Grazing-incidence X-ray analysis techniques which are commonly used for the nondestructive characterization of surfaces and thin films are reviewed. The X-ray reflectivity technicue is used to study surface uniformity and oxidation, layer thickness and density, interface roughness and diffusion, etc. The grazing-incidence in-plane diffraction technique is used to determine in-plane crystallography of epitaxial films. The grazing-incidence asymmetric-Bragg diffraction is used for surface phase identification and structural depth profiling determination of polycrystalline films. Typical examples to illustrate the types of information that can be obtained by the techniques are presented.

Ila group metal - Zr pcrovskitc type compounds (MZrO3, M=Ba. Sr and Ca) and other oxides were studied by XPS to know the effects of M atoms to Zr atoms. And the feasibility of using XPS and high-resolution XRF for the coordination analysis of Zr atoms was examined for some kinds of stabilized zirconia. An almost linear relationship between the energy of Zr 3d peaks and the radii of Ila group metal ions was found, and, a simple model to interpret this relationship has been proposed. However, no relationship between the energy shifts of Zr 3d spectra or Zr Lα1, 2 spectra and the coordination numbers of Zr atoms in the several Zr oxide compounds was found. Thus, the coordination analysis using XPS or high-resolution XRF is not feasible.

The structural characterization of thin films is important for research development and manufacturing of electronic, magnetic, optical, and other high-tech materials. The grazing incidence X-ray diffraction technique has bean used successfully for the determination of crystalline phases, structural-depth profiles, crystallite size, and strain, etc. of thin films with thickness's down to a few tens of Å, If the crystal structure, e.g. the distribution of atoms in the unit cell, or the crystallinity and texture (or preferred orientation) of a film is of interest, the conventional Bragg-Brentano diffractometer technique with the θ-2θ scanning geometry has been found to be appropriate.

The depth range d of x-ray photoelectron spectrometry (XPS) is determined by the inelastic mean free path λ of photoelectrons . The following considerations are dedicated to a correlation between d and λ.

This review will attempt to show how XPS now makes an important contribution to Materials Science and to highlight the developments which have brought it to this position. XPS is now a mature technique for surface analysis but it has in addition a major role as a specialised tool, being essential to studies in which derivitization methods are used to tag surface groups.

The requirements of users in this field have led to the development of X-ray sources which were not envisaged in the early development of the spectroscopy. The usual sources of aluminium Kα and magnesium Kα have limitations for those elements beyond magnesium in the periodic table which would have the Is lino as the principal peak - aluminium, silicon, oulphur and phosphorus for example. Higher energy sources such as silicon Kα or zirconium and silver Lα have made it possible to utilise the Is lines up to chlorine and have the additional advantage that a strong and well resolved series of Auger lines also becomes available. The higher energy radiations are thus particularly suited to the determination of relaxation energies in materials by use of relative shifts between the photo- and Auger lines of the spectrum. Such has been the utility of such relaxation energies that use is often made of Auger lines derived from the Bremmstrahlung component of the normal x-ray sources to make a similar measurement. This measurement is used in the study of insulating ceramics in which electrostatic charging makes measurement of binding energies uncertain.

Modern materials technology is particularly concerned with the manufacture of composites; particulate, fibre and laminate composites are all well known and the key to their success often lies within the interface between the phases. Transfer of load across the interface places particular requirements on adhesion at the phase boundary and an understanding of the locus of failure during destructive testing is crucial to the development of satisfactory bonding processes. In coated and laminated products there is no problem in the use of XPS, with its excellent chemical sensitivity but there is a problem of increasing magnitude in fibre and particulate composites as the substructures become finer. This stems, of course, from the difficulty of providing a focused source of X-rays of sufficient magnitude. Imaging XPS is slowly becoming a reality with several systems having a capability of 10μm now available, and one of the markets for such instruments is that of composite materials.

There are important areas of Materials Science in which XPS has been displaced by other techniques such as SIMS. One such area is that of polymer surface analysis. The selectivity of XPS for substituent groups in the surface region is not good. Derivitization methods have made an impact, enabling acidic or basic groups to be determined, but SIMS, which has the ability to detach molecular clusters, has obvious advantages which will become increasingly exploited aa the problems of charging become solved. Until then however XPS will continue to find a role in polymer research and development.

The use of grazing incidence parallel beam x-ray diffraction (GIXRD) in the characterization of lead zirconate titanate (PZT) films is described. This tool has enabled us to depth profile the films. The transmission electron microscopy (TEM) results obtained from a cross section of one film are shown to compliment the GIXRD results. The variation in crystallographic structure versus depth in the film was the primary focus of this study.

The insults from three PZT films having Zr/Ti ratios of 25/75, 48/52, and 75/25 are given. TEM results are reported from the sample with a Zr/Ti ratio of 48/52.

Depth profile analysis of phase composition, residual strain and crystallite size in ceramic specimens can be determined by varying the information depth (ID) as defined by Delhez et al. (1988) for an x-ray opaque specimen. The information depth may be controlled by making use of the dependence of ID on Bragg angle and by selecting wavelengths which give appropriate x-ray absorption within the specimen.

Procedures are outlined for extracting depth profiles for (i) composition from intensity data and (ii) residual strain and crystallite size from peak width data. Results are described for both discrete-peak and Rietvetd pattern-fitting analysis of zirconiaalumina specimens for which preliminary results have been reported by van Riessen et al. (1990).

X-ray excited Photoelectron Spectroscopy (XPS) has become an indispensable tool for the study of metals and semiconductors. Due to the small mean free path of the photoelectrons In solids of the order of a few nanometers for energies in the keV range, it is a surface analysis technique. Its capability of quantitative analysis of all elements except hydrogen and helium and their chemical bonding states has recently been combined with small area and imaging analysis to typical spatial resolutions of about 10 μm. After a brief survey of the basic capabilities and limitations of XPS, some illustrative examples in typical metals and semiconductor research areas are presented, such as surface contamination and failure analysis in microelectronics, oxidation and corrosion, segregation at surfaces and interfaces, oxide/metal and oxide/semiconductor interfaces, and thin film analysis using angle resolved XPS and sputter depth profiling. Recent developments emphasize improved data evaluation and quantification schemes as well as instrumental capabilities with respect to both high spatial and energy resolution, and high power excitation sources such as synchrotron radiation.

For the application of TXRF in trace element analysis, two characteristic features of the total reflection of X-rays are exploited. These are the high reflectivity on flat surfaces and the low penetration depth of the primary radiation. This allows the application of TXRF for both chemical trace and ultra-trace element analysis on the one hand and surface analysis on the other. For chemical trace clement analysis, total reflection on a highly polished substrate is characterized by a high reflectivity, which leads to a drastic reduction of the spectral background. The sample to be analyzed is prepared on the substrate as a residue of small quantities by evaporation from solutions or fine-grained suspensions. Instrumental detection limits of a few pg or sub-ng/ ml−1 arc state of the art for commercially available equipment. Besides the high detection power, internal standardization is another important feature of TXRF, enabling very simple quantification of the detected elements. The small sample mass required enables especially ultra-micro analytical questions to be tackled. For trace element analysis in surfaces the low penetration depth of the primary radiation under the conditions of total reflection is exploited. The penetration depth is in the range of a few nanometers, hence, TXRF is intrinsically surface sensitive. Detection limits better than 1010 atoms/cm2 are obtained for metal impurities on silicon wafers. For the examination of layered structures elemental composition, layer thickness, and density can be derived from die angle-dependent fluorescence intensities. The present paper describes the basic features of the total reflection of X-rays and gives some representative examples of the different uses of TXRF in trace element analysis.

The evaluation and understanding of the x-ray diffraction properties of multilayer structures is critical in predicting the degree of success in their utilization in x-ray optics applications. A key material parameter affecting the diffracting efficiency of multilayer structures is the roughness of the interfaces between the deposited layers. This paper will use measured roughness to predict the integral reflection coefficient as a function of diffraction order for several multilayer structures.

We have made atomic force microscope (AFM) measurements of the detailed displacement distribution for me surface roughness of W/C and W/Si multilayer structures. This information has been introduced into a theoretical model to predict the reduction of the integral reflection coefficient induced by surface roughness. In a fashion analogous to the Debye-Waller factor, this reduction in diffracted intensity is predicted to be strongly dependent on the diffraction order. These predictions have been compared with experimental integral reflection coefficient data. The measured diffraction results indicate a greater reduction in reflection than is predicted by the AFM measurements. A possible explanation for this discrepancy is that the AFM measurements underestimate the roughness. Possible reasons for the differences between these methods will be discussed.

Improving the detection limits in TXRF by optimizing the excitation conditions is the goal of this work. The properties of the exciting radiation due to spectral distribution, polarisation, intensity and energy are investigated and compared to find best conditions. Results are given from experiments performed with synchrotron radiation, Bragg polarized monoenergetic x-rays, high energy cut-off reflector in the primary beam path of a high power x-ray tube and several geometries for the sample reflector.

The pioneering work of Marra, Eisenberger and Cho (1979) demonstrated that powder diffraction from near surface and interfacial regions could be obtained using glancing incidence geometry. This has generated considerable interest in research at synchrotron sources, but also several slit attachments have been developed for commercial diffractometers. By adding a focussing mirror, we demonstrate here a simple arrangement that produces adequate intensity with a sealed tube to examine ultra thin films.

We have studied a series of laminated thin films by x-ray diffraction to correlate their structural and magnetic properties. Previous works have shown that the signal-to-noise characteristics of laminated magnetic films with non-magnetic interlayers can exceed that of single layer magnetic films. In the case where the magnetic layer is known to have low signal-to-noise performance, the signal has been observed to increase as the number of layers whereas the noise increases as the square root of the number of layers. This yields a net improvement of the signal-to-noise ratio, making the overall film more attractive as a magnetic recording medium. In this paper, we investigate films which are laminated layers of magnetic CoPtCr and non-magnetic Cr. The films were deposited with sputtering parameters that generally give low noise characteristics in single layer films. Up to four layers of CoPtCr films were made with Cr spacer layers of 2 nm. We observe some improvement in signal-to-noise characteristics and reduction in coercivity. X-ray diffraction analysis shows that the crystallographic c-axis, which corresponds to the magnetic easy axis, becomes more preferentially oriented perpendicular to the film plane with each additional layer. This change in preferred orientation is consistent with the reduced in-plane coercivity of the film. In the double CoPtCr layer with one Cr spacer layer experiment, we see that as the Cr spacer layer is increased from 0.5 to 8 nm, the c-axis of the CoPtCr again becomes more preferentially oriented out of the film plane, resulting in decreased in-plane coercivity. The media signal-to-noise improves once the Cr spacer layer is beyond 2 nm, consistent with previous observations.

This article describes the instrumentation for a total reflection fluorescent x-ray spectrometer. The reflecting intensity and the angular divergence were studied with respect to various kinds of monochromators. Using silicon wafers, the angular divergence effect of the incident beam, surface roughness influences and the smoothing of background x-ray intensity for the improvement of the lower limit of detection were investigated.

Total Reflection X-ray Fluorescence Spectrometry (TXRF) has been used for the characterisation of a 20 nm thick Ni/Fe/Cr-layer on a silicon substrate. Instrumental aspects of the technique as well as the data evaluation procedure on the basis of modelling calculations are outlined in this paper. The effect of standing waves is discussed by means of the selected example. This particular layer serves also as an illustration of the capabilities and limitations of TXRF. At least three surface parameters are covered by the technique, elemental composition, density and layer thickness.

This is a report of an investigation by XRD and SEM of thin coatings such as are applied by plasma spray methods for improving properties, such as are wanted in electronic devices, and for increasing durability in service. Samples were studied that had been coated under controlled conditions: Physical Vapor Deposits (PVD) of titanium nitride on steel plate and plasma spray coatings of molybdenum on steel plate. X-Ray determinations were made of x-ray lattice constants, crystallite size, lattice strain, orientation and residual stress, before and after strain was applied to the specimens.

Total Reflection X-Ray Fluorescence Analysis (TXRF) has become a powerful analytical tool for trace element analysis. Because of its advantages in excitation and background reduction TXRF has been applied for the analysis of light elements (C,O,F,Na,...). A special Ge(HP) detector offering an ultra thin window in combination with a spectrometer specially designed for the requirements of light element analysis was used. Also a new windowless X-ray tube for efficient excitation of the light elements was tested. The system was checked with standard aqueous solutions; detection limits in the ng range (7 ng for O) are obtained.

Many analytical problems cannot be solved using a single XRD measurement. One example is the epitaxial growth of thin films of High Tc superconductors. To fully characterise such a sample it is necessary to study both the orientation (texture) and the phase composition of the layer.

Thin films of BaTiO3 and Pb(Zr53 Ti47)O3 (PZT) have been deposited on Pt and Pt-coated silicon substrates using both Nd-YAG and excimer lasers. The BaTiO3 films were prepared using heated substrates and were crystalline. The PZT films were deposited at room temperature and were amorphous; on annealing, they crystallized and gave rise to well-defined powder x-ray diffraction patterns.

To compare and correlate the properties and processing conditions of these thin films, characterizations were performed using a variety of analytical techniques including x-ray diffraction, TEM, SEM/EDX and ferroelectric and dielectric property measurements. The x-ray diffraction technique was used for identifying the various phases formed and also for analyzing the profiles of the diffraction peaks. Both the PZT films annealed below 800°C and the BaTiO3 films typically show polycrystalline x-ray diffraction patterns corresponding to a pseudo-cubic structure (i.e no peak splitting) instead of the tetragonal patterns characteristic of the target materials. It was found that for the BaTiO3 films the pseudosymmetry was due to crystallographic alignment of the longer c-axis In the substrate surface to relieve strain. In the FZT films annealed below 900°C, it is suggested that the residual surface strain and/or small crystallite size of these materials may have precluded the peak splitting; at higher annealing temperatures, the tetragonal symmetry was recovered.

In the framework of interdisciplinary research projects TXRF has been applied for multielement analysis of rainwater, size-fractionated airborne particulates, throughfall samples and litter fall in forests, soil solutions, seepage water, river water filtrates and suspended particulate matter. Essential aspects of sample preparation techniques are briefly described. Some results are given on trace element fluxes in a forest ecosystem and on contaminant transport phenomena in estuaries in order to demonstrate the outstanding capabilities of TXRF in demanding environmental research projects.