Surface and in-depth characterization of TiC/C and Ti(C,N) layers by means of AES and Factor Analysis

Magnetron sputtered TiC/C multilayers and Plasma Vapour Deposited Ti(C,N) layers have been investigated by AES. The carbon sensivity factor has been calibrated for the correct composition of a TiC standard sample. Nitrogen has been measured indirectly based on the Ti_L3M23M23/Ti_L3M23V peak area ratio in the direct EN(E) spectrum using Ti, TiC and TiN standard samples. The influence of Tougaard background removal has been tested. As the less accurate method taking the Ti peak-to-peak ratio has been found to give adequately good results. It has been possible to recalculate AES depth profiles, where only peak-to-peak values and no peak areas in the direct spectrum are available. Factor Analysis has been applied to AES depth profiling results. The data matrix in each column contains the linked experimental spectra of the measured elements. Based on the standard spectra the main components of a TiN layer on silicon have been identified by Factor Analysis. The structure of a TiC/C multilayer system has been resolved by the characteristic C_KLL peak shape in C and TiC. Factor Analysis enables to calculate the individual profiles for Ti, TiC and C.     

Growth of TiC films by Pulsed Laser Evaporation (PLE) and characterization by XPS and AES

Summary Thin films of TiC with a thickness of some 100 nm have been grown on Si(100) substrates by Pulsed Laser Evaporation (PLE). Advantages of PLE in comparison with more conventional growth methods e. g. PVD or CVD are reported. The feasibility of growing stoichiometric thin films of TiC by PLE was investigated. These films produced have been analysed in situ by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). XPS results and Auger sputter depth profiles indicate that the films grown between RT and 500°C are stoichiometric TiC. Film/substrate interdiffusion is observed at 600°C substrate temperature and higher.     

Characterization of Laser-Arc deposited multilayer systems by means of AES, Factor Analysis and XPS

In a vacuum chamber at 5 · 10^–4 Pa, multilayer systems (single layer thickness 20 nm) consisting of Ti/C and Al/C, respectively, have been deposited on Si (111) disks by the laser assisted coating (Laser-Arc). Structure and composition have been investigated by means of Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), and Auger Electron Spectroscopy (AES) in conjunction with Factor Analysis. AES depth profile measurements through the outermost part of the layers show for both the Ti/C and the Al/C samples a regular structure of the layer sequence metal/ carbon with a constant distance along the sample normal and sharply formed interfaces. In the metallic layers an oxygen enrichment was found, which is more intensive in the Ti/C deposit than in the Al/C one. By means of Factor Analysis in the evaluation of the differentiated spectra as a function of sputtering time, the formation of carbides at the metal/carbon interfaces has been detected. However, in the present state of the investigations it can not be decided, whether the observed carbide formation is the result of the energy impact due to ion sputtering or the coating fabrication process itself.     

Ti(C,N)粉中氧的测定

Ti（C,N）是TiC和TiN的无限固溶体,也可表示为Ti（C1-x,Nx）的形式（0〈x〈1）。它具有良好的高温强度、耐热性、耐磨性和化学稳定性以及良好的导电、导热性等优点,广泛用于制备金属陶瓷。在机械、化工、汽车制造和航天航空等许多领域得到应用。尤其是这种物质的超细粉末作为复合材料的增强相,具有很大的开发价值和应用前景。研究表明,为了制备优质的Ti（C,N）粉,控制氧含量是一个重要的技术指标。     

Analysis of AlGaAs/GaAs superlattices by means of sputter-assisted AES,SEM and TEM

This paper reports the developments of evaluation methods on epitaxially grown superlattices by means of sputterassisted Auger electron spectroscopy (AES), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). AlGaAs/GaAs semiconductor superlattics were grown epitaxially by metal–organic chemical vapour deposition (MOCVD). The layer thickness of the superlattices ranged from a few to ten nanometers. Firstly, developments of Auger depth profiling were tried by using: (1) a differential pumping-type ion gun instead of a static pressure type to reduce the oxygen adsorbates on the AlGaAs layer; (2) low-energy Auger signals instead of high-energy ones to shorten the escape depth; and (3) the lowest ion etching energy of 0.2 keV instead of 1 keV to reduce the surface roughening effects. It is shown that the depth resolution of sputter-assisted AES is attainable to 1.5 nm. Secondly, high-resolution SEM can be used as an easy evaluation method by observing the cleaved surface of superlattices, since the layers can be distinguished by signal contrast. Also, TEM can be used as an evaluation method by observing the (110) cross-section thinned sample. The dark field image has a high contrast between AlGaAs and GaAs using the (002) diffraction. It is confirmed from these AES, SEM and TEM evaluations that the hetero-interface abruptness of AlGaAs/GaAs superlattices grown by MOCVD is of the order of one monoatomic layer.     

Evaluation of Auger Electron Spectroscopy (AES) depth-profiles by application of Factor Analysis

Summary AES is a useful tool in order to determine the quantitative composition of a solid surface. Conventional methods of evaluating AES concentration profiles leave chemical information about the bonding state of an element contained in the spectra unused. To extract these Factor Analysis (FA) was employed as a mathematical technique to form a physical model of the composition of a sample. With FA the correlation function between the measured spectra is evaluated. Thus it is possible to determine number and quantity of chemical components influencing the data. The feasibility of FA is demonstrated by its application to the evaluation of AES concentration profiles. We investigated in some detail heterostructures consisting of a Si₃N₄/-Si:H/SiO₂ and Ti/Si Schottky contacts on Si substrates, respectively.     

In-situ characterization of MgLi composite materials by means of AES and factor analysis

During manufacture of -Al₂O₃ fibre reinforced MgLi alloys the high mobility and reacitivity especially of the Li metal can cause damage of the fibres and loss of the good mechanical behaviour. Because of the low fibre diameter (2 to 5 m), and the necessity to detect Li, laterally highly resolved Auger electron spectroscopy was used to study the fibre-matrix-interaction. The measurements were performed at sample surfaces, which had been uncovered by in-situ fracture in the UHV apparatus. Due to the bad signal/noise ratio (which was tolerated to achieve high lateral resolution) and the overlapping spectral features, and in order to make an attempt to classify the large amount of spectra obtained, factor analysis in conjuction with cluster analysis was used in the interpretation of AES data. So it was possible to detect the chemical species which are responsible for the apperance of the experimental spectra and to draw conclusions concerning the fracture morphology (inter granular, trans granular).Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

SIMS-analysis on B, N, and C containing layers

B, N, and C containing layers produced by the “Chemical Vapour Deposition” (CVD) method were investigated by SIMS in respect of their elemental composition and impurities. The atomic B/N ratios found are between 1:0.15 and 1:0.46 referred to an h-BN powder (B/N = 1:1 supposed) as reference material. The carbon content was 5 to 12 at-%, additional H and O impurities were detected. Dependencies of the film composition on process parameters and the problems occurring during SIMS measurements of such layers are discussed.     

Determination of carbon in thin layers by means of the12C(d,n)13N nuclear reaction using a 2 MeV Van de Graaf accelerator

A nondestructive method for carbon determination in layers of 3–10 m thickness is considered. The method is based on using the¹²C(d, n)¹³N nuclear reaction with simultaneous account of surface contamination by means of the¹²C(d, p)¹³C competitive reaction. The total cross sections for the¹²C(d, n)¹³N reaction were measured from 0.4 to 1.7 MeV. Proton beam annealing was applied with the purpose of lowering surface carbon content. The detection limit of carbon by this method is 0.5 ppm, relative standard deviation is 0.06. Disturbing effects of carbon diffusion and¹³N recoil backs cattering are also taken into account.     

TiC nanocrystal formation from carburization of laser-grown Ti/O/C nanopowders for nanostructured ceramics

Refractory carbide ceramics (TiC and ZrC) raise interest as promising materials for high-temperature applications such as structural materials for the future generation of nuclear reactors. In this context, nanostructured ceramics are expected to exhibit improved thermomechanical properties as well as better behavior under irradiation when compared to conventional materials. It is therefore necessary to synthesize carbide nanocrystals of such materials to elaborate the ceramics. We report here the formation study of TiC nanocrystals through the direct carburization of Ti/O/C nanopowders grown by laser pyrolysis. A spray of titanium tetraisopropoxide was laser pyrolyzed with ethylene as the sensitizer, leading to Ti/O/C nanopowders with various C contents controlled by the synthesis conditions. Annealing treatments performed on these nanopowders under an inert atmosphere without any C addition enabled the formation of TiC grains through the carburization of the oxide phase by free C incorporated during the synthesis. The powders were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The final TiC grain size was about 80 nm, and the grains were monocrystalline. The influence of the free C content on the grain growth during the annealing step, together with its effects on the densification of the ceramics after sintering by high-pressure flash sintering, was examined. A 93% densification was finally achieved.     

A class of luminescent cyclometalated alkynylgold(III) complexes: synthesis, characterization, and electrochemical, photophysical, and computational studies of [Au(C=N=C)(C triple bond C-R)] (C=N=C = kappa(3)C,N,C bis-cyclometalated 2,6-diphenylpyridyl)

A new class of luminescent cyclometalated alkynylgold(III) complexes, [Au(RC=N(R')=CR)(CCR' ')], i.e., [Au(C=N=C)(C triple bond CR')] (HC=N=CH = 2,6-diphenylpyridine) R' ' = C6H5 1, C6H4-Cl-p 2, C6H4-NO2-p 3, C6H4-OCH3-p 4, C6H4-NH2-p 5, C6H4-C6H13-p 6, C6H13 7, [Au(tBuC=N=CtBu)(C triple bond CC6H5)] 8 (HtBuC=N=CtBuH = 2,6-bis(4-tert-butylphenyl)pyridine), and [Au(C=NTol=C)(CCC6H4-C6H13-p)] 9 (HC=NTol=CH = 2,6-diphenyl-4-p-tolylpyridine), have been synthesized and characterized. The X-ray crystal structures of most of the complexes have also been determined. Electrochemical studies show that, in general, the first oxidation wave is an alkynyl ligand-centered oxidation, while the first reduction couple is ascribed to a ligand-centered reduction of the cyclometalated ligand with the exception of 3 in which the first reduction couple is assigned as an alkynyl ligand-centered reduction. Their electronic absorption and luminescence behaviors have also been investigated. In dichloromethane solution at room temperature, the low-energy absorption bands are assigned as the pi-pi* intraligand (IL) transition of the cyclometalated RC=N(R')=CR ligand with some mixing of a [pi(C triple bond CR') --> pi*(RC=N(R')=CR)] ligand-to-ligand charge transfer (LLCT) character. The low-energy emission bands of all the complexes, with the exception of 5, are ascribed to origins mainly derived from the pi-pi* IL transition of the cyclometalated RC=N(R')=CR ligand. In the case of 5 that contains an electron-rich amino substituent on the alkynyl ligand, the low-energy emission band was found to show an obvious shift to the red. A change in the origin of emission is evident, and the emission of 5 is tentatively ascribed to a [pi(CCC6H4NH2) --> pi*(C=N=C)] LLCT excited-state origin. DFT and TDDFT computational studies have been performed to verify and elucidate the results of the electrochemical and photophysical studies.     

Microstructural and in-depth electrochemical characterization of Zn diffusion layers on aluminum 3xxx alloy

AA 3XXX alloys are widely used in heating, ventilation, and air conditioning (HVAC) field. Diffusion joining using a filler metal together with flux is employed in some applications as for heat exchangers. In this work, the effect of diffusion of a Zn-based flux on both microstructure and electrochemical behavior has been investigated. In particular, an AA3xxx was coated with a Zn-rich flux and subjected to controlled atmosphere brazing (CAB). Glow discharge optical emission spectroscopy (GDOES) composition profiles were acquired in order to determine the Zn distribution in the diffusion layer. The GDOES was also employed to produce a controlled erosion of the surface in order to obtain craters with defined depths in the Zn diffusion layer, in which electrochemical analyses could be performed. The Volta potential maps at different depths in the Zn diffusion layer were obtained by scanning Kelvin probe force microscope (SKPFM). The Zn diffusion layer was also investigated by means of Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy (SEM-EDXS) and the chemical composition of the phases present in the regions was investigated by SKPFM. Finally, the electrochemical microcell was used in the produced craters in order to determine the electrochemical behavior along the Zn diffusion profile. SKPFM and microcell results showed a correlation between the Zn content and the electrochemical properties. In particular, a higher Zn content in the diffusion layer leads to an increase of the Volta potential difference between the intermetallic particles and the matrix. The electrochemical measurements also showed that the Zn diffusion layer provides galvanic protection to the underlaying aluminum alloy.     

Surface characterization of unbleached kraft pulps by means of ESCA

The effect of digestion conditions (amount of effective alkali, digestion time) on the surface compositions of unbleached softwood (Pinus sylvestris) kraft pulp has been investigated by electron spectroscopy for chemical analysis (ESCA). The quantities monitored were the angular dependence of the total O/C ratio, the relative amounts of carbons in different states of oxidation and the adsorption of Al and Ca ions to the carboxyl groups in the surface. Examination of the angular dependence of ESCA intensities shows that the concentration of alkyl carbon is high in a very thin surface layer and that it decreases linearly with decreasing kappa number. The concentration of alkyl carbon is decreased by extraction of the fibres with dichloromethane, but the amount remaining in the surface after extraction still decreases linearly with decreasing kappa number (i.e. it decreases with increasing digestion time). It is suggested that the observed enrichment of alkyl carbon in the outermost surface layers most probably is due to reprecipitation of lignin. In pulp that has not been extracted, there is also strong enrichment of extractives in the surface. This amount increases with increasing effective alkali but is relatively independent of digestion time. ESCA analysis of the Al and Ca bound to the carboxyl groups shows that the amount depends on digestion time; the results are consistent with the notion that the reprecipitated lignin contains carboxyl groups.     

Surface chemistry of PVD (Cr,Al)N coatings deposited by means of direct current and high power pulsed magnetron sputtering

(Cr,Al)N protective coatings were deposited using direct current (DC) and high power pulse magnetron sputtering (HPPMS) technology. The chemical analysis of the surface near region of the coatings was performed by means of X‐ray photoelectron spectroscopy (XPS) and was correlated to the deposition parameters and resulting coating morphology. A surface oxidation process was observed by means of angle resolved XPS studies and XPS sputter profiles. Both DC and HPPMS coatings showed a non‐stoichiometric chemical composition with a significant excess of cations (chromium and aluminum) in the bulk structure, leading to a metastable phase. The passivation reaction of the surface near region leads to an anion to metal ratio which goes along with an enrichment of aluminum in the surface near region as a thermodynamically favored composition in equilibrium with the ambient atmosphere. Interestingly, the variation of the pulse duration of the HPPMS process, which led to a change of the peak current, had a strong influence on the resulting composition of the surface near region. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization of metallic layer composites by means of AES/depth profile analysis

The adherence mechanism of arc sprayed Ni layers on structure steel St37 is investigated. AES depth profiles are obtained on single Ni particles still adhering to the substrate after the Ni layer has been separated from it. A comparison of interface shapes and results of adherence measurements reveals Fe-Ni layered structures for the best adhering layers, whereas less adhering layers are characterized by narrower interfaces caused by diffusion. Areas with no adherence are covered with oxidic layers.     

Analysis of thin layers by means of spark-source mass spectrometry

Summary A device has been constructed with which the surface of a specimen can be scanned with a spark drawn from a fixed counter electrode. The mean depth of penetration is of the order of microns and limits of detection of 0.1 ppm are possible. Repeated scanning allows profile analysis, too.

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Analyse dünner Schichten mit Hilfe der Funken-Massenspektrometrie

Zusammenfassung Eine Anordnung wurde konstruiert, mit der eine sich drehende Probenoberfläche durch eine feste Gegenelektrode abgetastet werden kann. Die mittlere Eindringtiefe pro Funkenentladung liegt in der Größenordnung von Mikrometern. Nachweisgrenzen von 0,1 ppm sind möglich. Durch wiederholtes Abtasten können auch Profilanalysen durchgeführt werden.