Analysis of powder X-ray diffraction resolution using collimating and focusing polycapillary optics

Focusing X-ray optics can be used to increase the intensity onto small samples, greatly reducing data collection time. Typically, the beam convergence is restricted to avoid loss of resolution, since the focused beams broaden the resulting powder diffraction rings. However, with smooth Gaussian peaks, the resolution defined by the uncertainty in peak location can be much less than the peak width. Polycapillary X-ray optics were used to collimate and focus X-rays onto standard inorganic powder diffraction samples. Comparisons were made of system resolution and diffracted beam intensity with and without focusing and collimating optics using a standard small spot rotating anode system in point source geometry. The area detector and optics also allowed for the use of a low power 60 W source, without increasing either the collection time or the peak center error compared to the rotating anode no optic case. Resolution and intensity were in good agreement with those obtained from a simple geometrical model developed for the optics, which allows for system design and optimization for the desired sample characteristics. Foils and powders were used to model thin film samples while allowing both reflection and transmission measurements to more effectively verify theoretical modeling of beam parameters.     

New opportunities at the Materials Science Beamline at ESRF to exploit high energy nano-focus X-ray beams

A new end station for high energy (30–70 keV) X-ray diffraction experiments with nano-focus (150–500 nm) beam sizes has been installed at beamline ID11 at the ESRF. We review some of the early results from this instrument. High resolution crystal structure determination and refinement could be achieved with samples smaller than 3 μm in size. Near surfaces, the in-plane strain has been mapped as a function of depth in an oxide coating only 6 μm in thickness with 200 nm resolution. Via scanning diffraction tomography methods, then type-III intra-grain strain fields have been measured for fine-grained materials (<5 μm grain size). With the ESRF Extremely Brilliant Source upgrade (ESRF-EBS project), as well as new detectors coming online, we expect many new opportunities in the near future. Higher X-ray flux will bring about decreased scanning times, higher spatial resolution, and larger Q ranges. While scanning techniques can pose challenges for data reduction, they offer a new way to study a wide range of materials, and mapping of larger sample volumes at the highest spatial resolution becomes feasible.     

High resolution X-ray diffraction using a high brilliance source, with rapid data analysis by auto-fitting

In a production environment in particular, fast data collection and analysis, which are also highly reliable, are desirable. Measurement can be speeded up by increasing the diffracted intensity, thus reducing the time required to measure it reliably. Increased intensity with a smaller beam footprint at the sample have been achieved in a double-crystal diffractometer by the use of a novel ellipsoidal mirror working by total external reflection, positioned before the reference crystal. To optimise the performance of the mirror and provide high brightnesses, an X-ray source with a very small focal spot is required. Such a high brightness source has been made that uses electromagnetic focusing of the electron beam onto the target. Rapid data analysis is achieved by the use of an auto-fitting program that employs a genetic algorithm and the full dynamical theory of X-ray diffraction. Choice of an appropriate error function produces a deep global minimum while the genetic algorithm avoids convergence on local minima. From the model that produces the best fit, samples parameters such as layer thickness and alloy composition are extracted with quantified goodness of fit.     

High resolution X-ray diffraction studies of real structure of nearly perfect single crystals

Real structure together with composition and elemental purity of single crystals controls their properties. This paper reviews recent work carried out at the National Physical Laboratory on application of high resolution X-ray diffractometry, topography and diffuse X-ray scattering for direct observation and characterization of real structure of single crystals of silicon, gallium arsenide, diamond and LiNbO₃. A series of six multicrystal X-ray diffractometers have been designed, developed and fabricated indigenously. The most versatile of these systems is a five crystal X-ray diffractometer with state-of-the-art level resolution. These techniques and equipments have been applied in studying several interesting problems. Even in dislocation-free crystals of silicon, remarkable differences in the defect structure have been observed if the growth method was changed from float zone to Czochralski. Study of effect of externally applied electric fields and ion implantation on real structure of crystals has yielded interesting results. Images of ‘filaments’ which show nonhomogeneous distribution of electric current through semiconductors and insulators have been recorded for the first time in high resolution traverse topographs. Diffracted X-ray intensities could be modified by externally applied electric fields. It has been shown that implantation of BF ₂ ⁺ ions in silicon for producing shallow junctions does not produce homogeneous distribution of boron. The impurity is partially in clustered form. Biaxial stress introduced by thin depositions in substrate crystals are of considerable applied concern. The value and nature of stress have been determined in a number of systems. Typical results obtained on GaAs: multilayer metallizations are described. Also, degradation of perfection of substrates has been monitored. This work has shown that the stress is not homogeneously distributed and is quite anisotropic. A new high resolution X-ray diffraction technique has been developed for direct observation and study of forward diffracted X-ray beam and anomalous transmission of X-rays through ‘thin’ diamond crystals of varying degrees of perfection.     

Ellipsometer measurements using focused and masked beams

While optical spectroscopic measurements using ellipsometry may be made in air and are non-destructive, the relatively large (> 2 mm) spot size has limited their use to surface regions greater than 2 mm in lateral extent. Recent developments in focusing instruments have made spot sizes on the order of 20 to 25 μm possible. The work to be presented explores the use of the 25 μm spot size to probe non-uniform nanostructured thin films. Measurements were performed on a highly non-uniform film (0 to 2 μm in thickness across 4 mm in lateral dimension) using such a 25 μm spot. Further reduction of the spot size is possible using mechanical masking with a slit. Measurements have been made to the range of a few microns in width. The practical resolution limits of beam masking may be decreased by increasing incident light intensity, improving slit alignment, and improving detection methods.     

聚对苯二甲酸乙二酯轧制及加热过程中的织构研究

用X射线面探测器研究了半结晶态聚对苯二甲酸乙二酯(PET)在轧制和随后的加热过程中的织构变化.实验结果表明,PET的初始取向接近随机分布状态,轧制形变后的织构包括{100}<001>组分和不完全纤维织构(<001>∥轧制方向),并且形变量愈大,织构愈强;对轧制形变后的PET进行加热处理,发现上述织构组分增强,并且随加热温度升高和加热时间延长进一步增强.X射线平均衍射强度法计算PET结晶度的结果表明,结晶度在轧制形变后大幅下降,然后随加热温度升高和加热时间延长逐渐上升.分析认为,PET在轧制形变后的织构演化符合(100)[001]分子链滑动机制.     

Effect of heat treatment on characteristics of nanocrystalline ZnO films by electron beam evaporation

Zinc oxide thin films have been grown on glass substrate at room temperature by electron beam evaporation and then were annealed in annealing pressure 600 mbar at different temperatures ranging from 250 to 550 °C for 30 min. Electrical, optical and structural properties of thin films such as electrical resistivity, optical transmittance, band gap and grain size have been obtained as a function of annealing temperature. X-ray diffraction has shown that the maximum intensity peak corresponds to the (002) predominant orientation for ZnO films annealed at various temperatures. The full width at half maximum, decreases after annealing treatment which proves the crystal quality improvement. Scanning electron microscopy images show that the grain size becomes larger by increasing annealing temperature and this result agrees with the X-ray diffraction analysis.     

Expanded beam (macro-imaging) ellipsometry

Our aim was to make possible to use spectroscopic ellipsometry for mapping purposes during one measuring cycle (minimum one rotation period of polarizer or analyzer) on many sample points. Our new technique uses non-collimated (non-parallel, mostly diffuse) illumination with an angle of incidence sensitive pinhole camera detector system and it works as an unusual kind of imaging ellipsometry. Adding multicolour supplemets, it provides spectral (a few wavelengths on a 2D image or a full spectrum along a line) information from rapid measurements of many points on a large (several dm2) area. This technique can be expanded by upscaling the geometry (upscaling the dimensions of the instrument, and characteristic imaging parameters such as focal lengths, distances, etc.). The lateral resolution is limited by the minimum resolved-angle determined by the detector system, mainly by the diameter of the pinhole. (The diameter of the pinhole is a compromise between the light intensity and the lateral resolution.) Small-aperture (25 mm diameter) polarizers are incorporated into both the polarization state generator (PSG) and polarization state detection (PSD) components of the instrument.The detection is almost without background because the pinhole serves as a filter against the scattered light. One rapid measuring cycle (less than 10 s) is enough to determine the polarization state at all the points inside the illuminated area. The collected data can be processed very fast (seconds) providing nearly real-time thicknesses and/or refractive index maps over many points of the sample surface even in the case of multilayer samples. The speed of the measuring system makes it suitable for using even on production lines. The necessary (in each sample-point different) angle-of-incidence and the mirror-effect calibration are made via well-known and optimized structures such as silicon/silicon-dioxide samples. The precision is suitable for detecting sub-nanometer thickness and a refractive index change of 0.01.The method can be used for mapping and quality control in the case of large area solar cell table production lines even in a vacuum chamber with 5-10 mm lateral resolution.     

Metal organic chemical vapor deposition and investigation of ZnO thin films grown on sapphire

A new type of large area metal organic chemical vapor deposition (MOCVD) system for the growth of high quality and large size ZnO materials is introduced. Materials properties of the un-doped, n- and p-doped ZnO epi-films grown on sapphire substrates by this MOCVD system are studied by various techniques, including high resolution X-ray diffraction (XRD), UV-Visible optical transmission (OT), photoluminescence (PL) and photoluminescence excitation (PLE), synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS). The wurtzite (w) ZnO crystal structures grown with primary (0002) orientation were identified. Results have shown the high crystalline quality of MOCVD-grown ZnO films, indicated by the narrow XRD, PL and Raman line widths, strong PL signals, sharp OT edge and smooth surface. In particular, high p-type carrier concentration of > 10¹⁷ cm^− 3 have been achieved besides the good n-type doping in ZnO.     

Strain and temperature distribution in broad-area high-power laser diodes under operation determined by high resolution X-ray diffraction and topography

Broad-area lasers were investigated by high resolution X-ray diffraction (HRXRD) and topography, before and during laser operation. Rocking curves were taken at different positions of the 150 μm wide and 2 mm long laser stripe, using high-precision motorized slits with a spatial resolution of 40×40 μm². From the series of rocking curves recorded at different lateral positions and driving currents, the curvature and temperature profiles along the stripe could be estimated for different driving currents. X-ray topographs revealed regions with higher strain compared to the surrounding area. At lateral positions within the stripe, where the highest temperature was determined by HRXRD, regions of dark contrasts, indicating defects, were detected by cathodoluminescence. Transmission electron microscopy revealed that the highly strained regions act as sinks for point defects, since no dislocations or dislocation loops were detected. Thus, a clear correlation between temperature rise, high local strain and defect formation was found.     

InGaAsP/InP long wavelength quantum well infrared photodetectors

High quality InGaAsP/InP MQWs structures, grown by solid source molecular beam epitaxy, with different doping concentrations in the wells were investigated. High doping concentrations benefits absorption but is not good for dark current. The photocurrent spectra and peak values are sensitive to applied voltage. The total photocurrent comes from the electrons excited to two excited states. The decrease of the photocurrent peak value at high voltage can be explained by the reduction of photogenerated electrons. The detectivity of the InGaAsP/InP QWIP measured at a bias of − 2.5 V at 20 K is greater than , which is comparable to the GaAs/AlGaAs QWIPs.     

Energy-dispersive X-ray reflectivity and GID for real-time growth studies of pentacene thin films

We use energy-dispersive X-ray reflectivity and grazing incidence diffraction (GID) to follow the growth of the crystalline organic semiconductor pentacene on silicon oxide in-situ and in real-time. The technique allows for monitoring Bragg reflections and measuring X-ray growth oscillations with a time resolution of 1 min in a wide q-range in reciprocal space extending over 0.25-0.80 Å^− 1, i.e. sampling a large number of Fourier components simultaneously. A quantitative analysis of growth oscillations at several q-points yields the evolution of the surface roughness, showing a marked transition from layer-by-layer growth to strong roughening after four monolayers of pentacene have been deposited.     

Composition and crystallinity of silicon nanoparticles synthesised by hot wire thermal catalytic pyrolysis at different pressures

The effect of pressure on the structure and composition of silicon nanoparticles synthesized by hot wire thermal catalytic pyrolysis (HW-TCP) of pure silane has been investigated. Light brown powders were produced at silane pressures of 10 and 50 mbar, at a flow rate of 50 sccm, using a tungsten filament at temperatures of 1900 °C and 1800 °C respectively. As determined by transmission electron microscopy and X-ray diffraction, the particles produced at lower pressure have sizes around 10 nm, whereas those produced at higher pressure are typically 50 nm. High resolution transmission electron microscopy (HR-TEM) shows a surface layer of between 2 and 5 nm thickness, which was confirmed by X-ray photoemission spectroscopy to be an oxide shell. Both X-ray diffraction and HR-TEM confirm a high degree of crystallinity in both sets of particles, with Raman spectroscopy indicating an increase in crystalline fraction with synthesis pressure.     

Hydrogen sorption properties of MgH2–NiCo2O4 composites activated mechanically under argon and hydrogen atmospheres

The effect of the mechanical activation medium on the hydrogen absorption–desorption properties of MgH₂ with NiCo₂O₄ additives is investigated. The composite 90 wt.% MgH₂–10 wt.% NiCo₂O₄ mechanically activated for 180 min under hydrogen reaches a higher absorption capacity as compared to the composite ground for the same time in an argon medium. At T = 573 K and P = 1 MPa the composite activated mechanically in a reactive medium shows a value of 5.67 wt.% while for the composite ground under argon the value is 4.36 wt.% only, both samples preserving a high absorption capacity at temperatures below 573 K. Addition of nickel cobaltite is found to have a favorable effect on the hydriding kinetics of magnesium. In order to elucidate this effect, a composite containing a large amount of NiCo₂O₄ (50 wt.%) is also investigated.     

X-ray orientation microscopy using topo-tomography and multi-mode diffraction contrast tomography

Polycrystal orientation mapping techniques based on full-field acquisition schemes like X-ray Diffraction Contrast Tomography and certain other variants of 3D X-ray Diffraction or near-field High Energy Diffraction Microscopy enable time efficient mapping of 3D grain microstructures. The spatial resolution obtained with this class of monochromatic beam X-ray diffraction imaging approaches remains typically below the ultimate spatial resolution achievable with X-ray imaging detectors. Introducing a generalised reconstruction framework enabling the combination of acquisitions with different detector pixel size and sample tilt settings provide a pathway towards 3D orientation mapping with a spatial resolution approaching the one of state of the art X-ray imaging detector systems.     

Large-scale preparation of powder composites xNiO/(1-x)Al2O3 in reactions of solution combustion synthesis

The conditions for the production of composites by Solution Combustion Synthesis (SCS) from reaction solutions of aluminum and nickel nitrates of various concentrations with glycine have been studied. The concentration of reaction solutions increases the product yield and the productivity of SCS process. The effect of the presence of Al³⁺ cations in reaction solutions on the combustion reaction intensity reduction has been established. The SCS precursors contained metallic nickel, nickel oxide and amorphous alumina. The phase composition of the samples changed in the process of annealing: nickel oxidation, crystallization of γ-Al₂O₃ (600 °C) and formation of NiAl₂O₄ spinel (600–800 °C) were observed. The maximal specific surface area value recorded after annealing at 800 °C was 59–63 m²/g. In samples obtained with a lower fuel content, γ-Al₂O₃ or a mixture of γ-Al₂O₃ and NiAl₂O₄ crystallize on the surface of composite particles. The concentration of NiO on the surface of composites obtained from precursors synthesized from concentrated solutions at φ = 1.4 is close to the nominal composition.     

Investigation of the growth of In2O3 on Y-stabilized ZrO2(100) by oxygen plasma assisted molecular beam epitaxy

Thin films of In₂O₃ have been grown on Y-stabilised ZrO₂(100) substrates by oxygen plasma assisted molecular beam epitaxy over a range of substrate temperatures between 650 °C and 900 °C. Growth at 650 °C leads to continuous but granular films and complete extinction of substrate core level structure in X-ray photoelectron spectroscopy. However with increasing substrate temperature the films break up into a series of discrete micrometer sized islands. Both the continuous and the island films have excellent epitaxial relationship with the substrate as gauged by X-ray diffraction and selected area electron diffraction and lattice imaging in high resolution transmission electron microscopy.     

First experimental implementation of pulse shaping for neutron diffraction on pulsed sources

One of the central issues in the design and the use of pulsed neutron sources is the control of pulse length in elastic scattering experiments, most significantly diffraction on crystalline matter. On the existing short pulse spallation sources the strongly wavelength dependent source pulse length that determines the resolution is permanently fixed on each beam line by the type of the moderator it faces. We have experimentally implemented for the first time the wavelength frame multiplication (WFM) multiplexing chopper method, an earlier proposed variant of the by now fully tested repetition rate multiplication technique for inelastic scattering spectroscopy on pulsed neutron sources. We have operated the time-of-flight diffractometer at the continuous reactor source at BNC in an unconventional multiplexing mode that emulates a pulsed source. As a full proof of principle of the WFM method we have experimentally demonstrated the extraction from each source pulse a series of polychromatic, chopper shaped neutron pulses, which can continuously cover any wavelength band. The achieved 25 μs FWHM pulse length is shorter than that can be obtained at all at short pulse spallation sources for cold neutrons. The method allows us to build efficient, high and variable resolution diffractometers at long pulse spallation sources.     

On the structure and surface chemical composition of indium-tin oxide films prepared by long-throw magnetron sputtering

Structures and surface chemical composition of indium tin oxide (ITO) thin films prepared by long-throw radio-frequency magnetron sputtering technique have been investigated. The ITO films were deposited on glass substrates using a 20 cm target-to-substrate distance in a pure argon sputtering environment. X-ray diffraction results showed that an increase in substrate temperature resulted in ITO structure evolution from amorphous to polycrystalline. Field-emission scanning electron microscopy micrographs suggested that the ITO films were free of bombardment of energetic particles since the microstructures of the films exhibited a smaller grain size and no sub-grain boundary could be observed. The surface composition of the ITO films was characterized by X-ray photoelectron spectroscopy (XPS). Oxygen atoms in both amorphous and crystalline ITO structures were observed from O 1 s XPS spectra. However, the peak of the oxygen atoms in amorphous ITO phase could only be found in samples prepared at low substrate temperatures. Its relative peak area decreased drastically when substrate temperatures were larger than 200 °C. In addition, a composition analysis from the XPS results revealed that the films deposited at low substrate temperatures contained high concentration of oxygen at the film surfaces. The oxygen-rich surfaces can be attributed to hydrolysis reactions of indium oxides, especially when large amount of the amorphous ITO were developed near the film surfaces.     

Herstellung von Präzisionsschichten mittels Ionenstrahlsputtern

Precise thin film synthesis by ion beam sputter deposition Ion beam sputter deposition (IBSD) is a promising technique for the fabrication of high performance thin films because of the well defined and adjustable particle energies, which are rather high in comparison to other PVD techniques. Recent developments concerning long‐term stability and lateral uniformity of the ion beam sources strengthen the position of the IBSD technique in the field of precise thin film synthesis. Furthermore, IBSD offers a more independent choice of relevant deposition parameters like particle energy and flux, process gas pressure and deposition rate. In this paper we present our currently installed large area IBSD facility “IonSys 1600”, which was developed by Fraunhofer IWS Dresden and Roth & Rau company (Hohenstein‐Ernstthal). Substrate sizes of up to 200 mm (circular) or up to 500 mm length (rectangular) can be coated and multilayer stacks with up to six different materials are possible. Tailored 1‐ or 2‐dimensional film thickness distributions with deviations of < 0.1 % can be fabricated by a relative linear motion of the substrate holder above an aperture. In order to demonstrate the advantages of the IBSD technique especially for sophisticated materials and films with high requirements concerning purity, chemical composition or growth structure, several examples of deposited multilayers for various applications are presented.