Experimental determination of ruthenium L-shell fluorescence yields and Coster-Kronig transition probabilities

The L-shell fluorescence yields and the Coster-Kronig factors of ruthenium (and the corresponding uncertainty) were determined for the first time experimentally by applying radiometrically calibrated instrumentation of the Physikalisch-Technische Bundesanstalt. The resulting fluorescence yields ($\omega_{L_3}=0.0459(20)$, $\omega_{L_2}=0.0415(26)$, $\omega_{L_1}=0.0109(9)$) and the Coster-Kronig factors ($f_{23}=0.177(32)$, $f_{13}=0.528(90)$, $f_{12}=0.173(73)$) agree reasonable well with parts of the data from the literature

Characterization of sub-monolayer coatings as novel calibration samples for X-ray spectroscopy

With the advent of both modern X-ray fluorescence (XRF) methods and improved analytical reliability requirements the demand for suitable reference samples has increased. Especially in nanotechnology with the very low areal mass depositions, quantification becomes considerably more difficult. However, the availability of suited reference samples is drastically lower than the demand. Physical vapor deposition (PVD) techniques have been enhanced significantly in the last decade driven by the need for extremely precise film parameters in multilayer production. We have applied those techniques for the development of layer-like reference samples with mass depositions in the ng-range and well below. Several types of reference samples were fabricated: multi-elemental layer and extremely low (sub-monolayer) samples for various applications in XRF and total-reflection XRF (TXRF) analysis. Those samples were characterized and compared at three different synchrotron radiation beamlines at the BESSY II electron storage ring employing the reference-free XRF approach based on physically calibrated instrumentation. In addition, the homogeneity of the multi-elemental coatings was checked at the P04 beamline at DESY. The measurements demonstrate the high precision achieved in the manufacturing process as well as the versatility of application fields for the presented reference samples

Accurate experimental determination of gallium K- and L3-shell XRF fundamental parameters

The fluorescence yield of the K- and L3-shell of gallium was determined using the radiometrically calibrated (reference-free) X-ray fluorescence instrumentation at the BESSY II synchrotron radiation facility. Simultaneous transmission and fluorescence signals from GaSe foils were obtained, resulting in K- and L3-shell fluorescence yield values consistent with existing database values(omega_Ga_K=0.515 +- 0.019, omega_Ga_L3=0.013 +- 0.001). For the first time, these standard combined uncertainties are obtained from a properly constructed Uncertainty Budget. These K-shell fluorescence yield values support Bambynek's semi-empirical compilation from 1972: these and other measurements yield a combined recommended value of omega_Ga_K=0.514 +- 0.010. Using the measured fluorescence yields together with production yields from reference Ga-implanted samples where the quantity of implanted Ga was determined at 1.3% traceable accuracy by Rutherford backscattering spectrometry, the K-shell and L3-subshell photoionization cross sections at selected incident photon energies were also determined and compared critically with the standard databases.Comment: 17 pages, 6 figure

Characterization of ultra-shallow aluminum implants in silicon by grazing incidence and grazing emission X-ray fluorescence spectroscopy

In this work two synchrotron radiation-based depth-sensitive X-ray fluorescence techniques, grazing incidence X-ray fluorescence (GIXRF) and grazing emission X-ray fluorescence (GEXRF), are compared and their potential for non-destructive depth-profiling applications is investigated. The depth-profiling capabilities of the two methods are illustrated for five aluminum-implanted silicon wafers all having the same implantation dose of 1016 atoms per cm2 but with different implantation energies ranging from 1 keV up to 50 keV. The work was motivated by the ongoing downscaling effort of the microelectronics industry and the resulting need for more sensitive methods for the impurity and dopant depth-profile control. The principles of GIXRF and GEXRF, both based on the refraction of X-rays at the sample surface to enhance the surface-to-bulk ratio of the detected fluorescence signal, are explained. The complementary experimental setups employed at the Physikalisch-Technische Bundesanstalt (PTB) for GIXRF and the University of Fribourg for GEXRF are presented in detail. In particular, for each technique it is shown how the dopant depth profile can be derived from the angular intensity dependence of the Al Kα fluorescence line. The results are compared to theoretical predictions and, for two samples, crosschecked with values obtained from secondary ion mass spectroscopy (SIMS) measurements. A good agreement between the different approaches is found proving that the GIXRF and GEXRF methods can be efficiently employed to extract the dopant depth distribution of ion-implanted samples with good accuracy and over a wide range of implantation energies

Titanium and titanium oxides at the K- and L-edges: validating theoretical calculations of X-ray absorption and X-ray emission spectra with measurements

Using well-calibrated experimental data we validate theoretical X-ray absorption spectroscopy (XAS) as well as X-ray emission spectroscopy (XES) calculations for titanium (Ti), titanium oxide (TiO), and titanium dioxide (TiO$_2$) at the Ti K- and L-edges as well as O K-edge. XAS and XES in combination with a multi-edge approach offer a detailed insight into the electronic structure of materials since both the occupied and unoccupied states, are probed. The experimental results are compared with ab initio calculations from the OCEAN package which uses the Bethe-Salpeter equation (BSE) approach. Using the same set of input parameters for each compound for calculations at different edges, the transferability of the OCEAN calculations across different spectroscopy methods and energy ranges is validated. Thus, the broad applicability for analysing and interpreting the electronic structure of materials with the OCEAN package is shown

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

Structure and stability of 7-mercapto-4-methylcoumarin self-assembled monolayers on gold: an experimental and computational analysis

Self-assembled monolayers (SAM) of 7-mercapto-4-methylcoumarin (MMC) on a flat gold surface were studied by molecular dynamics (MD) simulations, reference-free grazing incidence X-ray fluorescence (GIXRF) and X-ray photoelectron spectroscopy (XPS), to determine the maximum monolayer density and to investigate the nature of the molecule/surface interface. In particular, the protonation state of the sulfur atom upon adsorption was analyzed, since some recent literature presented evidence for physisorbed thiols (preserving the S-H bond), unlike the common picture of chemisorbed thiyls (losing the hydrogen). MD with a specifically tailored force field was used to simulate either thiol or thiyl monolayers with increasing number of molecules, to determine the maximum dynamically stable densities. This result was refined by computing the monolayer chemical potential as a function of the density with the bennet acceptance ratio method, based again on MD simulations. The monolayer density was also measured with GIXRF, which provided the absolute quantification of the number of sulfur atoms in a dense self-assembled monolayer (SAM) on flat gold surfaces. The sulfur core level binding energies in the same monolayers were measured by XPS, fitting the recorded spectra with the binding energies proposed in the literature for free or adsorbed thiols and thiyls, to get insight on the nature of the molecular species present in the layer. The comparison of theoretical and experimental SAM densities, and the XPS analysis strongly support the picture of a monolayer formed by chemisorbed, dissociated thiyls

Experimental determination of X-ray atomic fundamental parameters of nickel

Abstract X-ray atomic properties of Nickel were investigated in a singular approach that combines different experimental techniques to obtain new and useful reliable values of atomic fundamental parameters for X-ray spectrometric purposes and for comparison to theoretical predictions. We determined the mass attenuation coefficients in an energy range covering the L- and K- absorption edges, the K-shell fluorescence yield and the Kb/Ka and Kb1,3/Ka1,2 transition probability ratios. The obtained line profiles and linewidths of the Ka and Kb transitions in Ni can be considered as the contribution of the satellite lines arising from the [KM] shake processes suggested by Deutsch et al. [1] and Ito et al. [2]. Comparison of the new data with several databases showed a good agreement but also discrepancies were found with existing tabulated values