Total reflection X-ray fluorescence spectrometry for quantitative surface and layer analysis

Measurements of X-ray fluorescence spectra versus grazing incident angles provide information on elemental composition as well as density and thickness of near surface layers. Calculations of fluorescence intensities are presented, which are used for the evaluation of data obtained by total reflection X-ray fluorescence (TXRF) spectrometry. The calculation is based on a matrix formalism to account for standing wave phenomena due to transmission and reflection in layered material. For the determination of concentrations the model makes additional use of the fundamental parameter technique in order to include absorption and enhancement effects of the fluorescence radiation. On the basis of experimental data some capabilities of this nondestructive and contactless probing technique are presented.     

Evaluation of Ni/Mn multilayer samples with glancing-incidence and take-off X-ray fluorescence analysis

A Glancing-Incidence and Take-off X-Ray Fluorescence (GIT-XRF) apparatus with which both incident angle of primary X-ray and take-off angle of fluorescent X-rays can be controlled has been newly developed for characterizing surfaces and interfaces. Using this apparatus, Ni/Mn multilayer samples were evaluated obtaining Take-off-Angle-Dependent X-Ray Fluorescence (TAD-XRF) curves at arbitrary incident angles of primary X-ray. In particular, we could obtain information on the near surface by measuring TAD-XRF curves at the incident angle less than the critical angle of total reflection for primary X-rays.     

Chemical analysis of semiconducting and metallic SmS thin films by X-ray photoelectron spectroscopy

We studied the chemical state of semiconducting and metallic SmS thin films by X-ray photoelectron spectroscopy (XPS), which were fabricated using dual-target magnetron sputtering by controlling the power applied to both metal and chalcogenide targets. On the basis of the valence band spectra obtained, it was suggested that semiconducting SmS has the final state corresponding to the Sm²⁺(4f⁶) configuration below the Fermi level, and metallic SmS has mainly the Sm³⁺(4f⁵) final state and a virtual band state in the Sm 5d band, contributing to the delocalization of 4f electrons and the emergence of metallic conductivity (4f⁶d⁰-4f⁵d¹). Thus, the spectra of our fabricated SmS thin films correspond to the band structure obtained from the dielectric property. This is the first work performed on the intrinsically prepared metallic SmS while the former works done for the sample transformed from semiconductor to metal phase by hard polishing.     

Refraction effect of scattered X-ray fluorescence at surface

The angular distribution of X-ray fluorescence shows anisotropic radiation. We proved that the origin of the anisotropic radiation is X-ray refraction by using a scattered X-ray fluorescence model. Utilizing the refraction effect of X-ray fluorescence, we can obtain much information: for example, surface density, chemical condition, surface roughness, and particle diameter of element, as a new tool of studying surfaces and interfaces. We introduce a new X-ray dispersive system utilizing X-ray refraction.     

Method of observation of low density interface states by means of X-ray photoelectron spectroscopy under bias and passivation by cyanide ions

X-ray photoelectron spectroscopy (XPS) measurements under bias can observe low density interface states for metal-oxide-semiconductor (MOS) diodes with low densities. This method can give energy distribution of interface states for ultrathin insulating layers for which electrical measurements cannot be performed due to a high density leakage current. During the XPS measurements, a bias voltage is applied to the rear semiconductor surface with respect to the ∼3 nm-thick front platinum layer connected to the ground, and the bias voltage changes the occupation of interface states. Charges accumulated in the interface states shift semiconductor core levels at the interface, and thus the analysis of the bias-induced shifts of the semiconductor core levels measured as a function of the bias voltage gives energy distribution of interface states. In the case of Si-based MOS diodes, the energy distribution and density of interface states strongly depend on the atomic density of silicon dioxide (SiO₂) layers and the interfacial roughness, respectively. All the observed interface state spectra possess peaked-structures, indicating that they are due to defect states. An interface state peak near the Si midgap is attributable to isolated Si dangling bonds at the interface, while those above and below the midgap to Si dangling bonds interacting weakly with Si or oxygen atoms in the SiO₂ layers. A method of the elimination of interface states and defect states in Si using cyanide solutions has been developed. The cyanide method simply involves the immersion of Si in KCN solutions. Due to the high Si-CN bond energy of ∼4.5 eV, the bonds are not ruptured at 800 °C and upon irradiation. The cyanide treatment results in the improvement of the electrical characteristics of MOS diodes and solar cells.     

X-ray photoelectron spectroscopy study of NiSi formation on shallow junctions

The influence of boron (B)/arsenic (As) on X-ray photoelectron spectroscopy (XPS) study of NiSi formation on shallow junctions is investigated in this paper. The Ni-silicide film was formed after 30 s soak anneal at 450 °C on ultra shallow p+/n or n+/p junctions. The atomic ratio of Ni/Si profile in depth was probed by XPS and the results show that a uniform NiSi layer forms on B-doped p+/n junction while a non-uniform, Ni-rich silicide layer forms on As-doped n+/p junction. It does not agree with the results of other independent phase identification methods such as X-ray diffraction, Rutherford backscattering spectroscopy, and Raman scattering spectroscopy, which all demonstrate the formation of NiSi on both n+/p and p+/n junctions. Comparing the raw binding energy spectra of Ni and Si for each silicide film, the similar spectra for Ni signals are revealed. But the Si signals with an obviously smaller intensity is found to be responsible for the apparent Ni rich silicide formation on As-doped n+/p junction. It indicates that As atoms in the silicide film can affect the sputtering yield of Ni and Si, while no noticeable effect is observed for B atoms. More As atoms than B atoms segregation into the silicide layer is indeed verified by secondary ion mass spectroscopy. And micro-Raman scattering spectroscopy further confirms that the degree of crystallinity for NiSi on n+/p junction is inferior to that on p+/n junction.     

Chemical effects in TiO2 and titanates due to bombardment with Ar+ and O 2 + ions of different energies (3.5-10 keV)

Compositional and chemical changes in TiO₂ and Ph, Ni, Al and Ba titanates induced by bombardment with Ar⁺ and O ₂ ⁺ ons of different energies have been studied quantitatively by XPS. An increase of preferential loss of oxygen and, in case of PbTiO₃, of lead has been observed when increasing the Ar+ ion energy from 3.5 to 10 keV. Because of oxygen loss, Ti⁴⁺ species reduce to Ti³⁺ and Ti²⁺. In addition, the loss of oxygen from PbTiO₃ and NiTiO₃ leads to the metallic state of nickel and lead, whereas aluminium and barium in Al₂TiO₅ and BaTiO₃ maintain their chemical state (i.e., Al³⁺ and Ba²⁺). Bombardment with OZ ions of PbTiO₃ and NiTiO₃ leads to a partial reduction of Pb and Ni. This metallization and the preferential loss of lead are more efficient at higher ion energies for both, O ₂ ⁺ and Ar⁺ bombardment. The results are discussed in terms of chemical stabilities and the possibility of oxygen diffusion in the bombarded oxides.     

Effects of surface roughness on surface analysis via soft and ultrasoft X-ray fluorescence spectroscopy

A model for calculating surface roughness effect on the intensity of emitted X-rays in the soft and ultrasoft X-ray region is presented and discussed. The results of calculations based on this model are compared to the results obtained experimentally using Al gratings as models for rough surfaces. It is shown that the correspondence between calculated and experimental intensities for Al–K is sufficient to corroborate the use of this model as a means of estimating maximum allowable surface roughness without a significant loss in intensity. It is also shown that this maximum allowable roughness estimate can be calculated with a knowledge of only the sample density and wavelength of the X-ray emission.     

Structure and dynamics of clean and adsorbate-covered crystal surfaces studied by surface X-ray diffraction

Received: 24 March 1998/Accepted: 21 August 1998     

Electrostatic forces in micromanipulations: Review of analytical models and simulations including roughness

Manipulations by contact of objects between 1 m and 1 mm are often disturbed by adhesion between the manipulated object and the gripper. Electrostatic forces are among the phenomena responsible for this adhesive effect. Analytical models have been developed in the literature to predict the electrostatic forces. Most models are developed within the framework of scanning probe microscopy, i.e. for a contact between a conducting tip and a metallic surface. Models are reviewed in this work and compared with our own simulations using finite elements modeling. The results show a good correlation. The main advantage of our simulations lies in the fact that they can integrate roughness parameters. For this purpose, a fractal representation of the surface topography was chosen through the use of the Weierstrass-Mandelbrot function. Comparisons with experimental benchmarks from the literature show very good correlation between experimental results and simulations. It demonstrates the importance of surface topography on electrostatic forces at very close separation distances.     

Influence of concentration gradients and surface roughness on measured reduced thicknesses of overlayers

In principle, one expects from a method for the determination of thicknesses of thin overlayers no angular dependence (take-off angle ϵ) of the results, which means d/λ = const. Earlier investigations, however, gave evidence for such a constant response of d/λ versus ϵ only up to about ϵ = 40 to 70° (depending on the value of d/λ) followed by a drop. This drop is explained by the finite solid angle of detection and elastic scattering of photoelectrons. As a concentration gradient exists in the interface, a horizontal portion (d/λ = const.) is only obtained for thick overlayers on thin interfaces. Surface roughness causes a restriction of the horizontal portion and in addition systematic errors.     

AFM lateral force imagining of modified polychloroprene: A study based on roughness analysis

Films of a binary polymer blends comprising polychloroprene (PCP) and piperylene-styrene copolymer (PSC) have been prepared by solution casting. The dependence of the surface morphology of the free blend films on PSC content was studied with both roughness and correlation analysis of lateral force microscopy (LFM) images. Significant changes in roughness and lateral parameter values of different blend film sides have been observed depending on the blend composition. It was shown that up to 15 wt.% PSC is distributed continuously in PCP bulk. The increase of roughness and lateral parameter values at the air/film surface shows the enrichment of PCP in the blends containing 25 wt.% or more PSC. The enrichment of PCP on the air/film surface favours the increase of PSC concentration at the backing/film surface. The films underside morphology becomes similar to that of PSC, when its content reaches 40 wt.%.     

Structure reorganization in polymer films of nafion due to swelling studied by scanning force microscopy

The surface morphology of dry and swollen Nafion films was investigated on the micrometer and nanometer scale by scanning force microscopy. The results show that the disordered network structure of dry films undergoes a reorganization process in the course of swelling and transforms into an ordered structure of parallel fibrils. No substantial changes in the fibril dimensions were found in the swollen state. This can be an indicator that swelling occurs at the supramolecular level.     

Application of total reflection X-ray fluorescence spectrometry for trace elemental analysis of rainwater

Applicability of total reflection X-ray fluorescence (TXRF) spectrometry for trace elemental analysis of rainwater samples was studied. The study was used to develop these samples as rainwater standards by the National University of Singapore (NUS). Our laboratory was one of the participants to use TXRF for this study. The rainwater sample obtained from NUS was analysed by TXRF and the trace elements Mn, Fe, Ni, Cu, Zn, V and Pb were determined as required by the NUS. The average precision was found to be within 16% and the TXRF-determined elemental concentrations of these elements were below 20 μg/l. The average deviation of TXRF-determined values from the certified values were 20% (excluding the deviation for Fe and V which were comparatively high). Apart from the above elements, S, K, Ca, Rb, Sr, Ba and Br were also determined by TXRF and were found to be in the range of 0.2 to 191 μg/l. TXRF-determined values of our laboratory played an important role in the certification of concentration of seven elements in this rainwater sample which was later developed as a rainwater standard.     

Depth profile and interface analysis in the nm-range

In modern technology, thin films are shrinking more and more to a thickness of few nanometers. Analytical investigations of such thin films using the traditional sputter depth profiling, sputtering in combination with surface-analytical techniques, have limitations due to physical effects especially for very thin films. These limitations are pointed out and some alternatives are discussed. Non-destructive analysis with angle-resolved X-ray photoelectron spectroscopy is demonstrated to be a useful method for such investigations. Both qualitative and quantitative results can be obtained even for complex layer structures. Nevertheless, there are also limitations of this method and some alternatives or complementary methods are considered.     

X荧光分析系列实验

介绍了能量色散X射线荧光分析的原理、应用以及用X荧光谱仪开设的系列实验。     

Electronic structure and interactions in well-defined coadsorbate layers

A synopsis of results and models for weakly and strongly interacting, well-defined coadsorbate systems is presented. Some experimental examples are given for various adsorbates on Ni(111) representing weak (different N₂ states, Ar/Xe+N₂) as well as strong (N₂+K) interaction. Models for coadsorbate interaction, in particular between molecules (CO, N₂) and alkali atoms, are discussed.     

Atomic Diffusion in Cu/Si （111） and Cu/SiO2/Si （111） Systems by Neutral Cluster Beam Deposition

The Cu films are deposited on two kinds of p-type Si （111） substrates by ionized duster beam （ICB） technique. The interface reaction and atomic diffusion of Cu/Si （111） and Cu/SiO2/Si （111） systems are studied at different annealing temperatures by x-ray diffraction （XRD） and Rutherford backscattering spectrometry （RBS）. Some significant results are obtained： For the Cu/Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs when annealed at 230℃. The diffusion coefficients of the samples annealed at 230℃ and 500℃ are 8.5 ×10^-15 cm^2.s^-1 and 3.0 ×10^-14 cm^2.s^-1, respectively. The formation of the copper-silicide phase is observed by XRD, and its intensity becomes stronger with the increase of annealing temperature. For the Cu/SiO2//Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs and copper silicides are formed when annealed at 450℃. The diffusion coefficients of Cu in Si are calculated to be 6.0 ×10^-16 cm^2.s^-1 at 450℃, due to the fact that the existence of the SiO2 layer suppresses the interdiffusion of Cu and Si.     

X-ray interface analysis of aperiodic Mo/Si multilayers

We present the non-destructive analysis of aperiodic Mo/Si multilayers by X-ray emission spectroscopy induced by electrons. The Si 3p occupied valence states of the silicon atoms present within these structures are analysed. Because of the great sensitivity of these states to the physico-chemical environment of the Si atoms, it is possible to distinguish the emission from the center of the Si layer (amorphous silicon) to that of the interfacial zones between the Mo and Si layers. Thus, the presence of molybdenum silicides is evidenced in the interfacial zones. It is also shown that the relative proportion of interfacial silicides depends on the deposition conditions.     

Quantitative analysis of thin samples by differential absorption imaging using a laser-plasma soft X-ray source

We consider the application of the differential absorption imaging technique in the soft X-ray region. The surface-density maps of test samples containing bromine, resulting from the application of the differential absorption imaging technique, are presented. Images of the samples were obtained in an X-ray monochromatic projection imaging scheme based on a spherically bent crystal using line emission close to the $L_2$ edge of bromine from a microplasma produced by focusing a nanosecond laser on the surface of an aluminum target.