Lattice Dynamics and Inelastic Nuclear Resonant X-Ray Scattering

Measurement of thermal and elastic properties of materials, like phonon density of states, specific heat or speed of sound, by a new X-ray scattering technique is presented. Inelastic nuclear resonant scattering of X-rays produced from new electron storage rings, coupled with advances in high-energy-resolution crystal optics and fast detectors has enabled the development of a new method of analyzing the energy loss in a scattering process with a resolution of 10⁷ or better in the X-ray region of 6–30 keV. Some unique aspects like element (isotope) selectivity, the amount of material needed for analysis (nanograms) and physical size that X-rays can be focused (5 micrometer or better) favors this approach over more established techniques of neutron scattering, Mössbauer, and Raman spectroscopy. Applications to several unique cases (e.g., multilayers and high pressure) are discussed.     

Measurement of diffusion process of iron atoms under high pressure of hydrogen by time-domain analysis of nuclear resonant scattering of X-rays

We applied the time-domain analysis of nuclear resonant scattering (NRS) of X-rays for the study of the hydrogen-induced enhancement of atomic diffusion. The time-domain analysis of NRS is a powerful technique for studying diffusion processes on an atomic scale. The NRS measurement combined with high-pressure technique enables the direct measurement of self-diffusion processes under high hydrogen pressures. In this preliminary experiment, self-diffusion in 4 μm thick ⁵⁷Fe foils at 0.8 GPa was investigated. The samples of the ⁵⁷Fe were encapsulated with MgO or NaCl. Faster decays caused by diffusion of Fe atoms were observed in the time spectra of NRS at high temperatures. This enhancement of diffusion is believed to be the hydrogen-induced effect. In the present experiment, hydrogen should have been supplied to the samples by reaction with water originally adsorbed on NaCl/MgO powder particles. It was concluded that the diffusion of ⁵⁷Fe atoms under high pressure can be studied by nuclear resonant scattering of X-rays using a compact cubic-anvil press. The NRS method can also be extended to the study of atomic diffusion in the subsurface region by doping ⁵⁷Fe layer(s) at known depths.     

Polarization of photons emitted in the process of resonant coherent excitation of relativistic ions under planar channeling conditions

Owing to the recent observation of the strong anisotropy of characteristic X-ray radiation accompanying the resonant coherent excitation of relativistic Fe²⁴⁺ ions under planar channeling conditions in a silicon crystal, the resonant coherent excitation method can be considered as a candidate for a source of polarized X-ray radiation. The Stokes parameters of the radiation have been calculated using the density matrix approach. The behavior of the polarization characteristics of the radiation in various directions has been explained by considering the properties of the resonance part of the crystal field, which excites an ion and has the form of an elliptically polarized electric field.     

硫化锰电子结构的软X射线共振非弹性散射研究

利用软X射线共振非弹性散射谱(resonant inelastic soft X-ray scattering, RIXS)对3d过渡金属硫化物中的硫化锰(MnS)电子结构进行了研究.通过分析Mn²⁺的2p⁶3d⁵→2p⁵3d⁶→2p⁶3d⁵二次光子过程，得到了共振非弹性散射谱中的两类非弹性峰，d-d电子跃迁和电荷转移(charge-transfer)跃迁.这两部分跃迁分别共振增强于L边附近及伴随峰附近.基于Hartree-Fock方法的多重态计算分别模拟了原子近似下和立方体O_h对称群下共振非弹性散射谱及吸收谱.计算得MnS实际晶体场10Dq值介于0.80eV—0.85eV之间.对MnS和MnO CT跃迁差异的讨论表明MnS较强的CT跃迁来源于其较窄的能隙宽度. 关键词： 软X射线共振非弹性散射 软X射线吸收谱 d-d跃迁 电荷转移     

X-ray scattering study on the electric field-induced interfacial magnetic anisotropy modulation at CoFeB / MgO interfaces

The electric field-induced modifications of magnetic anisotropy in CoFeB/MgO systems are studied using X-ray resonant magnetic scattering and magneto-optical Kerr effect. Voltage dependent changes of the magnetic anisotropy of −12.7 fJ/Vm and −8.32 fJ/Vm are observed for Ta/CoFeB/MgO and Hf/CoFeB/MgO systems, respectively. This implies that the interfacial perpendicular magnetic anisotropy is reduced (enhanced) when electron density is increased (decreased). X-ray resonant magnetic scattering measurements reveal that the small in-plane magnetic component of the remanent state of CoFeB/MgO systems with weak magnetic anisotropy changes depending on the applied voltage leading to modification of the magnetic anisotropy at the CoFeB/MgO interface.     

Deduction of the temperature-dependent structure of the four-layer intermediate smectic phase using resonant X-ray scattering

A binary mixture of an antiferroelectric liquid-crystal material containing a selenium atom and a highly chiral dopant is investigated using resonant X-ray scattering. This mixture exhibits a remarkably wide four-layer intermediate smectic phase, the structure of which is investigated over a temperature range of 16K. Analysis of the resonant X-ray scattering data allows accurate measurement of both the helicoidal pitch and the distortion angle as a function of temperature. The former decreases rapidly as the SmC ^* phase is approached, whilst the latter remains constant over the temperature range studied at 8^°±3^° . We also observe that the senses of the helicoidal pitch and the unit cell of the repeating four-layer structure are opposite in this mixture and that there is no pitch inversion over the temperature range studied.     

The chromium spin density wave: magnetic X-ray scattering studies with polarisation analysis

We report on X-ray magnetic diffraction studies of the spin density wave antiferromagnetism formed in the conduction electron band of chromium. Non-resonant X-ray magnetic scattering was used to directly determine that chromium has zero orbital magnetisation. Furthermore, the azimuthal dependence of this scattering provides unique evidence that chromium forms a linearly polarised wave. In the vicinity of the K absorption edge, resonant X-ray magnetic scattering was observed. A consistent model of the magnetic scattering has been derived from the resonant and non-resonant magnetic amplitudes. The enhancement of the magnetic intensity arises primarily from dipole transitions from the core 1s level to 4p states. Quadrupole transitions to the magnetic 3d states are essentially non-existent due to their sensitivity to (and the absence of) orbital moment. This effect is predicted from atomic considerations of the 3d⁵ ( = 0) transition metal ions. Received 22 September 2000     

Resonant X-ray scattering from a rotating medium: The Nuclear Lighthouse Effect

A coherently excited nuclear state is carried with a rotating sample so that its radiative decay is redirected by the rotation angle that has developed during its lifetime. As a result, the time spectrum of the nuclear decay is mapped to an angular scale. This effect has been observed in nuclear resonant scattering of synchrotron radiation from a rotating ⁵⁷Fe metal foil. Applications with respect to elastic and inelastic nuclear resonant scattering are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Charge-magnetic interference resonant scattering studies of ferromagnetic crystals and thin films

The element- and site-specificity of X-ray resonant magnetic scattering (XRMS) makes it an ideal tool for furthering our understanding of complex magnetic systems. In the hard X-rays, XRMS is readily applied to most antiferromagnets where the relatively weak resonant magnetic scattering (10⁻²–10⁻⁶ I _c ) is separated in reciprocal space from the stronger, Bragg charge scattered intensity, I _c . In ferro(ferri)magnetic materials, however, such separation does not occur and measurements of resonant magnetic scattering in the presence of strong charge scattering are quite challenging. We discuss the use of charge-magnetic interference resonant scattering for studies of ferromagnetic (FM) crystals and layered films. We review the challenges and opportunities afforded by this approach, particularly when using circularly polarized X-rays. We illustrate current capabilities at the Advanced Photon Source with studies aimed at probing site-specific magnetism in ferromagnetic crystals, and interfacial magnetism in films.     

Resonances in the dtµ molecular ion between tµ(n=2) and dµ(n=2) thresholds

Elastic and inelastic cross sections in collisions of a tµ atom in 2s and 2p states on deuteron have been obtained within the framework of a four-channel adiabatic approximation for the case of total orbital angular momentumJ=0. The calculated data has been applied to verify the existence of resonance in the dtµ molecular ion at 0.8 eV above the tµ(n=2) threshold. It appears that the second and third resonant states (at 0.8 eV and at 7 eV above the tµ threshold) in a series converging to the dµ(n=2) threshold do not produce any resonant structure in the energy spectrum. The higher vibrational states are visible in the spectrum, however their widths are about 0.1 eV and therefore their life-times are about 10^–15 s which allows to conclude that these states could not play an important role in the µCF cycle as well as in processes of diffusion of muonic atoms.     

Triple‐resonant two‐phonon Raman scattering in graphene

The triple‐resonant (TR) second‐order Raman scattering mechanism in graphene is re‐examined. It is shown that the magnitude of the TR contribution to the photon‐G′ mode coupling function in graphene is one order of magnitude larger than the widely accepted two‐resonant coupling. Enhancement of the order of 100 in the Raman intensity, with respect to the usual double‐resonant model, is found for the G′ band in graphene, and is expected in the related sp²‐based carbon materials, as well. Copyright © 2011 John Wiley & Sons, Ltd.     

Co掺杂ZnO薄膜的局域结构和电荷转移特性研究

采用磁束缚电感耦合等离子体溅射沉积法在不同的氧气分压下制备了Zn_0.95Co_0.05O和Zn_0.94Co_0.05Al_0.01O薄膜.利用X射线吸收精细结构技术对薄膜O-K,Co-K和Co-L边进行了局域结构研究,结果表明：Co²⁺取代了四配位晶体场中的Zn²⁺而未改变ZnO的六方纤锌矿结构,高真空条件下制备的薄膜 关键词： Co掺杂ZnO 稀磁半导体 X射线吸收精细结构 共振非弹性X射线散射     

Characterisation of the oxygen transfer in BIMEVOX membranes under applied current conditions

Oxygen isotopic exchange has been studied for a number of materials in the BIMEVOX family of compounds. The exchanges were undertaken at 620 °C with gold grid electrodes on the samples and with a constant current flowing through the samples during the exchange anneals. These conditions simulate those used when these materials are employed in oxygen separation devices where substantial oxygen fluxes can be sustained using such simple gold grid electrodes.The results showed that samples exchanged under current flow conditions exhibit substantial oxygen exchange at the cathode, in contrast to samples where no electrical bias is applied. This effect was sustained in regions remote from the sputtered gold electrode. Complementary studies of the samples using X-ray diffraction revealed subtle changes in the diffraction patterns following experiments with current flow. These changes are ascribed to a reduction of V⁵⁺ to V⁴⁺ at the cathode locally transforming the BIMEVOX material into a mixed conducting material, and hence enhancing the oxygen isotopic exchange process.     

Resonant Raman scattering by N-related local modes in AlGaAs/InGaAsN multiquantum wells

We report resonant Raman scattering and secondary ion mass spectrometry measurements on InGaAsN/AlGaAs multiquantum wells grown by plasma-assisted molecular beam epitaxy. The appearance of a strong TO band at resonance with nitrogen (N)-related electronic levels has been observed. The N-induced vibration mode at 470 cm⁻¹ changes in intensity and shape with increasing N and In content. A new vibration mode has been observed at 320 cm⁻¹, whose intensity scales with the N concentration. This mode is not present in InGaAsN films, so it is linked to the presence of Al. Its frequency is close to the B₁ silent mode of wurtzite GaN. It is attributed to the formation of GaN pairs, near the MQW interfaces as a consequence of the preferential Al–N bonding.     

Extension of the resonant scattering technique to liquid crystals without resonant element

We report X-ray resonant scattering experiments performed on the prototype liquid-crystalline compound MHPOBC doped with a chemical probe containing a resonant atom (selenium). We determined directly for the first time the microscopic 3- and 4-layer structure of the ferrielectric subphases ( SmC_FI1^* and SmC_FI2^*) present in MHPOBC. Despite the low fraction of the selenium probe, the resonant signal is strong enough to allow an unambiguous determination of the basic structure of the ferrielectric subphases. These experiments demonstrate that the resonant scattering technique can be extended to liquid crystalline materials without resonant element and may stimulate new studies. A non-resonant Bragg reflection was also found in the SmC_FI1^* phase in pure MHPOBC, consistent with the 3-layer distorted model, but never detected before.     

Studying the luminescence efficiency of Lu<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu nanophosphor material for digital X-ray imaging applications

Scintillator materials are widely used in X-ray medical imaging detector applications, coupled with available photoreceptors like radiographic film or photoreceptors suitable for digital imaging like a-Si, charge-coupled devises (CCD), complementary metal-oxide-semiconductors (CMOS) and GaAs). In addition, scintillators can be utilized in non-medical imaging detectors such as industrial detectors for non-destructive testing (NDT) and detectors used for security purposes (i.e. airport luggage control). Image quality and dose burden in the above applications is associated with the amount of optical photons escaping the scintillator as well as the amount of optical photons captured by the photoreceptor. The former is characterized by the scintillator efficiency and the latter by the spectral matching between the emission spectrum of the scintillator and the spectral response of the photoreceptor. Recently, a scintillator material, europium-activated lutetium oxide (Lu₂O₃:Eu), has shown improved scintillating properties. Lu₂O₃:Eu samples of compact nanocrystalline non-agglomerated powder were developed in our laboratory using homogeneous precipitation from a water-toluene solution in the presence of polyvinyl alcohol as a surfactant. In order to test their light-emission properties, experimental measurements under the excitation of X-ray spectra with X-ray tube voltages between 50 kVp and 140 kVp were performed. This range of applied voltages is appropriate for X-ray radiology, NDT and security applications. Lu₂O₃:Eu was evaluated with respect to output yield and spectral compatibility of digital imaging photoreceptors (CCD-based, CMOS-based, amorphous silicon a:Si flat panels, ES20 and GaAs). High light yield and spectral compatibility increase the performance of the medical detector and reduce the dose burden to the personnel involved. In addition a theoretical model was used to determine the values for the Lu₂O₃:Eu optical photon light propagation parameters. The inverse diffusion length was found to be equal to 33 cm²/g. In addition Lu₂O₃:Eu was found to match well with several photoreceptors capable of digital imaging (i.e. GaAs).     

Sound velocities of compressed Fe3C from simultaneous synchrotron X‐ray diffraction and nuclear resonant scattering measurements

The applications of nuclear resonant scattering in laser‐heated diamond anvil cells have provided an important probe for the magnetic and vibrational properties of ⁵⁷Fe‐bearing materials under high pressure and high temperature. Synchrotron X‐ray diffraction is one of the most powerful tools for studying phase stability and equation of state over a wide range of pressure and temperature conditions. Recently an experimental capability has been developed for simultaneous nuclear resonant scattering and X‐ray diffraction measurements using synchrotron radiation. Here the application of this method to determine the sound velocities of compressed Fe₃C is shown. The X‐ray diffraction measurements allow detection of microscale impurities, phase transitions and chemical reactions upon compression or heating. They also provide information on sample pressure, grain size distribution and unit cell volume. By combining the Debye velocity extracted from the nuclear resonant inelastic X‐ray scattering measurements and the structure, density and elasticity data from the X‐ray diffraction measurements simultaneously obtained, more accurate sound velocity data can be derived. Our results on few‐crystal and powder samples indicate strong anisotropy in the sound velocities of Fe₃C under ambient conditions.     

A New Method to Measure Small Amounts of Solute Atoms on Planar Defects and Application to Inversion Domain Boundaries in Doped Zinc Oxide

We demonstrate the application of a new method of analytical transmission electron microscopy for measuring very accurately small amounts of solute atoms within a well-defined planar defect such as a stacking fault, grain boundary or an interface. The method is based on acquiring several spectra with different electron beam diameters from the same position centred on the defect. It can be applied to energy-dispersive X-ray microanalysis (EDXS) or electron energy-loss spectroscopy (EELS) and does not necessitate a scanning unit. The accuracy has been tested numerically under different conditions using simulations for a specific geometry and has been found to be substantially better than that of any other current standard technique. Our calculations suggest an extremely high accuracy theoretically achievable in the determination of e.g. the Gibbsian solute excess or the doping level of a grain boundary down to about ±1% of an effective monolayer, i.e. ±0.1 atoms/nm² under typical experimental conditions. The method has been applied to zinc oxide, which forms inversion domain boundaries (IDBs) when doped with different transition metal oxides such as SnO₂ or Sb₂O₃. We obtained an experimental precision of ±0.4 atoms/nm², which has allowed us to solve the atomic structure of the IDBs.     

X-ray resonant powder diffraction

X-ray resonant diffraction can be applied in structural chemistry studies on powder samples. It enables an important limitation of powder diffraction to be overcome. This limitation is related to the low ability of powder diffraction to differentiate elements with close atomic numbers when they occupy the same or close crystallographic sites (mixed occupancy case) and also to discriminate cations with different valence states in different sites. However the resonant effect usually has a second order influence on the measured intensity. As a consequence, the efficiency of this method directly implies the need for excellent quality data collection and has generally been better assessed on elements present in single phase powder samples. In recent years, instrumental developments have been made in synchrotron radiation facilities which allow easier use of resonant powder diffraction for site-specific contrast and valence i.e. oxidation state analyses. Moreover, resonant contrast diffraction tools also have been proposed for better visualization of the anomalous effect both in direct and reciprocal space by using differences between electron density maps or diffraction patterns. Finally the potentialities of this technique for de novo structure solution on macromolecular systems are mentioned.     

Temperature variation of the Debye-Waller factors of metal and halide ions in CsCl and CsBr powders by X-ray diffraction. I. Debye-Waller factors of Cs+ and Cl− ions in CsCl from room temperature to 90°K

The temperature variation of the Debye-Waller factors of Cs⁺ and Cl⁻ ions in CsCl powder has been studied using X-ray powder diffraction. A continuous flow cryostat has been used to record the diffractograms and the integrated intensities of the Bragg peaks at different temperatures have been obtained. The integrated intensities of the odd and even reflections have been analysed following the structure of the CsCl compound and the Debye-Waller factors of the Cs⁺ and Cl⁻ ions have been estimated. The results have been verified by structure factor least squares refinement. Theoretical shell model lattice dynamical calculations have been done using a 7-parameter model in the harmonic approximation and the values compared with the present X-ray measurements.