Te 4d core-level, change in binding energy and peak shapes is also negligible. We assume that the Te atom is fixed at a site between the amorphous and crystalline phases. Although the structural environment of the Ge atoms changes during the structural phase transition, the chemical environment does not.     

Identification of minority compounds in natural ilmenites by X-ray absorption spectroscopy

Natural ilmenites are used all over the world as raw materials in white pigment (TiO₂) production. Besides the FeTiO₃ in the raw material many other compounds are present. The chemical compounds based on the minority elements influence quality of the final product and are difficult to identify. The knowledge about chemical bonding of the minor elements enables to properly adjust chemical reactions during production processes and to improve quality of the final product. In this paper the X-ray absorption spectroscopy (XAS) identification of the chemical compounds formed by Mg, Mn and Cr in natural ilmenites originating from different places is presented.