Single-crystal Raman spectroscopy and X-ray crystallography at beamline X26-C of the NSLS

Three-dimensional structures derived from X-ray diffraction of protein crystals provide a wealth of information. Features and interactions important for the function of macromolecules can be deduced and catalytic mechanisms postulated. Still, many questions can remain, for example regarding metal oxidation states and the interpretation of `mystery density', i.e. ambiguous or unknown features within the electron density maps, especially at ～2 ? resolutions typical of most macromolecular structures. Beamline X26-C at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory (BNL), provides researchers with the opportunity to not only determine the atomic structure of their samples but also to explore the electronic and vibrational characteristics of the sample before, during and after X-ray diffraction data collection. When samples are maintained under cryo-conditions, an opportunity to promote and follow photochemical reactions in situ as a function of X-ray exposure is also provided. Plans are in place to further expand the capabilities at beamline X26-C and to develop beamlines at NSLS-II, currently under construction at BNL, which will provide users access to a wide array of complementary spectroscopic methods in addition to high-quality X-ray diffraction data.     

Quasi-universality and scaling behaviour of three-wave X-ray interference in crystals: A novel way for the quantitative determination of X-ray reflection phases

A quasi-universal function describing the intensity distribution of three-wave X-ray interaction in single crystals is derived for the first time from X-ray dynamical theory under the Bethe approximation for inversion-symmetry related reflections. The intensity distributions of three-wave interference can be scaled down to this dimensionless universal function with proper scaling factors. A newly derived intensity-ratio formula provides a new way of analyzing three-wave diffraction data for direct quantitative determination of X-ray reflection phases of complex systems involving macromolecules.     

一种点光源的自适应束斑X射线衍射仪的研制

为同时实现微米量级待测区域和毫米量级待测区域的物相分析,以及对表面不平整样品准确的物相分析,本实验室结合X射线衍射技术、CCD相机成像技术和毛细管微会聚X光调控技术,研制了一款能根据待测区域大小自适应调节照射X射线束斑直径的点光源X射线衍射仪Hawk-Ⅱ,其主要组成包括X射线源系统、六维联动运动系统、CCD相机、X射线探测系统和基于LabVIEW的软件控制系统.为验证设备的可行性,对表面不平整的人民币五角硬币进行分析,发现Hawk-Ⅱ测得的衍射图与标准PDF卡基本一致,而帕纳科X-Pert Pro MPD测得的衍射图最大偏移角度高达0.52°.对清代红绿彩瓷白釉和表面镀Cu,Fe的纳米材料采用不同直径的X射线束进行分析,发现白釉的晶体分布较为均匀,而纳米材料的表面镀膜不均匀.应用Hawk-Ⅱ分析一片西汉青铜,根据其锈蚀点的大小自适应调节照射X射线束斑直径,从而实现了物相的精确分析.由分析结果可知,Hawk-Ⅱ不仅拥有准确分析不规则样品的能力,而且拥有从微米级到毫米级待测区域的物相分析能力,并兼具能量色散X射线荧光分析功能,在诸多领域具有广泛的应用前景.     

Mo/Si多层膜小角X射线衍射结构表征

为了实现对Mo/Si多层膜的结构表征,测量了多层膜样品的小角X射线衍射谱。介绍了小角X射线衍射谱的分析方法,包括Bragg峰值拟合法,傅里叶变换法,反射谱拟合法。Bragg峰值拟合法和反射谱拟合法得到多层膜的周期厚度为7.09nm,两种模型的反射谱拟合法得到界面的粗糙度(扩散长度)为0.40～0.41nm(Si在Mo上),0.52～0.70nm(Mo在Si上),前者要比后者小,这与透射电镜法(TEM)得到的结果0.40nm(Si在Mo上),0.6～0.65nm(Mo在Si上)是一致的。通过基于扩散模型的反射谱拟合法得到的折射率剖面也与由高倍率透射电镜(HRTEM)积分得到的灰度值剖面在趋势上是一致的。通过X射线衍射谱和TEM图像对Mo/Si多层膜进行综合表征,得到了多层膜的精细结构信息,这对多层膜制备工艺的优化具有十分重要的意义。     

X-ray point- and line-projection microscopy and diffraction

A theoretical framework is presented to treat both imaging and diffraction experiments performed with point-focus and line-focus X-ray sources, with particular emphasis on two-dimensional and planar X-ray waveguides. In particular, point-projection and line-projection microscopy has been approached within the Huygens-Fresnel formalism; point-projection and line-projection diffraction, such as spatially-resolved Bragg/Laue diffraction of crystalline samples in a regime of dynamical scattering, has been treated both by means of the Huygens-Fresnel formalism and of the Takagi-Taupin dynamical theory. Both in point- and line- projection geometry, simply rotating the investigated crystalline samples, it is possible to switch from Fresnel self-imaging to Bragg/Laue diffraction conditions. This means to image, within the same experiment, either morphological features, with a sub-micrometric resolution, out of the exact diffraction condition, or the structure order on an atomic scale if placing the sample in diffraction.     

Advances in the histopathological characterization of breast tissue using combined X-ray fluorescence and X-ray diffraction data in a multivariate analysis approach

Previous studies have shown that the combination of X-ray fluorescence and X-ray diffraction data can be used as a histopathological characterization tool for breast tissue. Recent advances in energy-dispersive X-ray fluorescence techniques have allowed for benchtop systems to produce useful results in a reasonable time frame, allowing for clinical implementation to be realized. Using a polarized energy-dispersive X-ray fluorescence and energy-dispersive X-ray diffraction system optimized for measuring soft tissues, 38 breast tissue samples (19 normal and 19 diseased) were interrogated. The measured elemental concentrations and adipose and fibrous tissue contents were used in a principal component analysis study to determine the variables that produced the most differentiation between the normal and diseased tissues. For each sample, a soft independent modeling of class analogy technique was utilized to create classification models using the K, Fe, and Zn concentration and adipose and fibrous tissue content of all other breast samples. The class model produced from both X-ray fluorescence and X-ray diffraction data correctly classified 31 of 38 samples with no false positives or false negatives, showing improvement from solely X-ray fluorescence models or X-ray diffraction models alone, and demonstrates the usefulness of such a technique.     

Materials Research with X-ray Micro-beams at the Advanced Photon Source

X-ray scattering has had a rich and prominent place in the history of materials research. For samples that are large single crystals, X-ray diffraction provides very detailed, high-quality information about the atomic structure of almost every kind. However, most engineering materials are not a large single crystal, but mixtures of materials or a poly-crystalline material. Still, X-ray diffraction using X-ray beams significantly larger than the structures being investigated has produced much excellent information. Examples of this are powder diffraction, texture analysis, strain analysis, etc. While these types of analyses have been very useful in providing a microscopic understanding, they do not provide the microscopic information that we really want. What we really want to have is this useful X-ray diffraction information for every volume element in our sample; not just the diffraction information about small volume elements, but all of the volume elements, exactly where they are in our sample, and how each one diffracts. This detailed spatial and structural information is what is needed for a full understanding of the source of the properties that we find in engineering materials.     

X射线衍射进展简介

100年前,劳厄等证明X射线对硫酸铜晶体具有衍射能力,揭开了X射线衍射分析晶体结构的序幕.100年的发展,X射线衍射已经成为自然科学乃至医学、考古、历史学等众多学科发展的必备技术.文章介绍了X射线衍射现象的发现历史,X射线运动学和动力学理论的发展概况,并举例说明了X射线衍射在粉末多晶体、单晶体和人工功能晶体以及人工薄膜材料中的具体应用情况,最后简要展望了X射线衍射技术的发展前景.     

3D structure of dendritic and hyper-branched macromolecules by X-ray diffraction

The atomic ordering in dendritic and hyper-branched macromolecules has been determined by X-ray diffraction. The approach of the atomic pair distribution function technique has been used due to the lack of 3D periodicity in these polymeric materials. Dendrimers are found to possess a semi-regular structure riddled with nanosize cavities. The cavities are joined into channels connecting dendrimer's surface and core. In contrast, hyper-branched polymers are rather irregular at the atomic scale and with less accessible interior.     

Structure of crystalline and amorphous Ge probed by X-ray absorption and diffraction techniques

Results of experiments dedicated to the study of the structure under high pressure of amorphous Ge (a-Ge) and crystalline Ge (c-Ge) are reported. Energy-dispersive X-ray diffraction measurements of c-Ge have been collected at the DW11A beamline (DCI, LURE) using a heatable diamond anvil cell as pressure device up to 500?K. The a-Ge measurements have been performed at the ESRF, using the advanced set-up available at the BM29 beamline, which allows the simultaneous collection of X-ray absorption spectroscopy data and diffraction patterns used to monitor pressure and crystallization of a sample in a Paris–Edinburgh large-volume cell. The new structural data allowed us to obtain a reliable determination of the lattice parameters as a function of pressure and temperature in c-Ge and of the first-neighbor distance distribution in a-Ge.     

用X射线衍射仪验证康普顿效应的实验研究

充分利用多晶X射线衍射仪的衍射、单转、定时计数、叠扫等功能测量数据,采用3种实验测量方法验证了康普顿散射波长的位移公式,分析了不同测量方法对实验结果的影响.     

上海光源硬X射线相干衍射成像实验方法初探

相干X射线衍射成像方法是一种先进的成像技术,分辨率可达纳米量级.国际上大多数的同步辐射装置和自由电子激光装置都建立了该成像方法,并有将其作为主要成像技术的趋势.上海光源作为目前国内唯一的一台第三代同步辐射光源,尚未建立基于硬X射线的相干衍射成像实验平台.随着一批以波荡器为光源的光束线站投入使用,使得该方法的建立成为了可能.本文基于上海光源BL19U2生物小角散射线站,通过有效的光路设计,搭建了相干衍射实验平台,在12 keV和13.5 keV能量点均获得了硬X射线相干光束,并基于小孔衍射测量了入射光束的空间相干长度.该平台支持常规和扫描相干衍射实验模式,对小孔衍射图样及波带片扫描衍射图样实现了正确的相位重建,证明了该平台初步具备开展硬X射线相干衍射成像实验的能力.硬X射线相干衍射成像实验平台为国内首次建立,将为国内该实验方法的发展和应用提供有效的软硬件支持.     

Modelling interdiffusion in epitaxial multilayer structures using X-ray simulation techniques

The analysis of X-ray diffraction data forms an important non-destructive technique for the study of interdiffusion in multilayer structures. A frequently used approach is that of Fleming et al. in which the characteristic X-ray diffraction satellites from a superlattice structure are shown to be related to the corresponding Fourier components of the real space composition modulation. This relationship is derived assuming the strain to be small although the limitations on this parameter are unclear. To clarify this limitation the Fleming technique has been tested for a range of x values, and hence strain, using as examples a series of model multilayer CdTe:Cd_1-xMn_xTe structures. The approach has been to use a simulation technique based on the kinematical theory of X-ray diffraction to model the X-ray rocking curves from a series of structures in which the Mn diffusion profiles had been calculated using a particular value of the diffusion coefficient D. The values of the diffusion coefficient, derived from the diffraction data using the Fleming method, agree with the input D at low x values but differ for high x, high strain, structures and a criterion is suggested for the range of validity of the method.     

An X-ray diffraction study of liquid chlorine

The static structure of liquid chlorine at room temperature is investigated by means of X-ray diffraction. From comparisons with previous neutron and X-ray data, it appears that most of the discrepancies present in the liquid structure factor between neutron and X-ray studies have been removed. Some experimental difference in the two structure factors still remains and one possible explanation is that the electron density distribution of liquid chlorine differs from that derived within the independent atom approximation.     

On the possibility of determining the structure of proteins in experiments using X-ray free electron lasers in the nonstationary scattering mode

The problem of determining the structure of proteins by X-ray analysis using X-ray free electron lasers at pulse intensities several orders of magnitude higher than those achieved to date is considered. In this case, due to radiation damage, the sample loses a significant fraction of its electrons during the pulse, so the scattering occurs in the nonstationary mode. In the present study, simulations are used to determine the resulting specific features of the diffraction data that should be taken into account in analysis, which, however, do not preclude determining the 3D structures. Estimates of the achievable resolutions show the prospect of using the nonstationary scattering mode for determining the structure of the most complex objects, such as large, poorly crystallizable proteins and complexes with a high resolution.     

Multiwavelength anomalous diffraction at high x-ray intensity

The multiwavelength anomalous diffraction (MAD) method is used to determine phase information in x-ray crystallography by employing anomalous scattering from heavy atoms. X-ray free-electron lasers (FELs) show promise for revealing the structure of single molecules or nanocrystals, but the phase problem remains largely unsolved. Because of the ultrabrightness of x-ray FEL, samples experience severe electronic radiation damage, especially to heavy atoms, which hinders direct implementation of MAD with x-ray FELs. Here, we propose a generalized version of MAD phasing at high x-ray intensity. We demonstrate the existence of a Karle-Hendrickson-type equation in the high-intensity regime and calculate relevant coefficients with detailed electronic damage dynamics of heavy atoms. The present method offers a potential for ab initio structural determination in femtosecond x-ray nanocrystallography.     

X-ray diffraction diagnostics methods as applied to highly doped semiconductor single crystals

Si(As, P, B) and GaSb(Si) single crystals are used as examples to demonstrate the possibilities of methods of X-ray diffraction for the diagnostics (examination of a real structure) of highly doped semiconductor crystals. Prominence is given to characterizing the state of impurity: whether it is in a solid solution or at a certain stage of its decomposition. An optimum combination of X-ray diffraction methods is found to obtain the most complete information on the microsegregation and structural heterogeneity in crystals with low and high X-ray absorption. This combination is based on X-ray diffraction topography and X-ray diffractometry methods having an increased sensitivity to lattice strains.     

X-ray diagnostics of semiconductor heterostructures: Some achievements and perspectives for development

Possibilities of new approaches for the interpretation of X-ray scattering data to characterize heterostructures with nanosized layers are demonstrated. These approaches are based on both simultaneous mathematical analysis of the experimental data of X-ray rocking curves from several crystallographic planes of the sample and joint processing of the experimental data of X-ray diffraction and reflectometry. Measurements are taken using the same device with the advanced technique of experiments. In the approaches proposed, the volume of the experimental information on one sought parameter increases significantly, which provides a greater reliability of reconstructing the structural parameters of the object under study. A mathematical apparatus is developed along with the software to solve the inverse problem with a large amount of input data and sought parameters. The proposed approaches are tested on nanosized Al_xGa_1-xAs/In_yGa_1-yAs and In_xAl_1-xAs/In_yGa_1-yAs heterostructures grown on GaAs and InP substrates, respectively. It is shown that the complex X-ray method allows a reliable determination of relationships between the real structure and electrophysical properties, and thus an improvement of the technology for producing these objects with predicted properties.     

Interfacial structure analysis of polymer laminate using SPring-8 X-ray microbeam

Interfacial structure of laminated polyethylene (PE)/polypropylene (PP) films was investigated by synchrotron X-ray microbeam. The X-ray microbeam (0.9 μm (vertical) × 1.7 μm (horizontal)) formed using a phase zone plate was irradiated on the cross-section of the laminated films. In order to irradiate X-ray microbeam in the direction perpendicular to the cross-section of the film sample, adjustment of the sample setting was performed by Thomson scattering method. The Thomson scattering intensity is proportional to the number of the irradiated electrons, so the irradiated position of the X-ray microbeam could be determined from the intensity profile with high spatial resolution. By changing the sample position, diffraction patterns could be obtained from the laminated films across the PE/PP interfacial region. The thickness of the interfacial region of the annealed laminate was estimated as 5 μm judging from the changes of the diffraction intensities from the PE crystallites to the PP ones. The interfacial thickness depended on the thermal treatment of the film. It was found that the adhesion strength of the PE/PP laminate increased with increasing the interfacial thickness. Both of PE and PP chains entangled each other during laminate processing. The entangled molecular chains play important role as anchoring effect at the PE/PP interdiffusion region. However, the phase separation progressed with further crystallization by annealing. Thus, the adhesion strength of the PE/PP laminate was considered to be influenced by the interfacial thickness.