Thickness determination from the GDOS depth profiles using piece-wise linear model functions

A data processing method is presented making it possible to determine thin film thickness from GDOS depth profiles. It consists of fitting a piece-wise linear function to the depth profile and in using positions (abscissae) of their knots as parameters which are proportional to film thickness. For thickness calibration, such a linear combination of these parameters is used, which gives minimum variation coefficient of the residuals between the real and the estimated thickness of calibration samples. Relative error lower than 3% was obtained in calibration using 4 samples with nickel film thickness ranging from 0.1 to 8.3 m, each analyzed four times.     

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.     

Quantitative depth-profiling with GDOS: application to ZnNi-electrogalvanized steel sheets

Summary Studies are made on quantitative GDOS depth profile analysis for ZnNi-coatings. Relative and absolute depth resolution on the interface ZnNi-coating/steel substrate were evaluated in a thickness range of 0.5 to 5 m using two different anode tube diameters. For quantification, an improved approach of the model of constant emission yield was established. The results are demonstrated on ZnNi-electrodeposits with different coating thickness and chemical content.     

Depth Profile Analysis on the Nanometer Scale by a Combination of Electron Probe Microanalysis (EPMA) and Focused Ion Beam Specimen Preparation (FIB)

Electron probe microanalysis (EPMA) offers high sensitivity and high accuracy in quantitative measurements of chemical compositions and mass coverages. Owing to the low detection limits of the wavelength-dispersive technique, monolayers with mass coverages of about 0.05µgcm^–2 can be detected. Assuming a density of 5gcm^–3 this corresponds to a thickness of 0.1nm. With these advantages in mind, EPMA was extended to depth profile analysis in the sub-micron range using a surface removal technique.The present paper shows how depth profile analysis can be improved by combining EPMA and the focused ion beam (FIB) technique. The focused ion beam system uses a Ga⁺ ion beam. The ion beam allows the milling of defined geometries on the nanometer scale, so that very shallow bevels with exactly defined angles in relation to the surface can be obtained. Low surface damage is expected due to low sputtering effects. Calibrated WDX measurements along the bevel deliver quantitative concentration depth profiles. First results obtained with this new combination of methods will be presented for a multilayered sample used in optical data storage.     

The angle-resolved self-ratio technique for surface depth profile investigations by XFS,EMA, XPS and AES

The angle-resolved self-ratio (AR/SR) technique is a non-destructive, low-damage measuring technique in which the intensity I of an excited, analyte-characteristic radiation is measured as a function of the take-off angle from the surface plane for the purpose of obtaining quantitative depth information about the chosen analyte from the gradient dI/d. The depth information may be any of the following: the type of depth profile, the centroid depth of this profile, the thickness of a uniform overlayer, the stoichiometry of a uniform overlayer, the thickness of a uniform buried layer, and others. The AR/SR technique is one of a number of variants of the angle-resolved technique which is particularly suited for practical application because this mode combines an acceptable measuring effort with a simplicity and transparency of evaluation (by use of analytical formulae) not available with other procedures. The capabilities and limitations of the AR/SR technique in particular are reviewed, with special reference to four methods with which the technique has found application, viz. X-ray fluorescence spectrometry (XFS), electron microbeam analysis (EMA), X-ray photoelectron spectrometry (XPS) and Auger electron spectrometry (AES). Emphasis is placed on the role assigned to AR/SR/XFS and AR/SR/EMA in certification of ion-implanted reference materials.Invited lecture at 15th Colloquium on Materials Analysis, Wien, May 27–29, 1991     

Nitrogen depth distribution, interface and structure analysis of SiNx layers produced by low-energy ion implantation

Thin silicon nitride (SiN _x ) layers with the stoichiometric N/Si ratio of 1.33 in the maximum of the concentration depth distributions of nitrogen were produced by implanting 10 keV¹⁵N ₂ ⁺ in 100 silicon at room temperature under high vacuum conditions. The depth distribution of the implanted isotope was measured by resonance nuclear reaction analysis (NRA), whereas the layer structure of the implanted region and the geometrical thickness of the layers were characterised by high resolution transmission electron microscopy (TEM). SiN _x layers with a thickness of about 30 nm were determined by NRA. Channeling Rutherford backscattering spectrometry was used to determine the disorder in the silicon substrate. Sharp interfaces of a few nanometers between the highly disordered implanted region and the crystalline structure of the substrate thickness were observed by TEM. The high thermal stability of SiN _x layers with N/Si ratios from under to over stoichiometric could be shown by electron beam rapid thermal annealing (1100 °C for 15 s, ramping up and down 5 °C/s) and NRA.     

Investigation of implanted gallium depth distributions in ZnSxSe-x by EPMA

In the present work EPMA combined with Monte Carlo simulation was applied to investigate implanted gallium depth distributions in ZnS_xSe_1–x layers. The layers of about 1 to 4 m thickness were grown by MOVPE on (100)-GaAs substrate. The overlap of the Ga and zinc L X-ray spectra and the low gallium net count rates were overcome by stripping the spectra of non implanted layers and by applying appropriate beam currents and counting times. Capabilities and limitations of the EPMA technique as applied to depth profile analysis are demonstrated.Despite the mentioned L interference, the detectability limit of EPMA for 340 keV Ga in ZnS_xSe_1–x is as low as 10¹⁴ cm^–2. The measured Ga L intensity versus beam energy curves reveal variations of the Ga depth profiles during annealing. Evaluation of the intensity curves by means of Monte Carlo simulations yields the implanted dose densities and the first two moments of the depth distributions, i.e. the projected range and its standard deviation. The nonannealed profiles agree well with expectations, but after thermal annealing the profiles were significantly shifted towards the surface. Comparison of EPMA and SIMS results with the example of a non annealed profile in ZnSe has shown good agreement.     

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.     

Quantitative ultratrace distribution analysis of tantalum wires with SIMS

Summary The potential of SIMS for multielement ultratrace bulk analysis in refractory metals has already been shown in previous publications [1, 2]. In this paper it will be demonstrated, that the high sensitivity of SIMS can be used advantageously for high resolution distribution analysis. Due to the high useful yield (0.5 to 10^–5) it is possible to perform distribution analysis in the ng/g range with a sample consumption of about 1 pg per data point. A good lateral resolution of about 1 m and the variability of the sputtering rate over 3 orders of magnitude allow an optimization of the measurement parameters with respect to the sample geometry. This is of special importance in our work, because small lateral dimensions, high total sputtering depth (300 m) and crooked surfaces have to be considered. In this paper also the technical significance of sensitive high resolution distribution analysis of tantalum wires, which are used for microelectronic applications, will be discussed.

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Quantitative Ultraspuren-Verteilungsanalyse von Tantaldrähten mit Hilfe von SIMS

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

Interpretation of Auger depth profiles of thin SiC layers on Si

Silicon carbide thin films, prepared by carbonization of Si-wafers are analysed by Auger depth profiling. The influence of atomic mixing is simulated with a Monte Carlo model. By using mixing simulations the dependence of the two mixing parameters (width of the mixing zone and recoil depth) on ion beam energy, incidence angle and ion mass can be calculated. For comparison of the simulated data with Auger measurements an Auger electron escape depth correction is necessary. The simulated and -corrected data of several layer structures show good qualitative agreement with Auger depth profiles of thin carbonized SiC-layers.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Influence of the Native Oxide Layer on the Silicon Surface During Initial Stages of Nitridation

 Thin SiO₂ layers were produced by thermal oxidation of Si wafer material. To study the effect of nitridation on the oxide layers, the specimens were nitrided in a furnace at high temperature. Non-destructive ion beam analysis was performed to determine changes in the elemental concentrations and depth profiles of the major components. In particular, N and O concentrations were measured using the non-resonant nuclear reactions ¹⁴N(d, α)¹²C and ¹⁶O(d, p)¹⁷O, respectively. To obtain depth profiles of the as-prepared and nitrided specimens, the samples were measured with RBS and heavy ion elastic recoil detection analysis. The ion beam analyses revealed an increase in thickness of the SiO₂ layers with temperature. The specimens nitrided at 1200 °C were almost free of N. Surface topology investigations with scanning electron microscopy revealed concentric annular artificial patterns at the surfaces. In the centre of the pattern, only silicon was measured. Additionally, a band consisting of Si, O, and N surrounding the pattern was discovered. The findings are in agreement with specimens prepared at higher temperatures. Received June 19, 2000. Revision December 9, 2000.     

Heterogeneous element distribution: a contribution to quantitative GDOS depth analysis

Summary The apparent enrichment of Cu, Mg, Mn and Si on the surface of Al cast-alloys, as observed by means of glow discharge optical emission spectrometry (GDOS), could be attributed to the heterogeneous distribution of the alloying elements. The samples under investigation were spectrochemical standards and hence assumed to be homogeneous. Different metallurgical phases were identified which induced selective sputtering. The findings point out that quantitative results obtained by GDOS in-depth analysis can be misleading and should be confirmed by other techniques such as Auger Electron Spectrometry and Energy Dispersive X-ray Spectrometry, which are free from sputter effects.     

Production and characterization of nitrided CVD-SiC films

Silicon Carbide (SiC) and SiC with free silicon [SiC(Si)] thin films were prepared by chemical vapor deposition (CVD) using a CH₃SiCl₃-H₂-Ar gas mixture at a temperature of 1223 K. Afterwards these layers were gas nitrided in an ammonia-hydrogen-argon mixture at 1273 K. The solid product is an extremely thin film of silicon nitride on SiC or SiC(Si)-basic layers. These ultra thin silicon nitride films were investigated by glow discharge optical spectroscopy (GDOS) and x-ray photoelectron spectroscopy (XPS). The thickness of the layers was determined to a maximum value of 30 nm.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Surface characterization and thermodynamics of adsorption of Sr2+, Ce3+, Sm3+, Gd3+, Th4+, UO 2 2+ on activated charcoal from aqueous solution

Surface parameters of the activated charcoal were measured using precise instrumental techniques for dehydration, carbon content, trace metals impurities, anions, bulk, tap and true densities, surface area, pore volume, porosity and average particle diameter. The adsorption of Sr²⁺, Ce³⁺, Sm³⁺, Gd³⁺, Th⁴⁺ and UO ₂ ²⁺ ions on activated charcoal from aqueous solution was studied as a function of temperature. Thermodynamic parameters such as HH ⁰ and S ⁰ were calculated from the slopes and intercepts of the linear variation of lnK ₁ vs. 1/T, whereK ₃ is obtained from Langmuir equation. The results show endothermic heats of adsorption, but negative free energy values indicate that the adsorption process of metal ions on activated charcoal is favored at high temperature. The value of isosteric heat of adsorption, calculated from the Clausius-Clapeyron equation, shows that the surface of the activated charcoal is heterogeneous with respect to activity. A wavelength dispersive x-ray fluorescence spectrometer was used for measuring the concentration of metal ions.     

Constructing nitrided interfaces for stabilizing Li metal electrodes in liquid electrolytes

Traditional Li ion batteries based on intercalation-type anodes have been approaching their theoretical limitations in energy density. Replacing the traditional anode with metallic Li has been regarded as the ultimate strategy to develop next-generation high-energy-density Li batteries. Unfortunately, the practical application of Li metal batteries has been hindered by Li dendrite growth, unstable Li/electrolyte interfaces, and Li pulverization during battery cycling. Interfacial modification can effectively solve these challenges and nitrided interfaces stand out among other functional layers because of their impressive effects on regulating Li⁺ flux distribution, facilitating Li⁺ diffusion through the solid-electrolyte interphase, and passivating the active surface of Li metal electrodes. Although various designs for nitrided interfaces have been put forward in the last few years, there is no paper that specialized in reviewing these advances and discussing prospects. In consideration of this, we make a systematic summary and give our comments based on our understanding. In addition, a comprehensive perspective on the future development of nitrided interfaces and rational Li/electrolyte interface design for Li metal electrodes is included.

In this perspective, we make a systematic summary and give out our comments on constructing nitrided interfaces for stabilizing Li metal electrodes.     

Corrosion depth profiles of nitrided titanium alloy in acidified sulphate solution

Thick (400 µm) glow-discharge nitrided layers, TiN+Ti₂N + αTi(N) type, have been produced on the Ti-1Al-1Mn titanium alloy. Using a progressive thinning method, the polarization characteristics at different depths of nitrided layers have been measured. From the plots of obtained potentiodynamic polarization curves the depth profiles of characteristic anodic and cathodic currents (at potentials corresponding to (a) hydride formation, (b) hydrogen evolution, (c) primary passivation, (d) oxygen evolution and (e) secondary passivation) as well as polarization resistance have been determined in 0.5 M Na₂SO₄ solution acidified to pH = 2. The anomalously high slope of the polarization curves in the cathodic region has been ascribed to the formation of titanium hydride. It has been shown that outer nitrided layers (up to 25 µm) exhibit excellent acid corrosion resistance owing to strong inhibition of the anodic process by TiN phase. Corrosion resistance of deeper situated layers gradually decreases and at depths of 250–370 µm the corrosion process is accelerated by presence of TiO₂ precipitations. Nitrided layers, unlike the alloy core, allow oxygen evolution on the oxy-nitrided surface at potential of +1.6 V and at more positive potentials gradual transformation of the surfacial film into TiO₂ takes place. Secondary passivation on nitrided titanium is less efficient than that in the absence of Ti-N species.      

Molecular ion implantation in silicon

¹⁵N₂ ⁺ molecular ions were implanted with 10keV (j=10 A/cm²) under high vacuum conditions close to room temperature in 100 silicon (c-Si) to study the¹³N depth distributions, particularly the dependence of peak concentration and dose on the ion fluence. The analysis were performed by the resonant nuclear reaction¹⁵N(p, )¹²C(NRA). A maximum peak concentration of 65 at.% was measured. Thin stoichiometric silicon nitride layers with a thickness of approx. 20 nm (15 at.% nitrogen at the specimen surface) were produced by this low-energy implantation of¹⁵N₂ ⁺ ions with an ion fluence of 1.5·10¹⁷ ions/cm². NRA analysis of 38 keV¹⁵N₂ ⁺ and 19keV¹⁵N⁺ ion implantations were performed to compare the¹⁵N depth distributions. No significant changes in the depth distributions are measured, that means, the molecular¹⁵N₂ ⁺ ions are already disintegrated passing the very first atomic layers of the sample during implantation. Non-Rutherford RBS with⁴He⁺ ions and 3.45 MeV was performed in order to confirm the results obtained by NRA.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

The investigation of argon plasma surface modification to polyethylene: Quantitative ATR-FTIR spectroscopic analysis

This paper studied the surface modification of argon plasma to polyethylene by using ATR-FTIR analysis. The mass loss ratio has maximum value at discharge time of 70-120 s or discharge power of 62 W by using argon plasma treatment for polyethylene. New surface structure was formed after polyethylene was treated by argon plasma. The peroxide bond peak area also has maximum value at discharge time of 70-120 s or discharge power of 62 W. The CC nonsaturated double bond absorb peaks were appeared at 1640 cm⁻¹, 1549 cm⁻¹ and 1528 cm⁻¹ after polyethylene treated by argon plasma. The CC nonsaturated double bond absorb peak area has minimum value at discharge time of 60-70 s and the power of 65 W. The CC nonsaturated double bond absorb peak area has maximum value at discharge power of 62-72 W and the discharge time of 2 min. The absorption peak intensity of 2916 cm⁻¹ methylene nonsymmetry stretch vibration, 2848 cm⁻¹ methylene symmetry stretch vibration, 1463 cm⁻¹ methylene nonsymmetry changing angle vibration, and 719 cm⁻¹ methylene swing in plane vibration was decreased greatly. The four absorption peaks intensity has maximum value at discharge time of 120 s or discharge power of 62 W.