Quantitative analysis of trace levels of surface contamination by X-ray photoelectron spectroscopy Part I: statistical uncertainty near the detection limit.

We discuss the problem of quantifying common sources of statistical uncertainties for analyses of trace levels of surface contamination using X-ray photoelectron spectroscopy. We examine the propagation of error for peak-area measurements using common forms of linear and polynomial background subtraction including the correlation of points used to determine both background and peak areas. This correlation has been neglected in previous analyses, but we show that it contributes significantly to the peak-area uncertainty near the detection limit. We introduce the concept of relative background subtraction variance (RBSV) which quantifies the uncertainty introduced by the method of background determination relative to the uncertainty of the background area itself. The uncertainties of the peak area and atomic concentration and of the detection limit are expressed using the RBSV, which separates the contributions from the acquisition parameters, the background-determination method, and the properties of the measured spectrum. These results are then combined to find acquisition strategies that minimize the total measurement time needed to achieve a desired detection limit or atomic-percentage uncertainty for a particular trace element. Minimization of data-acquisition time is important for samples that are sensitive to x-ray dose and also for laboratories that need to optimize throughput.

EUV-induced oxidation of carbon on TiO2.

Previously we reported estimates of the maximum etch rates of C on TiO2 by oxidizers including NO, O3 and H2O2 when irradiated by a spatially-non-uniform beam of extreme ultraviolet (EUV) radiation at 13.5 nm (Faradzhev et al., 2013). Here we extend that work by presenting temporally and spatially resolved measurements of the C etching by these oxidizers as a function of EUV intensity in the range (0.3 to 3) mW/mm2 [(0.2 to 2) × 1016 photons s-1 cm-2]. We find that the rates for NO scale linearly with intensity and are smaller than those for O3, which exhibit a weak, sub-linear intensity dependence in this range. We demonstrate that these behaviors are consistent with adsorption of the oxidizing precursor on the C surface followed by a photon-stimulated reaction resulting in volatile C-containing products. The kinetics of photon-induced C etching by hydrogen peroxide, however, appear to be more complex. The spatially resolved measurements reveal that C removal by H2O2 begins at the edges of the C spot, where the light intensity is the lowest, and proceeds toward the center of the spot. This localization of the reaction may occur because hydroxyl radicals are produced efficiently on the catalytically active TiO2 surface.