Combined X-ray absorption and X-ray diffraction under high pressure

ABSTRACT

X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) are two complementary structural techniques. Their combination improves the understanding of the effect of pressure on materials as illustrated by examples taken from studies on different types of materials (semiconductors, molecular solid, ferroelectric perovskite and gas mixture). The introduction of nanopolycrystalline diamonds anvils has extended XAS to high-energy edges with the possibility to use energy-scanning XAS beamlines where XRD can be performed in addition to XAS experiments.     

锐钛矿金红石的高温原位X射线衍射研究

对TiO₂粉末进行了空气和真空条件下从室温到1200℃的加热原位X射线衍射实验, 得到了空气和真空条件下微米级锐钛矿颗粒转变为金红石的起始温度分别为850℃ 和855℃; 分别修正了空气条件下锐钛矿在(27–850℃)范围和金红石在(900–1200℃) 范围内的晶胞参数和真空条件下锐钛矿在(27–850℃)范围和金红石在(950–1200℃) 范围的晶胞参数, 从而得到了晶胞参数随温度变化的关系, 得到了锐钛矿和金红石在空气中和真空中的热膨胀系数, 并总结了热膨胀系数随温度变化的规律. 室温下锐钛矿在空气条件下的热膨胀系数为 α_a=4.55063×10^-6/℃, α_c=7.7543×10^-6/℃, β=16.85836×10^-6/℃; 真空下为 α_a=4.69429×10^-6/℃, α_c=9.02850×10^-6/℃, β=18.69688×10^-6/℃. 室温下, 金红石在空气条件下的热膨胀系数为 α_a=6.81243×10^-6/℃, α_c=8.71644×10^-6/℃, β=22.22178×10^-6/℃; 真空条件下为 α_a=6.05834×10^-6/℃, α_c= 8.39280×10^-6/℃, β=20.52362×10^-6/℃. 关键词： 2')" href="#">TiO₂ 原位X射线衍射 相转变 热膨胀     

Nanometric thinning of bonded silicon wafers using sacrificial anodic oxidation and investigated by X-ray reflectivity

X-ray reflectivity and atomic force microscopy are used to investigate silicon oxide ultra-thin films. Quantitative results are shown using a reflectivity simulation model based on kinematical X-ray theory. Changes in film thickness are discussed in relation to current density, voltage, charge and anodization time. The density and resistivity of silicon oxide are calculated and compared to that of thermal oxide. The electrical field existing in the layer during anodization is estimated. Surface roughness is also measured locally and averaged over the entire surface, producing a low value that meets microelectronic requirements. Thickness is carefully controlled. We show that ultra-thin silicon oxide films are of very high quality. Similar investigations are made on a twisted bonded silicon substrate obtained by the molecular bonding of two silicon wafers. It is shown that the silicon oxide is also of very good quality and can be used as a sacrificial silicon oxide in thinning down the upper silicon film. Controlled, accurate thinning is achieved down to a thickness of 10 nm, the level which is required for etching the dislocation network present at the bonding interface.     

Electrochemical Au deposition on stepped Si(1 1 1)-H surfaces: 3D versus 2D growth studied by AFM and X-ray diffraction

In order to grow magnetic layers on silicon substrates, a non-magnetic buffer layer is often needed to avoid silicide formation and to reproduce the perpendicular magnetic anisotropy obtained on metal single crystals, as in the case of Co on Au(1 1 1) and Pt(1 1 1). In this context, we have studied the electrochemical growth of Au buffer layers, and show that it is possible to obtain different film morphologies on hydrogen-terminated vicinal Si(1 1 1) surfaces by varying the electrochemical deposition parameters and solution composition. Two different morphologies have been obtained as observed by atomic force microscopy: continuous 2D Au films (chloride solution at pH 4), and films consisting in flat top 3D Au islands decorating the Si(1 1 1) step edges (cyanide solution at pH 14). X-ray diffraction measurements reveal that the gold layer and islands have Au(1 1 1) orientation and are in epitaxy with the Si(1 1 1) surface. In the case of islands, the lateral facets have also Au(1 1 1) orientation. Results are discussed within a model in which the breaking of the Si-H surface bonds plays a major role in the Au nucleation and growth mechanisms.     

In-situ high pressure X-ray diffraction studies of orthoferrite SmFeO_3

The high-pressure behaviors of SmFeO3 are investigated by angle-dispersive synchrotron X-ray powder diffraction under a pressure of up to 40.3 GPa at room temperature. The crystal structure of SmFeO3 remains stable at up to the highest pressure. The different pressure coefficients of the normalized axial compressibility are obtained to be βa = 0.60 × 10-3 GPa-1,βb = 0.79 × 10-3 GPa-1, βc = 1.28 × 10-3 GPa- 1, and the bulk modulus （B0） is determined to be 293（3） GPa by fitting the pressure-volume data using the Birch-Murnaghan equation of state. Furthermore, the larger compressibility of the FeO6 octahedra suggests the evolution of the orthorhombic structure towards higher symmetry configuration at high pressures.     

Thickness measurement of GaN epilayer using high resolution X-ray diffraction technique

In this paper we propose a new method for measuring the thickness of the GaN epilayer, by using the ratio of the integrated intensity of the GaN epilayer X-ray diffraction peaks to that of the sapphire substrate ones. This ratio shows a linear dependence on the GaN epilayer thickness up to 2 μm. The new method is more accurate and convenient than those of using the relationship between the integrated intensity of GaN epilayer diffraction peaks and the GaN thickness. Besides, it can eliminate the absorption effect of the GaN epilayer.     

Laboratory set-up for X-ray diffraction at high pressures

We describe here a simple set-up for X-ray diffraction under high pressure using a diamond anvil cell employing a sealed tube. The set-up works in angular dispersive geometry and is built using rather common components that are available in a research laboratory. We show that using this set-up one can routinely acquire good-quality data for the determination of structural properties under pressure and the equations of state. Technical details are presented along with examples of experimental results for sodium chloride and LiV₂O₄.     

Synchrotron X-ray diffraction study of phenacite at high pressure

We report the results of a natural phenacite from 0 to 30.9 GPa using in situ angle-dispersive X-ray diffraction and a diamond anvil cell at the National Synchrotron Light Source, Brookhaven National Laboratory. Over this pressure range, no phase change or disproportionation has been observed. The isothermal equation of state was determined. The values of V₀, K₀, and K₀′ refined with a third-order Birch-Murnaghan equation of state are V₀=1116.1±1.2 ų, K₀=223±9 GPa, and K₀′=5.5±0.8. Furthermore, we confirm that the linear compressibilities (β) along a and c directions of phenacite are elastically isotropic (β_a=1.50×10^-3 and β_c=1.34×10^-3 GPa^-1). Consequently, it can be concluded that the compressibility of phenacite under high pressures has been accurately constrained.     

A calculation model for X-ray diffraction by curved-graphene nanoparticles

An approximation of the positions of carbon atoms in a curved graphene sheet is suggested for calculation of X-ray diffraction (XRD) patterns of curved-graphene nanoparticles. The model is tested for carbon nanotubes and newly calculated carbon nanotoroids consisting of several hundreds of atoms. It is shown that the random distribution of carbon atoms with graphene surface-averaged density and the local graphene-like rearrangement of atoms in a curved lattice are sufficient for describing the XRD patterns of an ensemble of respective exact carbon nanoparticles of random isotropic orientation in the range of scattering wave vector's modulus q from several units to several tens of inverse nanometers. The model is of interest to a fast-routine identification of curved-graphene nanoparticles in carbonaceous materials.     

利用高分辨X射线衍射研究磷酸二氢钾晶体晶格应变应力

采用高分辨X射线衍射技术对大尺寸磷酸二氢钾(KDP)晶体的晶格应变进行了测量,并定量分析了其晶格应力.探讨出KDP晶体容易沿着[001]方向发生开裂,与实际工作中的开裂现象相符合;进一步归纳总结了晶体生长过程中引入内应力而导致晶体开裂的主要因素.研究结果为提出相应的晶体防裂措施提供了重要的理论基础.     

基于X射线衍射的GaN薄膜厚度的精确测量

结合Williamson-Hall plot方法和线型分析方法的优点,提出了一种有效分离有限晶粒尺寸和非均匀应力等X射线衍射展宽效应的方法,可以用于GaN外延层厚度等参数的快速精确测量.用该方法对一系列在蓝宝石衬底上生长的厚度在0.7—4.2μm的GaN外延膜进行了测量,并与椭圆偏振光谱法测量结果进行了比较,结果表明其差别<4%,反应了这种方法的准确性. 关键词： GaN薄膜 厚度测量 X射线衍射     

X-ray diffraction study of KOCN at room temperature

The room temperature structure of KOCN has been successfully refined in space group I4/mcm. The OCN anion is disordered through 180° head-tail flipping and the positional coordinates and displacement parameters could not be separated for the N and O end atoms. The displacement parameters are compared for isomorphous KOCN, KN₃ and KSCN.     

Thermal trapped iron(II) high spin state investigated by X-ray diffraction

The possibilities to trap by flash cooling the high spin (HS) state of iron(II) in the [Fe(PM-BiA)₂(NCS)₂] complex have been investigated by X-ray diffraction. This study reveals that trapping the HS state is possible under some conditions depending on the final temperature. If the latter is lower than the T(LIESST) temperature, the HS→LS (low spin) relaxation is slow enough to determine the trapped HS crystal structure by X-ray diffraction. The crystal structure of this complex in the 30 K trapped HS state shows differences from either the room temperature (HS) or the 30 K (LS) crystal structures, as for example differences in the strength of the S?H-C hydrogen bond like intermolecular interaction or the π-π interactions, known to play a crucial role in this compound for the propagation of the change in spin at the spin crossover (SCO), i.e. the cooperativity. The differences in intermolecular interactions are directly linked to the differences between the crystallographic unit cell modifications induced by pure thermal effects and those induced by the SCO.     

Design and fabrication of a high temperature X-ray powder diffraction camera

A high temperature X-ray powder diffraction camera has been designed and fabricated with indigenous material. The camera design is similar to the Unicam model but overcomes some inconvenient features of the latter. The camera incorporates a miniheater which is inexpensive and easily replaceable. The camera enables determination of lattice parameters with an accuracy of ±0.0002 Å up to 800°C.     

劳厄对晶体衍射的发现

介绍了劳厄提出晶体衍射思想的科学背景及当时的实验过程,并探讨在劳厄发现晶体衍射的过程中其科学思想的形成及X射线晶体衍射的发现带给我们的启示及影响．     

Nano structure of low crystallinity carbon materials analyzed by using high energy X-ray diffraction

In this study, we tried to characterize a kind of low crystallinity carbon materials. The structure of polyparaphenylene(PPP)-based carbon was analyzed by means of high energy X-ray diffraction using the apparatus of SPring-8. The experimental results revealed the existence of basic structural units (BSU) in the highly disordered materials like PPP-based carbon. It is thought that the PPP-based carbons consist of small turbostratic particles, which have a few piled up poly-aromatic layers. The structure of the PPP-based carbon which seemed to be amorphous was estimated to have hexagonal carbon layers with the size of up to 1 nm. The pores in the PPP-based carbon seem to be clearances formed among the BSUs and amorphous carbon. The pore size of PPP-based carbon was estimated from the result of N₂ absorption measurement. The experimental results suggested that the lithium ion charge mechanism in the PPP-based carbon differs from that in graphite.      

X射线衍射的发现

简单介绍了埃瓦尔德(Ewald P P)、劳厄(von Laue M)和布拉格父子(Bragg W H及Bragg W L)在1912年发现X射线衍射方面的贡献．1911年埃瓦尔德在索末菲的指导下在慕尼黑大学从事博士论文研究，劳厄在与他的讨论中了解到晶格的平移周期与X射线的波长属于同一量级，因此想到在二维光栅的两个衍射方程组中再加一个类似的方程，就可以描述X射线在三维晶体中的衍射．在此假设的指导下，Friedrieh W和Knipping P在1912年4月开始用CuSO4后来用闪锌矿(立方ZnS)进行实验，很快就得到X射线衍射的证据．这不但证明了X射线的波动性，还确定了晶体的三维周期性．老布拉格在1912年夏得知这个消息，与他儿子小布拉格一道尝试用X射线的粒子性解释它，并由小布拉格在剑桥大学重复这个实验．根据衍射斑点的椭圆形状和从Pope与Below那里学到的晶格理论(由此得知ZnS具有面心立方晶格)，小布拉格将X射线在晶体中的衍射看作是X射线从一些晶格平面的反射，从而推导出著名的布拉格方程．布拉格父子开拓了X射线晶体结构分析这门新兴学科，从简单的无机化合物和矿物，逐渐发展到有机化合物和生物大分子．劳厄和布拉格父子分别强调慕尼黑和剑桥的优良科学环境对发现X射线衍射的重要性．鉴于埃瓦尔德在发现X射线衍射的作用及他后来在倒易格子及动力学衍射理论方面的贡献，不少晶体学家认为他也应获得诺贝尔物理奖．     

Synchrotron X-ray diffraction study of haüyne at high pressure

The compression behavior of a natural haüyne has been investigated to about 8.1 GPa at 300 K using in situ angle-dispersive X-ray diffraction and a diamond anvil cell at High Pressure Experiment Station, Beijing Synchrotron Radiation Facility (BSRF). Over this pressure range, no phase change or disproportionation has been observed. The isothermal equation of state was determined for the first time. The values of V₀, K₀, and K′₀ refined with a third-order Birch-Murnaghan equation of state are V₀=751.6±0.4 Å³, K₀=49±1 GPa, and K′₀=3.3±0.3, respectively.     

Be薄膜应力的X射线掠入射侧倾法分析

由于铍薄膜极易被X射线穿透, 传统的几何模式下很难获得有效的X射线衍射应力分析结果. 本文采用掠入射侧倾法分析SiO₂基底上Be薄膜残余应力, 相比其他衍射几何方法, 提高了衍射的信噪比, 获得的薄膜应力拟合曲线线形较好. 对Be薄膜的不同晶面分析, 残余应力结果相同, 表明其力学性质各向同性; 利用不同掠入射角下X射线的穿透深度不同, 获得应力在深度方向上的分布; 由薄膜面内不同方向的残余应力相同, 确定薄膜处于等双轴应力状态. 关键词： Be薄膜 X射线衍射 应力