Analysis of extraterrestrial particles using monochromated electron energy-loss spectroscopy

A monochromated (scanning) transmission electron microscope was used to analyze individual sub-micron grains within interplanetary dust particles (IDP). Using low-loss and core-loss electron energy-loss spectroscopy, we analyzed fluid and gas inclusions within vesiculated alumosilicate grains. It is shown that nanometer-sized vesicles contain predominantly molecular oxygen (O(2)) beside a small fraction of H(2)O. Low-loss spectra reveal the Schumann-Runge continuum peaking at 8.6 eV and absorption bands reflecting vibrational excitation states of O(2) molecules between the first (12.1 eV) and second (16.1 eV) ionization energy. The presence of oxygen gas is supported by the corresponding oxygen K-edge fine structure. The valence state of Fe in iron-oxide within the IDP was also studied. Low-loss spectra provide qualitative information about the oxidation state of iron consistent with the Fe(2+)/Fe(3+) ratio quantitatively derived from the Fe L(2,3) edge.     

Determination of Ce/Ce in electron-beam-damaged CeO2 by electron energy-loss spectroscopy

We followed the reduction of Ce⁴⁺ in CeO₂ by observing changes in the shape of the Ce M_4,5 edge by parallel electron energy-loss spectroscopy with a transmission electron microscope. The energy-loss near-edge structure of the beam-damaged CeO₂ exhibits Ce M_4,5 and O K-edge shapes that are consistent with reduction to a Ce³⁺ oxide. During the damage process the spectrum of CeO₂ changes as follows: (a) decreases in energies of the M₅ and M₄ maxima; (b) changes in shape of the near-edge structure; (c) inversion of the M₅ to M₄ branching ratio; and (d) increase in the M₅ to M₄ area ratio. We simulated M_4,5 edges of damaged CeO₂ with a linear combination of Ce⁴⁺ and Ce³⁺ spectra and observed no intermediate oxidation states.     

Valence state mapping of cobalt and manganese using near-edge fine structures

The properties of transition metal oxides are related to the presence of elements with mixed valences. The spectroscopy analysis of the valence states is feasible experimentally, but a spatial mapping of valence states of transition metal elements is a challenge to existing microscopy techniques. In this paper, with the use of valence state information provided by the white lines and near-edge fine structures observed using the electron energy-loss spectroscopy (EELS) in a transmission electron microscope (TEM), a novel experimental approach is demonstrated to map the valence state distributions of Mn and Co using the ratio of white lines in the energy-filtered TEM. The valence state map is almost independent of specimen thickness in the thickness range adequate for quantitative EELS microanalysis. An optimum spatial resolution of approximately 2 nm has been achieved for a two-phase Co oxides.     

On the oxidation of CaF2 in transmission electron microscope

Electron stimulated oxidation of CaF₂ in transmission electron microscope has been thoroughly studied using various electron microscopy techniques, including imaging, electron diffraction and electron energy-loss spectroscopy. It found that the electron irradiation induced CaO locate on the edge of specimen. The oxidation process is associated with desorption of F by electron irradiation, and originates from O impurities in the specimen. Driven by electric field produced by electron irradiation, the O ions inside bulk diffuse to the edge region, occupying the interstitials of metallized Ca lattice. Therefore, the accumulation of O along the edge of specimen results in forming CaO.     

Oxidation states of Mn and Fe in various compound oxide systems

Energy-loss near-edge structure (ELNES) data of Mn-L(2,3) and Fe-L(2,3) ionization edges have been measured by means of quantitative electron energy-loss spectroscopy (EELS) for two series of Mn and Fe oxides with known formal cation oxidation states. In both series the absolute energy positions of Mn-L(2,3) and Fe-L(2,3) white-lines, as well as the white-line intensity ratio (L3/L2) vary with cation oxidation states. Additionally, spin-orbit spitting, i.e. the energy difference deltaE(L2-L3) between Mn-L(2,3) white-lines decreases with increasing Mn oxidation state. With these data from known standards calibration curves on white-line intensity ratio Mn(L3/L2) vs. Mn oxidation state, and Fe(L3/L2) vs. Fe oxidation state were established. EELS measurements on Mn and Fe doped ZnO thin films showed that the valence states of the dopants can unambiguously be determined by calibrating the Mn-L(2,3) and Fe-L(2,3) ELNES data against the measured standards. It is revealed that Mn in ZnO adopt a divalent state, thus Mn2+ ions substitute for Zn2+, whereas Fe dopants retain a trivalent oxidation state in the ZnO host lattice. Measurements on (Ba, Fe, Mn)-oxides revealed that both Fe and Mn cations are in a trivalent state. Thus, it is assumed that Mn3+ can partially be substituted for Fe3+ in barium hexaferrites.     

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.     

现代透射电子显微技术在多铁材料研究中的应用

文章简要介绍了材料科学研究中被广泛应用的透射电子显微(TEM)技术及其在多铁材料研究中的应用,并给出了几个典型案例：利用球差矫正原子分辨扫描透射电子显微术(STEM),并和电子能量损失谱(EELS)相结合,分析多铁异质结界面处的原子分布、离子价态和化学键的变化;结合球差矫正原子分辨透射电子显微图像(HRTEM)和STEM图像,分析多铁材料中的局域对称性破缺和电极化特性;利用原位变温及电/磁场加载技术,研究多铁材料中的结构相变和电畴/磁畴的动态演变特性。文章特别指出,现代透射电子显微学是全面分析理解多铁材料局域微结构,探讨多铁耦合机制及其物理根源的有效手段。     

Inner shell excitation,valence excitation and core ionization in NF3 studied by electron energy-loss and X-ray photoelectron spectroscopies

Electron energy-loss Spectroscopy (EELS) at impact energies of 2.5–3 keV has been used to obtain the electron excitation spectra for the N 1s (K-shell), F 1s (K-shell) and valence shell regions of NF₃. The inner shell spectra were recorded using small angle scattering (?1° ) while the valence shell spectrum was obtained at zero degree scattering angle. The inner shell excitation spectra show a strongly enhanced 1s→ δ^* type transition and continuum features which are typical for molecules with highly electronegative ligands. One of the peaks in an earlier published photoabsorption study of the N 1s region has been shown to be due to a N₂ impurity. The valence shell electron energy-loss spectrum shows a number of transitions which are considered to be mainly due to valence-valence type transitions, with also some evidence of Rydberg structure.The X-ray photoelectron spectra (XPS) of the N 1s and F 1s electrons along with their associated satellite structures have also been recorded using Al Kα (1486.58 eV) radiation. The vertical ionization potentials for the N 1s and F 1s electrons were found to be 414.36 (10) eV and 693.24 (10) eV, respectively. Both spectra exhibit a rich and different satellite structure. These “shake-up” features in the satellite XPS spectra are compared with continuum features of the inner shell electron energy-loss spectra and also with the valence shell spectrum.     

典型磁性材料价电子结构研究面临的机遇与挑战

目前在磁性材料磁有序现象研究中广泛使用的交换作用、超交换作用和双交换作用模型形成于1950年代及其以前,这些模型都涉及材料中的价电子状态,但那时还没有充分的价电子状态实验依据.1970年代以来,有关价电子结构实验结果的报道越来越多,这些实验结果表明传统的磁有序模型需要改进.首先,大量电子谱实验表明,在氧化物中除存在负二价氧离子之外,还存在负一价氧离子,并且负一价氧离子的含量可达30%或更多.这说明以所有氧离子都是负二价离子为基本假设的超交换和双交换作用模型需要改进.其次,一些实验证明,铁、钴、镍自由原子的一部分4s电子在形成铁磁性金属的过程中变成了3d电子,这为探讨金属磁性与电输运性质的关系提供了依据.此外,即使在现代的密度泛函计算中,仍不能给出磁性交换作用能的函数表达式,只能采取各种不同模型进行模拟计算,从而使磁性材料的模拟计算遇到严重困难.寻求一个磁有序能的函数表达式可能是解决这个困难的途径.这些研究表明磁性材料价电子结构研究面临着重大的机遇与挑战.本文首先介绍一些典型的实验例证,然后介绍了基于这些实验结果的一套典型磁性材料的磁有序新模型,随后介绍了基于新模型的磁性材料价电子结构与旧模型的主要区别,最后指出了未来研究工作面临的挑战.     

On the correlation between the X‐ray absorption chemical shift and the formal valence state in mixed‐valence manganites

Here the correlation between the chemical shift in X‐ray absorption spectroscopy, the geometrical structure and the formal valence state of the Mn atom in mixed‐valence manganites are discussed. It is shown that this empirical correlation can be reliably used to determine the formal valence of Mn, using either X‐ray absorption spectroscopy or resonant X‐ray scattering techniques. The difficulties in obtaining a reliable comparison between experimental XANES spectra and theoretical simulations on an absolute energy scale are revealed. It is concluded that the contributions from the electronic occupation and the local structure to the XANES spectra cannot be separated either experimentally or theoretically. In this way the geometrical and electronic structure of the Mn atom in mixed‐valence manganites cannot be described as a bimodal distribution of the formal integer Mn³⁺ and Mn⁴⁺ valence states corresponding to the undoped references.     

Local optical properties, electron densities, and london dispersion energies of atomically structured grain boundaries

Quantitative analysis of spatially resolved valence electron energy-loss spectra shows strong physical property contrasts for Sigma5 and near Sigma13 grain boundaries in Fe-doped SrTiO3, resulting in London dispersion interaction energies of 14 to 50 mJ/m(2) between the adjacent grains. The determination of local physical properties of grain boundary cores and the appreciable contribution of long-range London dispersion to interface energies provides new information on formation and control of interfaces in materials.     

Atomic structure of highly strained BiFeO3 thin films

We determine the atomic structure of the pseudotetragonal T phase and the pseudorhombohedral R phase in highly strained multiferroic BiFeO(3) thin films by using a combination of atomic-resolution scanning transmission electron microscopy and electron energy-loss spectroscopy. The coordination of the Fe atoms and their displacement relative to the O and Bi positions are assessed by direct imaging. These observations allow us to interpret the electronic structure data derived from electron energy-loss spectroscopy and provide evidence for the giant spontaneous polarization in strained BiFeO(3) thin films.     

Dependence of optical properties of monoclinic MnWO4 on the electric field of incident light

Considering the electric field of incident light along four particular directions [100], [110], [011], and [010], the optical properties of monoclinic MnWO₄ were investigated by the first-principle methods. The calculated electronic structures show that the O 2p states and Mn 3d states dominate the top of the valence bands, while the W 5d and Mn 3d states play a key role in the bottom of the conduction bands. The dielectric function and other optical properties, including absorption coefficient, reflectivity spectra, and energy-loss spectra, were calculated and analyzed. The results predicted the maximum static dielectric function when the electric field of incident light was along the [100] direction; meanwhile the absorption edge was calculated to be consistent with the energy band gap and the values and positions of peaks in absorption coefficient are related with the electric field of light. Otherwise, it is found that the appearance of peaks in the energy-loss spectra is also dependent on the electric field and simultaneously corresponds to the edge of absorption spectra and the peaks' position of reflectivity spectra.     

Valence changes of manganese and praseodymium in Pr1−xSrxMn1−yInyO3−δ perovskites upon cation substitution as determined with XANES and ELNES

Systematic valence changes in Pr_1−xSr_xMn_1−yIn_yO_3−δ upon cation substitution with Sr²⁺ and In³⁺ have been found using Mn K-edge and Pr L-edge X-ray absorption, and Mn L_II,III and Pr M_IV,V electron energy-loss spectroscopy. The average valence of the praseodymium ions is close to +3.0 and virtually constant over the sample set when the samples also contained manganese ions. Pr_0.5Sr_0.5InO_3−δ showed a distinct increase in the praseodymium valence state. In contrast, the average valence of the manganese ions changed from the trivalent state to intermediate values between +3.0 and +4.0 and approached the tetravalent state depending on the level of substitution. The knowledge of the valence is required to understand the conduction mechanisms in the material due to the small polaron hopping (electronic conductivity) and motion of oxygen ions along the vacancies (ionic conductivity). Addition of strontium and indium led to the formation of oxygen vacancies. A previously assumed intermediate valence of praseodymium as causal factor for the higher oxygen catalytic activity cannot be confirmed with room temperature measurements.     

Crystal and electronic structure of solid C76

The crystal and electronic structure of solidC ₇₆ has been studied using transmission electron microscopy and electron energy-loss spectroscopy in transmission. C₇₆ forms a close packed structure with an average facecentred cubic symmetry. From valence band and core electron excitations information on the dielectric function and the unoccupied density of states has been obtained.     

Polarity and inverse boundary of Sn-doped ZnO bicrystal nanobelts determined by electron energy-loss spectroscopy

Polarity in Sn-doped ZnO bicrystal nanobelts has been investigated using electron energy-loss spectroscopy. The nanobelts are composed of two domain boundaries extending along the axial direction. It is confirmed that the nanobelts are Zn terminated at both sides. Examinations of high-resolution transmission electron microscopy and electron energy-loss spectroscopy show that one domain boundary results from a stacking fault, and the other originates from Sn-ion insertion, which leads to an inverse domain boundary. A possible atomic stacking model is proposed.     

锂离子电池掺钴正极材料电子结构的DV-Xα研究

采用原子基表示的第一原理赝势方法 ,计算了正极材料LiMn2 O4的电子结构 ,发现LiMn2 O4的价带主要是由Mn(8)和Mn(9)的 3d轨道和O(7)、O(6 )、O(4 )的 2p轨道构成 ,导带主要是由Mn(8)和Mn(9)的 3d轨道和O(7)的 2 p轨道构成 .通过计算Li5Mn7CoO8的电子结构 ,发现在LiMn2 O4中用钴离子取代 16d位锰离子将使电极材料的费米能减小 ,放电电压降低 ;锂离子的净电荷增大 ,锂离子与氧离子的相互作用增强 ,可逆容量降低 ;同时由于价带宽度变窄 ,Co-O键间的相互作用比Mn -O键间的相互作用强 ,所以 ,结构稳定性增加 ,电极循环性能改善 .     

Intrinsic electron accumulation at clean InN surfaces

The electronic structure of clean InN(0001) surfaces has been investigated by high-resolution electron-energy-loss spectroscopy of the conduction band electron plasmon excitations. An intrinsic surface electron accumulation layer is found to exist and is explained in terms of a particularly low Gamma-point conduction band minimum in wurtzite InN. As a result, surface Fermi level pinning high in the conduction band in the vicinity of the Gamma point, but near the average midgap energy, produces charged donor-type surface states with associated downward band bending. Semiclassical dielectric theory simulations of the energy-loss spectra and charge-profile calculations indicate a surface state density of 2.5 (+/-0.2)x10(13) cm(-2) and a surface Fermi level of 1.64+/-0.10 eV above the valence band maximum.     

Imaging and spectroscopy of defects in semiconductors using aberration-corrected STEM

The distribution of single dopant or impurity atoms can dramatically alter the properties of semiconductor materials. The sensitivity to detect and localize such single atoms has been greatly improved by the development of aberration correctors for scanning transmission electron microscopes. Today, electron probes with diameters well below 1 Å are available thanks to the improved electron optics. Simultaneous acquisition of image signals and electron energy-loss spectroscopy data provides means of characterization of defect structures in semiconductors with unprecedented detail. In addition to an improvement of the lateral spatial resolution, depth sensitivity is greatly enhanced because of the availability of larger probe forming angles. We report the characterization of an alternate gate dielectric interface structure. Isolated Hf atoms are directly imaged within a SiO₂ thin film formed between an HfO₂ layer and the silicon substrate. Electron energy-loss spectroscopy shows significant changes of the silicon valence state across the interface structure.     

Crystal-field level inversion in lightly Mn-doped Sr3Ru2O7

Sr3(Ru(1-x)Mnx)2O7, in which 4d-Ru is substituted by the more localized 3d-Mn, is studied by x-ray dichroism and spin-resolved density functional theory. We find that Mn impurities do not exhibit the same 4+ valence of Ru, but act as 3+ acceptors; the extra eg electron occupies the in-plane 3d(x2-y2) orbital instead of the expected out-of-plane 3d(3z2-r2). We propose that the 3d-4d interplay, via the ligand oxygen orbitals, is responsible for this crystal-field level inversion and the material's transition to an antiferromagnetic, possibly orbitally ordered, low-temperature state.