Fe and/or Mn‐containing yellow ochre, red ochre, and umber earth pigments are omnipresent in 17th century paintings. Less common in the materials used in historical paintings of this period is the Fe and Mn‐rich earth pigment sienna. Different uses of historical pigments in one painting by Georg Flegel (1566–1638) and another version of the same painting but of disputed attribution were recently uncovered by means of macro‐x‐ray fluorescence (MA‐XRF) scanning and other non‐invasive analytical techniques. In this paper, an approach solely based upon the correlation of Fe and Mn MA‐XRF maps with the optical image of the painting is compared to the use of Mn/Fe correlation plots. The identification of clusters within a plot of the Fe counts vs. the Mn counts can aid to infer whether an area with a certain color matches with the use of the earth pigments found in the two paintings and to ultimately shed light on the different usage of these pigments. The analytical thresholds found in the Mn/Fe correlation plots allowed to identify clusters differing in composition, which matched an area of a certain color with the earth pigments used therein. This highlighted the differences and similarities between the two paintings, ultimately ascertaining the lower value of the painting of disputed attribution. The analysis of single‐pixel spectra allowed refining the interpretation of specific Mn/Fe correlation plots. The purpose of these data evaluation steps is presented and the limitations of the proposed methodology are also discussed.

The Altenberg Retable is one of the most important works of German art from the early 14th century. Composed of a shrine, a Madonna figure, and painted wings, it once adorned the high altar of the convent church in Altenberg/Lahn. The side and rear walls of the shrine were overpainted in 1609. Although conventional methods such as infrared reflectography and X‐ray radiography could not reveal the underlying medieval paint layer, we succeeded by conducting μ‐X‐Ray fluorescent studies. The latter measurements included a handheld spectrometer as well as μ‐X‐Ray fluorescent large area scanner. Nine sections of the side and rear walls were examined as well as a field on one of the wings (as a reference). In each section, spectra were recorded that comprised about 20 elements ranging from K to Bi. Maps of Ca, Fe, Co, Cu, Zn, As, Hg, and Pb were evaluated and interpreted on the basis of the results of prior color sampling analysis. By superposing several element maps, the original medieval iconographic program with its rows of standing saints could be revealed. With the help of iconographic comparison, these saints could be identified: St. Christopher in the central part of the rear wall, flanked by the 4 female saints Clare, Agnes, Dorothy, and Barbara. On the side walls, the apostles Peter and Paul, as well as the deacons Stephen and Lawrence were depicted. Discussed are not only different scenarios of usage for these images behind the altar but also the limits and possibilities of the measurement technology in this specific application.

Layered stacks of the structure Si(100)/Ni/BCxNy were produced by physical (Ni) and chemical (BCN) vapor deposition. The BCN layers were deposited at temperatures of 200, 300, 400, and 500 °C. The resulting samples were characterized by ellipsometry, X‐ray photoelectron spectrometry, secondary ion mass spectrometry, atomic force microscopy, and X‐ray reflectometry. The formed structures of the samples synthesized at 200 and 500 °C, respectively, were determined. For the synthesis temperature of 200 °C, compounds with Ni–C bonds were found at the interface Ni/BCxNy. For the sample produced at 500 °C, compounds with Ni–Si bonds were identified, dispersed as particles or droplets in the corresponding interface. Copyright © 2015 John Wiley & Sons, Ltd.

Metal-insulator-semiconductor field effect transistors play an important role in electronic devices. For sustainable applications of such nanolayered systems the chemical and physical interactions between the films should be known qualitatively and quantitatively. The fundamental problem is, to determine the elemental composition and the structure of each layer and to characterize the interfaces. Layered stacks of the structure Si/Ni/BCN were produced by physical (Ni) and chemical (BCN) vapor deposition. The BCN layers were deposited at the different temperatures. The resulting samples were characterized by XPS, SIMS, and GIXRF-NEXAFS methods. The precursor trimethylamine borane was investigated for the presence of trace contaminants by SRXRF. For the BCN-Ni systems, it was shown that Ni forms different bonds depending on synthesis temperature. For the temperature T = 200°C, an interface between the BCN and Ni occur and a Ni-C bond was identified. In the cases of T = 400°C and of T = 500°C, the Ni-C bond vanishes and Ni is existent in metallic form. The entire Ni layer exists as a metal for the temperature T = 200°C. With increasing temperatures up to 500°C, the nickel atoms react with silicon atoms of the substrate, and a considerable percentage of Ni-Si bonds become observable.

Improvement in the performance of functional nanoscaled devices involves novel materials, more complex structures, and advanced technological processes. The transitions to heavier elements and to thicker layers restrict access to the chemical and physical characterization of the internal material interfaces. Conventional nondestructive characterization techniques such as X-ray photoelectron spectroscopy suffer from sensitivity and quantification restrictions whereas destructive techniques such as ion mass spectrometry may modify the chemical properties of internal interfaces. Thus, novel methods providing sufficient sensitivity, reliable quantification, and high information depths to reveal interfacial parameters are needed for R&D challenges on the nanoscale. Measurement strategies adapted to nanoscaled samples enable the combination of Near-Edge X-ray Absorption Fine Structure and Grazing Incidence X-ray Fluorescence to allow for chemical nanometrology of internal material interfaces. Their validation has been performed at nanolayered model structures consisting of a silicon substrate, a physically vapor deposited Ni metal layer, and, on top, a chemically vapor deposited B(x)C(y)N(z) light element layer.

BCxNy films were produced from single‐source precursors in a chemical vapor deposition process. The boranes were introduced as precursors at low pressure conditions and at a temperature of 700 °C, whereas the borazine was handled at 400 °C and with a plasma enhancement at an electrical power input of 40 W. Additionally, as inert or reactive gases, H2, He, N2, and NH3, respectively, were used. The films deposited on Si(100) substrates were chemically characterized by X‐ray photoelectron spectroscopy and by synchrotron radiation‐based total‐reflection X‐ray fluorescence combined with near‐edge X‐ray absorption fine structure and quantified elementally by energy‐dispersive X‐ray spectroscopy. The results are critically compared. With the application of boranes without NH3, compounds with a dominating carbidic character were identified, whereas with the addition of NH3 to the boranes, a nitridic character was prevalent. In case of using borazine for the synthesis, the nitridic character was found at the application of all auxiliary gases. For both groups stoichiometric formulas derived from energy‐dispersive X‐ray spectroscopy are proposed: B3.5–4C4N2–2.5 for the carbidic region and B3.5C1.5N5 for the nitridic region. Copyright © 2012 John Wiley & Sons, Ltd.

During the last years the interest in silicon and boron carbonitrides developed remarkably. This interest is mainly based on the extraordinary properties, expected from theoretical considerations. In this time significant improvements were made in the synthesis of silicon carbonitride SiCxNy and boron carbonitride BCxNy films by both physical and chemical methods. In the Si–C–N and B-C-N ternary systems a set of phases is situated, namely diamond, SiC, ┚-Si3N4, c-BN, B4C, and ┚-C3N4, which have important practical applications. SiCxNy has drawn considerable interest due to its excellent new properties in comparison with the Si3N4 and SiC binary phases. The silicon carbonitride coatings are of importance because they can potentially be used in wear and corrosion protection, high-temperature oxidation resistance, as a good moisture barrier for high-temperature industrial as well as strategic applications. Their properties are low electrical conductivity, high hardness, a low friction coefficient, high photosensitivity in the UV region, and good field emission characteristics. All these characteristics have led to a rapid increase in research activities on the synthesis of SiCxNy compounds. In addition to these properties, low density and good thermal shock resistance are very important requirements for future aerospace and automobile parts applications to enhance the performance of the components. SiCxNy is also an important material in microand nano-electronics and sensor technologies due to its excellent mechanical and electrical properties. The material possesses good optical transmittance properties. This is very useful for membrane applications, where the support of such films is required (Fainer et al., 2007, 2008; Mishra, 2009; Wrobel, et al., 2007, 2010; Kroke et al., 2000). The structural similarity between the allotropic forms of carbon and boron nitride (hexagonal BN and graphite, cubic BN and diamond), and the fact that B-N pairs are isoelectronic to C-C pairs, was the basis for predictions of the existence of ternary BCxNy compounds with notable properties (Samsonov et al., 1962; Liu et al., 1989; Lambrecht & Segall, 1993; Zhang et al., 2004). This prediction has stimulated intensive research in the last 40 years towards the synthesis of ternary boron carbonitride. BCxNy compounds are interesting in both the cubic (c-BCN) and hexagonal (h-BCN) structure. On the one hand, the

Определение химических связей в тонких слоях карбонитрида бора BCxNy методами РФЭС и TXRF-NEXAFS С помощью рентгеновской фотоэлектронной спектроскопии и метода околокраевой тонкой структуры рентгеновского поглощения в комбинации с полным внешним отражением рентгеновской флуоресценции изучены типы связей в эталонных образцах гексагонального нитрида бора и карбида бора, а также в пленках BCxNy. Пленки карбонитрида бора были получены химическим осаждением из газовой фазы с использованием в качестве исходного вещества триметиламинборана и его смесей с водородом, гелием и аммиаком. При добавлении NH3 в газовую фазу в процессе синтеза пленок в спектрах появляются пики, характерные для эталонного образца h-BN. Полученные результаты свидетельствуют о наличии гексагонального окружения для бора, углерода и азота и могут быть объяснены образованием h-BN и графита, а также h-BCxNy.

Triethylamine borane (TEAB) and He, N2 or NH3 were applied as additional reaction gases in the production of BCxNy layers by low-pressure chemical vapor deposition (LPCVD). These layers were deposited on Si(100) wafers and characterized chemically by X-ray photoelectron spectroscopy (XPS) and synchrotron radiation-based total-reflection X-ray fluorescence analysis combined with near-edge X-ray absorption fine-structure spectroscopy (TXRF-NEXAFS). The composition of the material produced without NH3 was found to be dominated by B–C bonds with the stoichiometric formula B2C3N. B–N bonds with the formula B2CN3 were preferred when NH3 was added. A first attempt was made to compare the results obtained by applying trimethylamine borane and TEAB as single-source precursors.

SiC x N y nanolayers were synthesized by a remote plasma enhanced chemical vapour deposition (RPECVD) method and chemically characterized by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure investigations in total reflection X-ray fluorescence geometry (TXRF-NEXAFS). The results are compared with those obtained for standard samples SiC and Si 3 N 4 (and with spectra from the literature). As a first result, two or more compounds containing Si–N bonds (not Si 3 N 4 ), one compound with a Si–C bond (not SiC), and graphitic carbon were identified.

Films of BC x N y were produced in a plasma-enhanced chemical vapor deposition process using trimethylborazine as precursor and with H2, He, N2, and NH3, respectively, as auxiliary gas. These films deposited on Si(100) wafers or fused quartz glass substrates were characterized chemically by X-ray photoelectron spectroscopy and by synchrotron radiation-based total-reflection X-ray fluorescence combined with near-edge X-ray absorption fine structure. Independent of the auxiliary gas, the B–N bonds are dominating. Furthermore, B–C and N–C bonds were identified. Oxygen, present in the bulk (in contrast to the surface layer of some nanometers, where molecular oxygen and/or water are absorbed) as an impurity, is bonded to boron or to carbon, respectively. The relation of boron and nitrogen changes with the character of the auxiliary gas: c B/c N ≈ 4:3 (for H2 and He) and c B/c N ≈ 1 (for N2 or NH3). Furthermore, physical properties such as the refractive index and the optical band-gap energy were determined.

Multilayered samples consisting of Al, Co and Ni nanolayers were produced by MBE and characterized nondestructively by means of SRXRF, μ-XRF, WDXRF, RBS, XRR, and destructively with SIMS. The main aims were to identify the elements, to determine their purity and their sequence, and also to examine the roughness, density, homogeneity and thickness of each layer. Most of these important properties could be determined by XRF methods, e.g., on commercial devices. For the thickness, it was found that all of the results obtained via XRR, RBS, SIMS and various XRF methods (SRXRF, μ-XRF, WDXRF) agreed with each other within the limits of uncertainty, and a constant deviation from the presets used in the MBE production method was observed. Some serious preliminary discrepancies in the results from the XRF methods were examined, but all deviations could be explained by introducing various corrections into the evaluation methods and/or redetermining some fundamental parameters.

First results are presented for the identification of chemical bonds and structures (speciation) in boron and silicon carbonitrides, produced as layers of some hundred nm. The boron carbonitride (BCxNy) films are synthesized by low-pressure chemical vapor deposition (LPCVD) using the precursor substance trimethylamine borane. The samples of silicon carbonitride (SiCxNy) films are synthesized by plasma-enhanced chemical vapor deposition (PECVD) using hexamethyl disilazane. The measurements were performed by total reflection X-ray fluorescence analysis combined with near-edge X-ray absorption fine structure investigations (TXRF-NEXAFS) and by X-ray photo-electron spectroscopy (XPS). The results are compared with those obtained for standard samples boron carbide (B4C), boron nitride (e.g., h-BN, c-BN), silicon carbide (SiC), and silicon nitride (Si3N4).