Improving the oxidation resistance of AlCrN coatings by tailoring chromium out-diffusion

In this work, we have studied the improvement on the oxidation resistance of AlCrN-based coatings by adding a subsurface titanium nitride barrier layer. Since oxidation is interrelated with the inward diffusion of oxygen into the surface of Al_xCr_1−xN (x = 0.70) coatings and the outward diffusion of Cr to the surface, the oxidation behaviour of the aluminium-rich AlCrN coatings can be tuned by designing the coating in an appropriate layered structure. The buried depth of the embedded layer and the oxidation time were varied, and the changes in the AlCrN/TiN depth composition profiles and surface oxidation stoichiometry were analysed by means of Glow Discharge Optical Emission Spectroscopy (GDOES) and Cross Sectional SEM (X-SEM) maps. It was observed that when a TiN diffusion barrier of 300 nm was deposited near the top surface (500 nm from the surface) the inhibition of the inward diffusion of oxygen and formation of beneficial alumina surface layers was promoted and consequently an increase of the oxidation resistance is achieved. This is explained in terms of a limited surplus of chromium from the coating to the surface. This was corroborated after performing experiments using CrN as embedded barrier layer which resulted in a continuous surplus of chromium to the surface and the formation of Cr-rich oxides. GDOES, in combination with X-SEM elemental maps, was proved to be a fast and accurate technique to monitor composition in-depth changes during oxidation, providing unique information regarding the oxide structure formation.     

SIMS/XPS characterization of surface layers formed in 3 mass% Si‐steel by annealing in oxygen at low partial pressure

Selective oxidation in silicon steel shows several interesting phenomena, such as the formation of an internal oxidation zone that depends on the oxidation conditions and the steel composition. In this work, SIMS and XPS were used for characterizing the formation processes of surface layers formed during selective oxidation of a typical silicon steel. The starting material is a secondary‐recrystallized 3 mass% Si‐steel sheet with a surface orientation of (011). Sample sheets were annealed at a temperature of 948–1023 K under an atmosphere with a low partial pressure of oxygen. The SIMS depth profiles show that the internal oxidation zone thickens and an iron‐rich layer that formed on the internal oxidation zone expands as the annealing temperature increases. Manganese and chromium levels increase outside the internal oxidation zone, whereas tin exists in the internal oxidation zone. The XPS results of the sample surface show that silicon and manganese levels increase on the sample surface to form oxides, and the chemical composition and state of these elements depend on the annealing temperature. In addition, tin increases on the surface of a relatively thick iron‐rich layer that formed on the internal oxidation layer. These experimental results are discussed on the basis of the thermodynamic characteristics of the elements. Copyright © 2003 John Wiley & Sons, Ltd.     

SIMS Profiling and TEM of CVD Films on Multi-Filament Samples

 A suitable fibre coating is essential to obtain optimal fibre-matrix interaction in fibre-strengthened composite materials. Thin films (∼100 nm) of silicon carbide, turbostratic carbon, and boron nitride were deposited by CVD as single or double layers on commercial multi-filament fibres in a continuous process. The fibre material itself may be carbon, alumina, silicon carbide, or a quaternary ceramic of SiCBN. The application of MCs⁺-SIMS enables one to determine the composition (including impurities of H and O) of various fibre coating materials with an accuracy of at least 20% relative. Due to the special geometry of the multi-filament samples the depth resolution of the SIMS depth profiles is limited, nevertheless, layered structures and some details of the interface between coating and fibre can be studied. The depth calibration of the SIMS depth profiles is derived from sputter rates established on flat samples with a composition similar to that of the fibre coating material. However, the obtained film thicknesses are not extremely different from the values derived from TEM on cross sections of coated fibres.     

Strategy for Applying Microanalytical Techniques

A combination of microanalysis techniques is used to reveal with great precision the composition and microstructure of typical features in engineering materials. In this paper small particles, very thin films, interfaces and their contiguous region are considered. Small silicon nitride particles in an iron matrix produced by nitriding are characterized quantitatively with High Resolution Electron Microscopy (HREM) and Electron Probe Micro Analysis (EPMA) using Wavelength Dispersive X-ray Spectrometry (WDS). Thin aluminium-oxide films grown on aluminium substrates by thermal oxidation at low pressure are investigated with HREM and X-ray Photoelectron Spectroscopy (XPS). Their thickness, composition and degree of crystallinity are established as a function of oxidation temperature and time. At and near the oxide-layer/MCrAlY-coating (M=Ni and/or Co) interface the aluminium and chromium depletion behaviour of the coating material due to high-temperature oxidation is studied with high-resolution Scanning Electron Microscopy (SEM), EPMA and Auger electron spectroscopy (AES). The composition-depth profiles obtained for the coating material are used to determine the composition dependent diffusion coefficients. These properties are crucial for the prediction through computational modelling of the coating material oxidation behaviour and enable the development of new coating materials.     

The effect of glow discharge sputtering on the analysis of metal oxide films

The potential of radiofrequency glow discharge optical emission spectrometry (rf-GD-OES) for the quantification and the solid-state speciation of metal oxide films has been investigated in this work. Two types of oxide coatings, an iron oxide film deposited on silicon and a chromate conversion coating (CCC), were studied at 700 Pa of pressure and 30 W of forward power. The metal to oxygen ratios in the quantitative depth profiles (Fe/O and Cr/O, respectively) were used to evaluate the oxidation states of iron and chromium in the oxide films, demonstrating the capability of GD-OES technique for depth-resolved solid-state speciation. Furthermore, the effect of glow discharge sputtering on the samples surface in terms of modifications in the surface morphology and species transformations, were investigated by using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The iron and chromium oxidation states were carefully studied by XPS at the original samples surface and at the bottom of GD craters, and a systematic reduction of metal elements was observed after rf-GD-OES analysis. In the case of thin oxide films, preferential sputtering can be considered as a critical factor since oxygen atoms can be preferentially sputtered, leaving a metal-enriched surface and, therefore, promoting the reduction of metal elements. In the present study preferential sputtering was found to be sample dependent, changing the proportion of the metal reduction in the oxide film with its composition. Additionally, alternative sputter-depth-profiling techniques such as secondary ion mass spectrometry (SIMS), femtosecond laser ablation (fs-LA), and XPS ion gun were used for the analysis of the CCC in order to evaluate the reduction of Cr⁶⁺ to Cr³⁺ depending on the sputtering mechanism.     

Thermal oxidation of silicon studied by high resolution Rutherford backscattering

Rutherford backscattering provides a simple experimental technique for investigating the thermal oxidation of silicon containing heavy impurity species. The technique provides both mass and depth analysis of para-surface layers. Using conventional apparatus, typical depth resolution is 250Å N. This paper describes a simple method of improving the resolution to ～25 Å. The method is then illustrated with data on the analysis of thin (<300Å) layers of thermally oxidised silicon containing ion-implanted impurities. The effect of the type and dose of implanted ions on oxidation rate has been measured. The re-distribution of implanted ions during thermal oxidation is also investigated.     

The detection of oxygen in magneto-optical layers with SIMS

The detection of oxygen in magneto-optical layers is of fundamental importance for the characterization of the stability of RE-TM material. The magnetic properties are directly influenced by oxide formation. Oxygen depth profiles are carried out by using the SIMS technique. A comparison with magnetic measurements showed a clear conformity. We were able to study the oxidation behaviour of various layers at room temperature and at higher values up to 250° C for several hours. It could be shown that aluminum is a successful material for the protection of RE-films against oxidation. The difficulties of translating SIMS counting rates into concentration values were overcome by using EPMA. Specially prepared reference samples were measured by this technique and could then be used as standard samples for SIMS.     

Advanced surface characterization of silver nanocluster segregation in Ag–TiCN bioactive coatings by RBS, GDOES, and ARXPS

Surface modification by means of wear protective and antibacterial coatings represents, nowadays, a crucial challenge in the biomaterials field in order to enhance the lifetime of bio-devices. It is possible to tailor the properties of the material by using an appropriate combination of high wear resistance (e.g., nitride or carbide coatings) and biocide agents (e.g., noble metals as silver) to fulfill its final application. This behavior is controlled at last by the outmost surface of the coating. Therefore, the analytical characterization of these new materials requires high-resolution analytical techniques able to provide information about surface and depth composition down to the nanometric level. Among these techniques are Rutherford backscattering spectrometry (RBS), glow discharge optical emission spectroscopy (GDOES), and angle resolved X-ray photoelectron spectroscopy (ARXPS). In this work, we present a comparative RBS–GDOES–ARXPS study of the surface characterization of Ag–TiCN coatings with Ag/Ti atomic ratios varying from 0 to 1.49, deposited at room temperature and 200 °C. RBS analysis allowed a precise quantification of the silver content along the coating with a non-uniform Ag depth distribution for the samples with higher Ag content. GDOES surface profiling revealed that the samples with higher Ag content as well as the samples deposited at 200 °C showed an ultrathin (1–10 nm) Ag-rich layer on the coating surface followed by a silver depletion zone (20–30 nm), being the thickness of both layers enhanced with Ag content and deposition temperature. ARXPS analysis confirmed these observations after applying general algorithm involving regularization in addition to singular value decomposition techniques to obtain the concentration depth profiles. Finally, ARXPS measurements were used to provide further information on the surface morphology of the samples obtaining an excellent agreement with SEM observations when a growth model of silver islands with a height d?=?1.5 nm and coverage θ?=?0.20 was applied to the sample with Ag/Ti?=?1.49 and deposited at room temperature.

Towards nanometric resolution in multilayer depth profiling: a comparative study of RBS, SIMS, XPS and GDOES

An increasing amount of effort is currently being directed towards the development of new functionalized nanostructured materials (i.e., multilayers and nanocomposites). Using an appropriate combination of composition and microstructure, it is possible to optimize and tailor the final properties of the material to its final application. The analytical characterization of these new complex nanostructures requires high-resolution analytical techniques that are able to provide information about surface and depth composition at the nanometric level. In this work, we comparatively review the state of the art in four different depth-profiling characterization techniques: Rutherford backscattering spectroscopy (RBS), secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS) and glow discharge optical emission spectroscopy (GDOES). In addition, we predict future trends in these techniques regarding improvements in their depth resolutions. Subnanometric resolution can now be achieved in RBS using magnetic spectrometry systems. In SIMS, the use of rotating sample holders and oxygen flooding during analysis as well as the optimization of floating low-energy ion guns to lower the impact energy of the primary ions improves the depth resolution of the technique. Angle-resolved XPS provides a very powerful and nondestructive technique for obtaining depth profiling and chemical information within the range of a few monolayers. Finally, the application of mathematical tools (deconvolution algorithms and a depth-profiling model), pulsed sources and surface plasma cleaning procedures is expected to greatly improve GDOES depth resolution.     

Influence of surface structure on surface analytical statements

The influence of surface structure of technical materials on results and statements of surface analytical methods has been investigated. Especially surface roughness as a typical property of rolled products has been observed. For this purpose samples of steel (technical surface, roughness up to 5 m) and silicon wafers (polished surface) have been analyzed by SNMS and GDOS in order to get information about changes of the surface roughness as function of the sputtering time and their influence on the statements about the depth profiles obtained.     

Depth profile analysis of plasma assisted CVD hard materials coatings

The wear resistance of homogeneous and multilayer TiN_x., TiC_xN_y- and TiC_x-coatings is considerably determined by the layer composition and by the conditions at the interface. This work deals with the possibilities of different depth profile analysis methods for the study of TiN_x and TiC_x layers on hard metal and steel substrates prepared by plasma assisted CVD technique, and furthermore it demonstrates the performance of factor analysis for detailed investigation of a multilayer system consisting of amorphous C and TiC_x single layers.The hard materials coatings were investigated by different methods of depth profile analysis, which may be an important tool in the research of thin layer deposition for wear applications. The following techniques were used: GDOES, analytical TEM, electron microdiffraction and AUGER electron spectroscopy. By means of the combined application of energy dispersive X-ray spectrometry and microdiffraction a correlation of the depth profiles of both elemental concentrations and lattice parameters in TiC_x coatings could be revealed.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Surface- and microanalytical characterization of ion-implanted Si-C-N layers

The development of production methods for carbonitridic hard coatings needs information on depth distributions of the layer components as well as on stoichiometries and binding states of the layer constituents. Si-C-N samples were produced by implanting ¹³C- and ¹⁵N-ions into c-Si <111>, and the implanted layers were investigated by means of NRA depth profiling. Afterwards several samples were characterized by surface analytical techniques, and XPS- and AES depth profiles were measured for typical samples. The measurements confirm the NRA depth profiles and stoichiometries. Furthermore, in all depth ranges C 1s- and N 1s binding energies are observed which are consistent with those of carbonitrides.     

Depth-profiling of vertical sidewall nanolayers on structured wafers by grazing incidence X-ray flourescence

The Physikalisch-Technische Bundesanstalt (PTB), Germany's national metrology institute, developed an alignment strategy to specify elemental depth profiling in vertical sidewall layers on structured wafers. For this purpose, PTB's irradiation chamber for 200 mm and 300 mm silicon wafers was used to combine total-reflection X-ray fluorescence (TXRF) and grazing incidence XRF (GIXRF) techniques by employing monochromatized undulator radiation of the BESSY II electron storage ring. 3-D test structures were fabricated to develop an optimal alignment strategy allowing for depth profiling in such nanolayers. The test structures consisted of silicon bars with widths/spacings either in the μm or in the nm range. In order to be able to differentiate the sidewalls more easily from the remainder of the structures, they were provided with an additional silicon nitride layer. Four structure types of different bar width and density parameters on two 200 mm silicon wafers were investigated. The alignment procedure developed in the present work consists of three main steps and allows for distinct excitation of multiple sidewalls of one kind. Information about depth-dependent sidewall contamination, layer thickness and composition can be obtained by this approach. First results obtained on these test structures demonstrate the application potential of this new technique. In principle, depth-dependent chemical speciation should also be possible using GIXRF in combination with near edge absorption X-ray fine structure (NEXAFS).     

Natural resins and balsams from an eighteenth-century pharmaceutical collection analysed by gas chromatography/mass spectrometry

Historical nomenclature has not always been unequivocally associated with the botanical origin of natural resins. The availability of natural resins has changed throughout the centuries and so have their trade names. Furthermore, adulterations and lack of knowledge have led to variations in the composition of the products traded under the same name. This investigation aims at a new understanding of the interrelation between the historical and modern terms for natural resins. Different Pinaceae and Pistacia resins, mastic, sandarac, copaiba balm and burgundy pitch from Vigani’s Cabinet, a 300-year-old pharmaceutical collection owned by Queens’ College, Cambridge (UK) were investigated. Related reference materials from modern collections were analysed together with natural resins derived from reliable botanical sources. The analytical method was gas chromatography/mass spectrometry (GC-MS) with and without derivatisation with trimethylsulfonium hydroxide. This technique provided detailed molecular compositions of the studied materials, which in turn led to particular data profiles of the materials. Marker molecules of Copaifera, Pinaceae, Cupressaceae and Pistacia resins were identified. By comparing the GC-MS data profiles to the reference samples, a clearer picture of the connection between nomenclature and botanical origin was obtained. With the aid of the marker molecules and data profiles, it was then possible to clarify the nomenclature of the aged resins sampled from Vigani’s Cabinet.     

Low temperature plasma for the preparation of crater walls for compositional depth profiling of thin inorganic multilayers

An indirect, compositional depth profiling of an inorganic multilayer system using a helium low temperature plasma (LTP) containing 0.2% (v/v) SF₆ was evaluated. A model multilayer system consisting of four 10 nm layers of silicon separated by four 50 nm layers of tungsten was plasma‐etched for (10, 20, 30) s at substrate temperatures of (50, 75, and 100) °C to obtain crater walls with exposed silicon layers that were then visualized using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) to determine plasma‐etching conditions that produced optimum depth resolutions. At a substrate temperature of 100 °C and an etch time of 10 s, the FWHM of the second, third, and fourth Si layers were (6.4, 10.9, and 12.5) nm, respectively, while the 1/e decay lengths were (2.5, 3.7, and 3.9) nm, matching those obtained from a SIMS depth profile. Though artifacts remain that contribute to degraded depth resolutions, a few experimental parameters have been identified that could be used to reduce their contributions. Further studies are needed, but as long as the artifacts can be controlled, plasma etching was found to be an effective method for preparing samples for compositional depth profiling of both organic and inorganic films, which could pave the way for an indirect depth profile analysis of inorganic–organic hybrid structures that have recently evolved into innovative next‐generation materials. Copyright © 2016 John Wiley & Sons, Ltd.     

Applications of total reflection X-ray fluorescence spectrometry in trace element and surface analysis

Total reflection X-ray fluorescence spectrometry (TXRF) is presented as a genuine surface analytical technique. Its low information depth is shown to be the characteristic feature differentiating it from other energy dispersive X-ray fluorescence methods used for layer and surface analysis. The surface sensitivity of TXRF and its analytical capability together with the limitations of the technique are discussed here using typical applications including the contamination control of silicon wafers, thin layer analysis and trace element determination. For buried interfaces and implantation depth profiles in silicon a combination of TXRF and other techniques has been applied successfully. The TXRF method has the particular advantage of being calibrated without the need for standards. This feature is demonstrated for the example of the element arsenic.     

Corrosion resistance and bioactivity of titanium after surface treatment by three different methods: ion implantation,alkaline treatment and anodic oxidation

The paper compares the effects of various surface modifications, ion implantation, alkaline treatment and anodic oxidation, upon the corrosion resistance and bioactivity of titanium. The chemical composition of the surface layers thus produced was determined by XPS, SIMS and EDS coupled with SEM. The structure of the layers was examined by TEM, and their phase composition by XRD. The corrosion resistance was determined by electrochemical methods after the samples were exposed to the test conditions for 13 h. The bioactivity of titanium was evaluated in a simulated body fluid at a temperature of 37°C after various exposure time.     

Integrating methods for the analysis of oxide scales on high-temperature alloys using GDOS and EPMA

Summary The oxidation of Ni-based alloys leads to multiphase oxide scales with an inhomogeneous microstructure. By introducing an integrating method for EPMA it was possible to find a common basis with GDOS depth profiles for the chemical characterization of such layers. At first it was necessary to quantify the GDOS intensity profiles; thus the comparison of relative mass fractions supplied by both methods was successful. Generally it was found a substantial agreement also with quantitative SNMS profiles.     

Basic investigations for laser microanalysis: I. Optical emission spectrometry of laser-produced sample plumes

In order to find optimum conditions for laser ablation and atomization for analytical purposes, time resolved emission spectra of Nd:YAG laser-produced plasma plumes propagating into noble gas atmospheres of different pressures were measured with an optical multichannel analyzer. The time evolution of the plasma temperature was determined. Strong temperature changes were observed depending on the matrix composition. The analytical figures of merit of optical emission spectrometry (OES) of laser-produced sample plasmas were determined using, as examples, measurements of two analytes (silicon and chromium) in homogeneous and low-alloyed standard steel samples.     

Analysis of nitrogen-influenced surface near zones of ferrous materials by glow discharge spectroscopy (GDOS)

Glow discharge spectroscopy (GDOS) will be shown to be a quick, informative and simple method for quantitative depth profile analysis of elements of nitrided layers well suited for their quality control. By systematic variation of all glow discharge determining parameters it is possible to get an excellent depth resolution in the order of sub-m corresponding to a comparatively large analytical activated area (50 mm²). In this paper the behaviour of a number of important parameters related to sputtering of the activated area will be discussed. Some quantitative GDOS depth profiles of carbon and nitrogen of pure iron samples nitrided by different procedures will be shown as examples for application.