A. Kubala-Kukuś

Application of the high-resolution grazing-emission x-ray fluorescence method for impurities control in semiconductor nanotechnology

We report on the application of synchrotron radiation based high-resolution grazing-emission x-ray fluorescence (GEXRF) method to measure low-level impurities on silicon wafers. The presented high-resolution GEXRF technique leads to direct detection limits of about 1012 atoms/cm2. The latter can be presumably further improved down to 107 atoms/cm2 by combining the synchrotron radiation-based GEXRF method with the vapor phase decomposition preconcentration technique. The capability of the high-resolution GEXRF method to perform surface-sensitive elemental mappings with a lateral resolution of several tens of micrometers was probed.

Multiple ionization effects in low-resolution X-ray spectra induced by energetic heavy ions

Abstract The method of analysis of the multiple ionization effects in low-resolution X-ray spectra induced by heavy ions is described here. It is shown that, by fitting the X-ray spectra measured by a semiconductor detector with the proposed model, which accounts for the multiple ionization effects, the ionization probabilities can be determined as free fitting parameters. This approach is based on the assumption that the intensity distribution of emitted X-ray satellites is approximately described by the binomial distribution parameterized by the ionization probability at the moment of X-ray emission. In particular, we demonstrate that the excited X-ray satellites, when measured by a low-resolution semiconductor detector, appear as the Gaussian profile, which is shifted and broadened with respect to the diagram line. Moreover, we find that both X-ray line shift and width are expressed in terms of the multiple ionization probabilities, as well as the X-ray energy shifts per vacancy. These observations allowed to develop a novel method of X-ray spectra fitting. Detailed discussion of the approximations used in the present approach is given. The method developed, using the calculated Dirac–Fock X-ray energy shifts per vacancy, was applied to determine the multiple ionization probabilities in M- and N-shell by fitting the measured X-ray spectra for L γ (L→N,O) transitions induced by heavy ions in selected high-Z atoms.

PIXE and XRF analysis of honey samples

Abstract The systematic determination of trace-element concentrations in honey samples was done by the PIXE method using a 2 MeV proton beam and by the total reflection XRF method. The different kinds of honey samples were collected in the period of spring–summer in three places of Poland: in the centre of Warsaw (a highly polluted region) and about 100 km east of Warsaw and 70 km southwest of Warsaw (as regions free from industrial and transport pollution). The measured samples have shown that the concentrations of trace elements are similar in the honey samples from these places.

Analysis of Copper Concentration in Human Serum by Application of Total Reflection X-ray Fluorescence Method

The chemotherapy and photon radiotherapy are the most often applied methods in treatment of the cancer diseases because of their effectiveness and high cure rates. Apart from eligible destruction of the tumour, one of the side effects of these treatment methods is possible modification of main and trace element concentration in different human tissues and fluids. In this paper, the copper (Cu) level in human serum was determined by total reflection X-ray fluorescence method in 142 chemotherapy patients and in 44 healthy persons being a control group. The Cu concentration in the chemotherapy group was found to be on the level 1.78 ± 0.909 mg/L, while in the control group, it was 1.08 ± 0.551 mg/L. Performed measurements allowed for calculation of the parameters of copper concentration distribution (mean value, standard deviation, median) for both analysed groups. The theoretical nature of the concentration distribution was tested and found as a log-normal distribution (control group) and a log-stable distribution (chemotherapy group). The copper concentration distributions for both studied group were statistically compared using Kolmogorov-Smirnov test, and the conclusion was that the distributions are statistically different. Serum Cu levels were significantly higher in the chemotherapy group than in the control group. Taking into account the results for the control group, the copper concentration reference quantile ranges in human serum were obtained. The values of the mean, median and other quantiles determined in this case can be applied in two-group comparison studies. The obtained results can be used as a diagnostic tool for chemotherapy patients.

Depth profiling of low energy ion implantations in Si and Ge by means of micro-focused grazing emission X-ray fluorescence and grazing incidence X-ray fluorescence

Depth-profiling measurements by means of synchrotron radiation based grazing XRF techniques, i.e., grazing emission X-ray fluorescence (GEXRF) and grazing incidence X-ray fluorescence (GIXRF), present a promising approach for the non-destructive, sub-nanometer scale precision characterization of ultra shallow ion-implantations. The nanometer resolution is of importance with respect to actual semiconductor applications where the down-scaling of the device dimensions requires the doping of shallower depth ranges. The depth distributions of implanted ions can be deduced from the intensity dependence of the detected X-ray fluorescence (XRF) signal from the dopant atoms on either the grazing emission angle of the emitted X-rays (GEXRF), or the grazing incidence angle of the incident X-rays (GIXRF). The investigated sample depth depends on the grazing angle and can be varied from a few to several hundred nanometers. The GEXRF setup was equipped with a focusing polycapillary half-lens to allow for laterally resolved studies. The dopant depth distribution of the investigated low-energy (energy range from 1 keV up to 8 keV) P, In and Sb ion-implantations in Si or Ge wafers were reconstructed from the GEXRF data by using two different approaches, one with and one without a priori knowledge about the bell-shaped dopant depth distribution function. The results were compared to simulations and the trends predicted by theory were found to be well reproduced. The experimental GEXRF findings were moreover verified for selected samples by GIXRF.

Concentration distribution of trace elements: from normal distribution to Lévy flights☆

The paper discusses a nature of concentration distributions of trace elements in biomedical samples, which were measured by using the X-ray fluorescence techniques (XRF, TXRF). Our earlier observation, that the lognormal distribution well describes the measured concentration distribution is explained here on a more general ground. Particularly, the role of random multiplicative process, which models the concentration distributions of trace elements in biomedical samples, is discussed in detail. It is demonstrated that the lognormal distribution, appearing when the multiplicative process is driven by normal distribution, can be generalized to the so-called log-stable distribution. Such distribution describes the random multiplicative process, which is driven, instead of normal distribution, by more general stable distribution, being known as the Levy flights. The presented ideas are exemplified by the results ´ of the study of trace element concentration distributions in selected biomedical samples, obtained by using the conventional (XRF) and (TXRF) X-ray fluorescence methods. Particularly, the first observation of log-stable concentration distribution of trace elements is reported and discussed here in detail. 2003 Elsevier Science B.V. All rights reserved.

EFFECT OF TEMPERATURE ON HALLOYSITE ACID TREATMENT FOR EFFICIENT CHLOROANILINE REMOVAL FROM AQUEOUS SOLUTIONS

Monochloroanilines and dichloroanilines are important reagents or chemical intermediates in the production of dyes, pharmaceuticals, and agricultural chemicals. These toxic compounds have a large tendency to accumulate in the environment and a low natural biodegradability, so improved methods to remove or sequester them are needed. Halloysite is used as an efficient adsorbent to remove toxic compounds, such as aniline, from aqueous solutions. The purpose of this study was to evaluate whether acid-activated halloysites from the “Dunino” (Poland) strip mine could be effective in the removal of not just aniline but also of its chloro-substituted forms from aqueous solutions. The composition, structure, and morphology of activated halloysites were characterized using the following methods: wavelength dispersive X-ray fluorescence analysis (WDXRF), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), Fourier-transform infrared spectroscopy (FTIR), and N2 adsorption-desorption analysis. The acidactivated halloysites had an increased ability to remove aniline and chloroanilines from aqueous solutions as the acid activation temperature was increased. This suggests that the acid activation temperature is an important factor that influences the ability of acid activated halloysites to adsorb aromatic amines (anilines) from water. The efficiency of aniline and chloroaniline removal by halloysite activated at 80°C reached maximum levels, especially for the removal of aniline and 4-chloroaniline. The adsorption isotherm data were best described by the Langmuir adsorption model. The values of the Langmuir adsorption constants were calculated using the inverse liquid chromatography method.

Multielemental Analysis of Tobacco Plant and Tobacco Products by TXRF

The aim of this research is to develop a fast analytical method for multielemental analysis of the tobacco plant Virginia tobacco (cultivated in Poland) and tobacco products (cigarettes, cigars, cigarillos, snuff and two kinds of properly crafted tobacco such as a shisha and cigarette tobacco) distributed in Polish markets by means of a low-power benchtop total reflection X-ray fluorescence (TXRF) system. For this purpose, a set of certified tobacco materials and real samples was employed. In leaves and stalks of V. tobacco and tobacco products, a concentration of 18 elements (P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Rb, Sr and Pb) was determined. Analyzing elemental composition of tobacco plants, one can see that concentrations of S, Ca, Ti, Mn, Zn, Sr and Pb are higher in leaves, whereas the concentrations of P, Cl, K, Fe Cu and Br are higher in stalks; the levels of Cr, Ni, As and Rb are comparable in both these parts of the tobacco plant. All of the parameters affecting sample preparation and TXRF measurements conditions were carefully evaluated. The accuracy and precision of the TXRF measurements were verified using an internal standardization approach for quantification.

X-ray spectroscopy of multicharged xenon ions at the EBIT plasma

X-ray spectra of multicharged xenon ions created in an electron-beam ion trap (EBIT) were measured both with a low-resolution silicon drift detector (SDD) and a high-resolution Johann/Johannson type crystal diffraction spectrometer. The measurement were performed in the electron-beam ion source (EBIS) using the transmission, leaky and pulsed modes of the ion source operation with trapped xenon ions excited by an electron beams of energies 9-15 keV. Moreover, the dynamics and equilibration of the EBIT plasma was studied by measuring the X-ray spectra for different electron energies and trapping times. The results will be discussed using available theoretical models describing the atomic processes in the EBIT plasma.